Note: Descriptions are shown in the official language in which they were submitted.
-- 1 --
f 3
Thl~ l mon~lon provlde~ ~ c~e~lytlc proc~ for the
hydro~or~ylAelon of cerealn oloflnlc, ~lfur coneA~nlng. ch~rM-lly cracked
p~erol0u~ dl~elllat-s~ ro~dlly avalle~lo ~t low co~e, eo produco c~rtaln
d~lr-bl~ llln~ar nld~hyd~J and ~lcohol~. by r~actlng tha olQfln
co~pon~ntb wlth CO ~nd N2. Th~ c~caly~e~ ~rc yrof~r-bly dlssolvod
eranJieson ~ctal c~rbonyl co~pl~xcJ. E~p~clally prof~rr~d catAly~e~ aro
cob~le ~nd rhodLu~ carbonyl hydrld~ co~ploxc9 In ~hlch ~oo- of tho carbonyl
llg-nd~ hav- b~n rcpl~c~d ~y er~v~lone pho~phorw ll~und~. A prcfcrrcd
fcod 1~ produc~d by eh~ hlgh t~p8r~euro thor~l cr~cklng of vacuu~ r~slds,
partlcul~rly by Fluld-coking and Fl~xlcoklng.
On~ asp~ct of eh~ dlsclo3ura ~ a d~cripelon of ehc types and
truceur~3 of eha co~pound~ producod by ch~ ehor~l cr~ckin~ of p~erol~u~
re~lds. The n~phcha and ~ oll dl~tlllaea fracelon~ d~rlvod by the
cr~eklng of v~euun reaLda In fluld~zod bad proeo~sos waro lnvo~lgaeed by a
eonbSn~eion of hi8h reso1uelon eaplllary ga~ ehromaeography. mass
speeero~acry and nuele~r n~gnaele re~on-neo speeeroscopy. The differenc
eypa~ of ol-fln ro-etaneJ and cho pocenelal ~ulfur eo~pound inhlbieors vere
partieularly an41yzod. Tho dlserlbuclon of the sulfur compound eoQponencs
ln eha dlse~ eo foad~ uaJ an~ly2~d by u~lng a sulfur 5p~ciflc deeeeeor.
~ nothsr ~poec of cha dlselo3uro ls th~ eorrelatLon of che
~Crueeuro~ of tho l-n-olein and eha llne~r ineornal olafln reaetanc
couponQne~ oi tha foed and tha vArlou~ cypa~ of tran31tlon mncal eomplex
c~e~ly~es u~d wlth cha unlqua structura~ of che ss~illnear ~ld~hyda and
aleohol produet~. Iho hl&h pras~uro eobalc earbonyl eo~plax eataly~ed
hydrofor~yl~tlon of Cs co Cls naphsha and ga5 oll dl~tlllaea fraeclon~ and
tha resuleing aldahydo product Qlxtura~ conslsclng ~o~tly of che
eorra~pondlng n--ldahyd~s 2-methyl branehod a1dahyde3 and 2-subsclcuced
aehyl and hl8h~r n-alkyl aldehydei are p~rrlcularly do~erlbod. Th~ trace
sulfur eone~lnlng co~ponHne~ of cho aldchyd~- ~nd thoir alcohol derlvaCives
ware al~o studlad by ~ulfur 3paelfle ga ehro~togr~phy.
~k
3~ 3
-2-
A further aspect of the disclosure is the description of the
reactions of the present aldehyde and alcohol products. The esterification
of the alcohols leading to phthalate ester plasticizers having unique
properties is particularly discussed. Ethoxylated surfactant derivatives
of the alcohols are also described in some detail.
PRIO~ ART VE~SUS THE ~ S~T INV~NTION
~ ydroformylation is a well-known reaction for the conversion of
pure olefln streams with CO and H2 to aldahydes but has not been generally
suggested for use on dilute olefin streams, such as petroleu~ distillates,
which contain high concentrations of sulfur compounds and some nitrogen
compounds. Streams containing these sulfu-r and nitrogen containing
i~purities have been considered as unsuitable hydroformylation ~eedstocks.
Presen~ olefin feeds for hydro~ormylation are mostly propylene
and its oligomers plu5 ethylene oligomers. The C7 to C13 alcohols derived
from propylene oligomers and propylene/butenes copolymers are generally
highly branched. In contrast, the Cg to Cls alcohols derived from ethylene
oligomers are usually highly linear. Both types of higher alcohols are
widely used intermediates in the production of plasticizer esters and
ethoxylated surfactants. For most applications linear or semilinear
alcohol intermediates are preferred. However, ehe ethylene oligomer feeds
of linear alcohol production ara much more costly than the branched olefin
feeds derived from C3/C4 olafins.
~ s a part of the present invention it was discovered that
thermally cracked petroleum distillates, particularly those derived from
residual fuel oil by Fluid-coking and Flexicoking, contain une~pectedly
ma~or quantitias of linear olefins. These olefins are valued below
distillate fuel co~t, because such cracked distillates have high
concentrations of sulfur compounds and have to be extensively hydrogenated
before thay can be used as distillate fuels. The olefin components are
convarted to paraffins during such hydrogenation~.
Furtherm~re, it was found in the present invention, that the
sulfur compounds in such thermally cracked petroleum distillates are mostly
innocuous aromatic, thiophene type compounds rather than catalyst
inhibiting mercaptans. This finding led to the discovery of the present
hydroformyla~ion process which comprises reactlng ehe linear and lightly
branched olefin components oi thermally cracked patroleum distillates
-
3 ~29~9~3
containing sulfur compounds with C0 and H2 to produce semilinear aldehydes
and alcohols.
When such olefin componenta were reacted with C0/H2 in the
presence of cobalt carbonyl complex catalysts at high pressure, the major
aldehyde products were n-aldehydes, 2-methyl and 3-methyl substituted
aldehydes, 2-ethyl and higher alkyl substituted aldehydes in the order of
decreasing concentrations.
As such, the present procsqs produces novel, highly desired,
semilinear chemical intermediates at a low cost. Due to the unique olefin
composition of the present cracked distillate feeds, such a unique mixture
of compounds cannot be produced by known processes.
~ hen using thermally cracked petroleu~ residua of naphtha
distillatiGn range, it was found partlcularly advantageous to use narro~
boiling distillates rich in a particular l-n-olefin. Such distillates
mostly contain compounds having the same number of carbon atoms per
molecule. They were found enriched in 2-methyl-1-olefin and linear
internal olefins. They have much lower arom tic hydrocarbon and thiophenic
sulfur concentrations compared to the broad naphtha feed. They also
provide hydroformylation products of more linear character than broad cut
distillate feeds.
The process of tha present invention is particularly advantageous
when the cracked petroleum distillate is a high bolling gas oil fraction
containing 10 to 20 carbon atoms per molecule. In contrast to higher
molecular wei~ht branched olefin~ derived by the oligomerization of C3/C4
olcfins, these gas oils are surprisingly reactive feeds for
hydroforrylation without prior treatment.
A group of preferred thermally cracked distillates, not
previously considered as a hydroformylation feed, comprises naphtha and gas
oil fractions produced in fluidized coking units. Integrated fluidized
coking processes such as Fluid-coking and Flexicoking represent a superior
refinery me~hod for the conversion of residual fuel oil. The thermal
cracking step of Fluid-coking and Flexicoklng is identical. However,
Fluid-coking does not utilize the residual coke produced with the coker
distillate while Flexicoking employs the coke by-product for the production
of low thermal value gas. A discussion of these processes is found in U.S.
Patent Nos. 2,813,916; 2,905,629; 2,9Q5,733; 3,661,543; 3,816,084;
4,055,484 and 4,497,705.
73
The preferred Fluid-coking and Flexlcoking processes are low
severity ther~sl cracking operations. Low severity is usually achieved by
keeping the temperature relatively low in ths range of 482 to 538C (900 to
1000 F) while usin~ a long residence, i.e., contact, time of about 20 to
seconds. Alternately, low severity can be achieved using high
temperatures, in the order of 538 to 705~C tlOOO to 1300~) and contact
times of less than 5 secondQ. In a long residenc~ time operation,
additional amounts of the desired olefin compononts can be produced by
reinjecting the heavy gas oil distillate products into the cracking lLne.
The residual fuel feeds for the above coking processes are
usually vacuum residua which remain after most of the crude petroleum is
removed b~ refinery distillation processes. As such, these r sidua
typically possess boiling polnts above 565C (1050F) and have Conradson
carbon contents above 15X. These residua contain ~ost of the undesirable
components of the crude, i.e. sulfur and nitrogen compounds and metal
complexes. On coking, much of the sulfur ends up in the dLstillate
products. As a result of high tempera~ure thermal cracking, major amounts
of olefinic components are also formed and become ma~or constituents of
such distillates. In spite of their high monoolefin content such
distillates generally wera not considered as hydroformylation feeds because
of their high sulfur and conJugated diolefin content.
Other residual fuel type feeds for coking are produced from heavy
asphaltic oils and tar sands. The hlghly olefinic distillates produced by
the thermal cracking of heavy tar oil are suitable feeds for the process
for the present invention. A particularly attractive feed is produced by
the coking of Cold Lake and Athab~sca tar sands oil residues without prior
removal of sulfur co~pounds.
While coker naphtha and gas oil distillates resulting from the
high te~perature thermal cracking of residual oil can by hydroformylated as
such, their further fractionation i~ preferred. This results in feeds of
improved hydroformylation process characteristics which lead to superior
aldehyde and alcohol productQ.
The aldehyd2 and alcohol products of the present hydroformylation
process contain 20X by weight or more linear, i.e. nor~al, isomer. The
preferred products con~ain 20 to 50X normal iso~ers, 3 to 20X 2-methyl
branched compounds and 3 to 15X 3-methyl branched compounds. 2-Ethyl and
higher 2-alkyl branched co~pounds represent another slgnificant type of
constituents. The balancs is composed of monobranched aldehydes or
~?,~73
alcohols with minor amounts of dibranched aldehydes or alcohols. The
average number of alkyl branches per product molecule is less than 1. As
such the products have a unLquely branched semilinear character. They are
considered to be novel products and constitute further embodiments of this
invention.
The semilInear alcohol products of the present invention are
attractive intermediates for plasticizer and surfactant products. The
properties of these products critically depend on the branchiness of the
alcohol inter~ediates. The dialkyl phthalate ester plasticizer showed a
desirable combination of low temperature properties and heat stability.
The ethoxylated alcohol surfactants had superior wetting properties.
Surfactant and plasticizer derivatives of thes~ se~ilinear alcohols are
further embodi~ nts of this invention.
Although sulfur compounds in genaral were regarded as catalyst
inhibitors, the production of alcohols or aldehydes via the
hydroformylation of the olefinic components of so~e refinery streams has
been previously suggested. For instance, U.S. Patent No. 4,454,353 to
Oswald et al., issued June 12, 1984, teAches the use of trihydrocarbyl
silyl substituted diaryl phosphine transition metal carbonyl hydride
complex hydroformylation catalysts with ~refinery streams of olefins,
containing paraffin by-products such as Cl to C20 paraffins...n.
Haag and Whitehurst in U.S. patents 4,098,727 and 4,487,972
discloqe the production of aldehydes and alcohols via tha hydroformylation
of olefinic streams in the presence of insoluble, polymer anchored
complexes of Group VIII metals with nitrogen, sulfur, phosphine and arsine
ligands. Exa~ple 32 Yhows the hydroformyla~ion of a cracked gasoline feed
containing 230 ppm sulfur in the presence of a rhodium amine complex
attached to a styrene-divinylbenzene copolymer.
The process disclosed in U.S. Patent No. 4,417.973 to Angevine et
al., is one for ~upgrading~ various straight chain olefin-containing
feedstocks, such as shale oil, FCC light cycle oil, and coker liquids, to
branched paraffins. The process involves the sequential steps of
hydroformylation and hydrotreating/hydrogen reduction, preferably, in ehe
presence of heterogeneous supported Co/~o catalyst. The reaction products
of the hydr~formylation s~ep were neither separated nor idantified. The
final products are branched p~raffins. The sulfur content of the various
feedstoc~s are show~ in the Examples to be 0.29 to 1.33 wt. X.
-6~ 73
Other disclosures discussing the use of cobalt-based homogeneous
catalysts are known.
For instance, a series of papers by Marko et al. teach the
reaction of dicabalt octacarbonyl, a hydroformylation catalyst precursor,
with elemental sulfur and organic sulfur compounds. Various
sulfur-containing cobalt complexes were isolated. Reactlons with sulfur
led to [Co2StCO)s]n and Co3S(CO)g. See, Chem. Ber., 94, 847-850 (1961);
Chem. Ind., 1491-1492 (1961); Chem. Ber., 96, 955-964 (1963). Hydrogen
sulfida is said to react to give the sa~e complexes. Mercaptans and
disulfides lead mainly to sulfide derivatives of cobalt trimers and
tetramers. Marko et al. states that, under hydrofor~ylation conditlons,
all these complexes are converted to catalytically inactive cobalt sulfide
[Chem. Ber., ~, 926-933 (1964).] Cobalt thioether complexes are also said
to be either inactive or less active in hydroformylation than unsubstituted
dicobalt octacarbonyl ~Acta Chim. Sci. Hung., 59, 389-396 (1969)].
Another series of papers by Marko and co-workers describes the
hydroformylation/hydrogenation of C6/Cg olefins present in cracked
gasoline. The papers describe a process for converting a sulfur-containing
C7 ~raction of cracked gasoline using a 1 to 2 ratio of hydrogen ~o carbon
monoxide at 200C under 300 atm (4,409 p3i) pressure to produce 85X octyl
alcohol, an intermediate for a dioctyl phthalate plasticizer, with lOX
hlgher boiling by-product formation tJ. Berty, E. Oltay and L. Marko, Chem.
Tech., ~Berlln~ 9, 283-286 (1957); M. Freund, L. Marko and J. Laky, Acta
Chem. Acad. Sci. Hun~., 31, 77-84 (1962)). Under these reaction
condition~, using cyclohe~ene as a model olefin, ethyl mercaptan and
diethyl disulfida were found to be strong inhibitors of hydroformylation
even in small amounts while diethyl sulfide and thiophene had no effect in
molar concentration~ up to tenfold of cobalt [L. Marko, Proc. Symp. Coordn.
Chem. Tihany, Hungary, 271-279 (1964)]. Similar but more pronounced
effects were observed on ~he hydrogenation of aldehyde intermediates to
alcohols [J Laky, P. Szabo and L. Marko, Acta Chim. Acad. Sci. Hun~., 46,
247-254 tl965)]. Sulfur containing cobalt trimers, e.g., of the formula
Co3(CO)gS and Co3(CO)6(S)(SR) were postulated as intermediates in the
converslon of active Co2(CO)g into soluble inactlve CoS [L. Marko and M.
Freund, Acta Chi~. Acad. Sci. Hung., 57, 445-451 (1968)].
Russian researchers, particularly Rudkovskii and co-workers, also
published a series of articles on the hydrofor~ylation of olefin components
in patroleu~ distillstes with dicobalt octacarbonyl catalyst. These
7 ~ 73
distilla~0s were not characterized chemically. One paper describes the
production of Cll to C17 alcohols from high boiling distillate fractioos of
contact coking. The process entails hydroformylation, preferably at 170C
and 300 atm (4409 psi), followed by hydro~enation in a mixture with
unreacted hydrocarbons over a 2NiS.WS2 catalyst [R. A. Alekseeva, D. M.
Rudkovskii, M. I. Riskin and A. G. Trifel, Khim. i Tekhnol. Topliv i Masel
4 (5), 14-18 (1959)]. Another paper describes a similar hydrofor~ylation
of lower molecular weight cracked gasoline olefins [D. Rudko~skii, A. G.
Trifel and K. A. ~lekseeva, Khim. i Tekhnol. Topliv i Masel, 3(6), 17-24
(1958)]. Suitable C7 to C8 naphth~ feeds from thermal cracking of a
mixture of petroleum fractions, phenol extr~cts and petrol~um were later
described [P. K. Z~iewski, T. N. Klyukanova and G. ~. Kusakina, Neft. i Gas
Prom., Inform. Nauchn. Tekhn. Sb. (4) 48-49 (1964)].
Anotber journal article, appeared in a Russian ~ournal, Khim.
Tekhnol. Gotyuch. Slantssv i Produktov Lkh Pererabotki, on pages 325 to 332
of the 13th issue of 1964, and was authored by N. I. Zelenin and
co-workers. This publication considered the hydroformylation of che olefin
components of shale gasoline and diesel fractions to produce plasticizer
and surfactant alcohols. It particularly discussed the removal of sulfur
compounds which can be hydroformylation inhibitors.
A research report, Forschungsbericht T-84-064, was made to the
German Federal Department of Research and Technology in April 1984. The
authors, B. Fell, U. Buller, H. Classen, J. Schulz and J. Egenolf disclose
the hydroformylation of a Cs to C6 cracked gasoline between 150-175C at
200 atm (2939 psi) in the presence of 0.4-0.2X cobalt to obtain
oxo-products with 65X selectivity. The use of a triphenyl phosphine
rhodium complex ba~ed catalyst system at this high pressure was reported to
result Ln littl~ conversion.
Two monographs on the organic chemistry of carbon monoxide by
Falbu and co-workers of Ruhrchemie include ma;or chapters on
hydroformylation. The effsct of hydroformylation of cobalt catalys~
poisons, particularly sulfur compounds, is su~marized on pages 18 to 22 of
the first monograph [J. Falbe, Carbon Monoxide in Organic Synthesis,
Chapt~r I, The Hydro~ormyl&tion Reaction (Oxo Reaction~Roelen Reaction),
pages 1 to 75, Springer Verlag, New York tl970)1. The second monograph
also reviews the effect of poisons on modified rhodiu~ catalysts and
concludes that these catalysts, due to thoir low concentration, are more
susceptlbl~ to poisoning [New Syntheqis with Carbon Monoxide, Ed. J. Falbe,
-8-
Chapter 1 by B. Cornlls, pagQs 1 to 224, particularly page 73, Springer
Verlsg, Naw York, 1980].
Higher aldehydeY derived via hydroformylation are known versatile
chemical intermedia~eq. Thcy are utilized for the synthesis of primary
alcohols, carboxylic acids and amines. The so called oxo-alcohols are the
most important products. They are most widely used in the preparation of
phthalate ester plasticizers and surfactants. Howe~er, known methods for
the preparation of oxo-aldehydas and alcohols have carbon number and/or
product linearity llmitations.
Highly line~r oxo-alcohols are the most desired for most
applications. However, the~r preparat~on requires completaly linear olefin
feeds derived fro~ ethylene which ~re prohibitively expensive for many
applications. Highly branched oxo-~lcohols derived via the
hydroformylation of propylane oligomers are less costly to produce but
their plasticizer derivatives have poorer low temperature properties and
their surfactant derivatives are less biode~radable.
More recently, U.S. Patent 4,598,162 by D. Forster, G. F.
Schaefer and G. E. Barker disclosed the preparation of aldehydes and
alcohols via the aldolization of axo-aldehyde~ containing little branching
in the 2~position. The alcohols derived via this route are more
biodegradable than the prior art branched compounds. However, their
preparation requires an additional step and leads to products having more
than one branch per molecula.
Overall, the prior art taught away from the hydroformylation
process of thc present invention rather than suggesting it. In general,
the use of cracked petroleum distillates containing high concentrations of
sulfur was to be avoided. Soluble transition metal carbonyl complexas
containing trivalent phosphoruQ ligands were never used successfully for
the hydroformylation of such distillstes. Known low pressure
hydroformylation processes have low sulfur limits for the feeds.
Although the high prassure hydroformylation of cracked gasolina
of relativoly low sulfur content wa~ axtensl~ely studied by Marko et al. in
the presence of added dicobAlt octacarbonyl, the feeds and conditions of
the present process were neither used or sug~ested. It was not proposed to
utilize coker distillata feeds of high linear olefin and sulfur compound
content for tha production of aldehydes and alcohols by hydroformylation.
The high prossura, cobalt catalyzed C7 gasoline hydrofor~ylation/hydro-
genation process Marko et al. developed is run at 200C and produces
9 ~ 3
alcohol~ in one step. In contrast, th~ temperature range of the present
hi~h pr0ssure cobalt catalyzed process is 110 to 180~C, preferably 120 to
145C and the main products are aldehydes. Pure alcohol products in this
process are produced in a separaee stap.
The present cobalt carbonyl complex catalyzed high pressure
proce~ employ~ Cg to C20 di~tillatQ fQeds pxoduced by hi~h temperature
fluid-coking of vacuum resids. These feeds contain more than 0.1% sulfur
and more than 20X olefins of a unique isomer composition. More than 30X of
ehe total olsfins present are of Type I. More than 10~ of the olefins are
of Typ~ II. The most prevalent Typa III olefin components are
2-methyl-1-olefins.
Due to the spacific linear olsfinlc character of the present
feeds, such hydroformylations produce uniqua ald~hyde and alcohol products
of a semilinear charac~er having less than one branch per molecule. The
ma~or components of the primary aldehyde products are n-aldehydes,
3-methyl-branched aldehydes, and 2-methyl-branched aldehydes. Much of the
rest are 2-ethyl or higher 2-n-alkyl-branched ~ldehydes. However, the
amount of higher 2-alkyl-branched compounds is much les3 than in prior art
compositions prepared via aldolization. On hydrog~nation they provide the
corresponding alcohols. Such aldehyde and alcohol compositions cannot be
directly prepared by any othar method. Their prepar~tion by blending the
appropriate components would be economically prohibitive.
The novel semilinear alcohol product3 of the present inventlon
can be converted to ester plasticizers and ethoxylated surfactancs of
unique properties. The C6 to C13 alcohols provide the corresponding
dialkyl phth~lates having a combination of supsrior low temperature
properties and high temperature stability compared to branched alcohol
derlvatives. The Cg to C30 alcohols lead to ethoxylated surfactants of
hi&h biodegr~dability and superior wetting properties. In both, the case
of pla~ticlzers and surfactants, the unique properties are attributable to
the unique semilinear structure of the alcohol precursors.
Dialkyl phthalate ester are a well known, large volu~e group of
placticizers for polyvinylchlorida. As such they comp~te on the basis of
their propertiac and cost. Fro~ the viswpoint of mose of the desired
propereies, particularly the low eemperature properties of plastlcizad PVC,
phthalate esters derived from linear alcohols are supsrior to derivatives
of highly branched primary alcohol~. Howev~r, highly branched alcohols can
be producad in a broad carbon rznge at a cost ~ignificantly balow that of
~$4~973
-10-
linear alcohols. Thus, there has been a continuing effort to produce low
cost, less branched primary alcohols and their mixtures. However, to date,
no low cost primary plasticizer alcohol with less than one branch per
molecule is availabla.
Ethoxylated higher alcohols are a highly important class of
nonionic surfactants. They are dominating the detergent industry where
biodegradability is important. They ar0 also widely us~d as sulfate
derivatives. Most ethoxylated higher alcohols are derived from costly
linear alcohols to enhance their biodegradability. The higher linear
alcohols are solids and, as ~uch, difficult to handle. In contrast, the
present detergent range semilinear alcohols are low cost liquids of
biodegradable character. As such, they combine the advantages of both
branched and linear alcohol surfactant intermediates.
None of the references teach either alone or in co~bination the
presently described and claimed process and~or products.
D~S~RI~TIO~ OF TECL1~33E~
Figur~ 1 shows the capillary gas chromatogram of a Fluid-coker
naphtha feed $n the C4 to C12 range, with an indication of the major
l-n-olefin and n-paraffin components by a flame ionization detector and the
ma~or thiophenic components by a sulfur specific detector.
None of the references teach either alone or in combination the
presently described and claimed proce3s and products.
Figure 2 shows the 400 MHz proton nuclear magnetic resonance
spectrum of the olaiinic protons of Fluid~cokar naphtha feed, with an
indication of the chemical shift regions of various types of olefins.
Fi~ure 3 shows the capillary gas chromatogra2 of the C6 fraction
of a Fluid-coker naphtha feed, with an indication of the ma~or olefin and
parafiin corponents.
Figure 4 shows tha capillary gas chromatogra~ of the G8 fraction
of Flexicoker naphtha feed with an indication of the ma~or hydrocarbon
components.
Figure 5 shows the sulfur specific capillary gas chromatograms of
the narrow and broad C8 fractions of Flexicokar naph~ha with an indication
of the main methylthiophene and dimeehylthiophene components.
Figure 6 shows the capillary gas chromatogram of che Clo fraction
of a Fluid-coker naphtha faed ~ith an indication of the major olefin,
paraffin and aro~atic components.
Figure 7 shows the capillary gas chromatogram of the light
Fluid-cokar gas oil feed in the Cg to C16 range, with an indlcation of the
major l-n-olefln and paraffin components.
Figure 8 shows the 500 MHz proton nuclear magnetic resonance
spectrum of light Fluid-coker gas oil feed, with an indication of the
olefinic, paraffinic and aromatic components.
Figure 9 shows the capillary gas chromatogram on a highly polar
column of a C12 fractLon of ligh~ Fluid-coker gas oil, with separation of
various types of aliphatic and aromatic components and sulfur compounds.
Figure 10 shows the capillary gas chromatogram of a Fluid-coker
light gas oil mixture after ~rioctyl phosphine cobalt complex catalyzed
hydroformylation, with an indication of the ma~or n-paraffin and capped
n-alcohol components.
Figure 11 shows the capillary gas chromatogram of a Clo
Fluid-coker gas oil after trieehyl phosphine cobalt complex catalyzed
hydroformylation, with an indication of ths isomeric Cll alcohol products
formed.
Figure 12 shows the capillary gas chromatogram of a Fluid-coker
naphtha mixture after cobalt catalyzed hydroformylation, with an indication
of the major n-paraffin and n-aldehyde components.
Figure 13 shows the capillary gas chromatogram of ehe aldehyde
region of the reaction mixture obtained in the cobalt catalyzed
hydroformylation of a C6 Fluid-coker naphtha fraction.
Figure 14 shows the capillary gas chromatograms by flame
ionization and sulfur specific detectors of tha reaction mixture produced
by the cobalt catalyzed hydroformylation oP a C8 Flexicoker naphtha
fraction.
Figure 15 shows the capillary gas chromatogram of a Clo
Fluid-coker naphths after cobalt catalyzed hydroformylation, with an
indication o the isomeric Cll aldehyde produces formed.
Figure 16 shows the packed column gas chromatogram of a Clo
Fluid-coker naphtha after cobalt catalyzed hydroiormylation, with an
indication of the Cll aldehyde products and dimer and trimer by-products.
Figure 17 shows the capillary gas chromatogram of a Fluid-coksr
light ~as oil mixture after cobalt catalyzed hydroformylation, with an
indication of the ma~or n-paraifin and n-aldehyde components.
-12- 1 ~ Ci~ 3
Figure 18 shows the capillary gas chromatogram of the aldehyde
region of the reaction mixture obtained in the cobalt catalyzed
hydroformylation of C12 Fluid-coker light gas oil fraction.
So~U81LI~ IL_INV~NTION
ThLs invention describes a hydrofornylation process in which the
olefin components of a cracked petroleum distillate fractLon containing
substantial amounts of l-n-olefins and sulfur bearing compounds are reacted
with carbon monoxide and hydrogen in the presence of a homogeneous Group
VIII transition metal carbonyl cornplex catalyst. The invention is also
concerned with the novel products of the present process. These products
are aldehydes and/or alcohols of largely lineat- character and as such
pre~erably have less than one alkyl branch per molecule on the average.
The products may be separated by distillation fro~ the unreacted components
of the distillate feed.
The preierred catalysts are soluble rhodium or cobalt carbonyl
complex catalysts. The complex may be modified by a trivalent phosphoruc~
arsenic, nitrogen and/or sulfur li~and. Triorgano-phosphine ligands are
most preferred. Cobalt carbonyl catalysts may also desirably be used
without added phosphorus ligands.
The reaction conditions under which the feeds may be
hydroformylated cover broad ranges. Temperatures ranging from 50 to 250C
and pressures ranging from essentially atmospheric to 5000 psi (340 atm)
may be used. The more preferred condieions depend on the eype of the
olefin to be reacted and the type of transition metal catalyst to be used.
When phosphorus ligand rhodium complex based catalysts are
employed, low pressures between 50 and 2000 psi (3.4 and 136 atm),
preferably 100 to 1500 psi (~.8 to 102 atm), are used. A broad range of
temperatureq preferably from 50 to 250C, more preferably from 80 ~o 200C,
can be used.
Phosphine cobalt complex catslys~s can be advantageously employed
at pressures between 500 and 4500 psi (34 and 305 atm), preferably between
aboue 500 and 2500 psi (34 and 170 atm), and at reactLon temperatures
between 150 and 200C.
High pressure cobalt catalysts, in the absence of added ligands,
require pressures between 2500 and 6000 psi (170 and 408 atm), preferably
between 3000 and 4500 psi (204 and 306 at~). They are preferably employed
between 100 and 180C, more preferably between 110 and 170C, most
-13 ~Z~ 3
prsferably betwesn 120 and 145C. Higher pressures of reactant gas,
spacifically C0, allow the use of higher reaction temperatures without
catalyst decomposition and/or deactivation.
In summary, the dependence of reaction conditions on the type of
catalyst systems employed is shown by the following tabulation:
Group VIII Trivalent _______~eaction ConditiQn~ __
Metal P LigandTemperature _ P~rU~gJQL________
Employed Employed C psi atm
e~ . _ __
Rh Yes 50 - 250 50 - 2000 3.4 - 136
Co Yes 150 - 200 500 - 4500 34 - 306
Co No 100 - 180 3000 - 4500 204 - 306
In ehe prssent process, the feed for the high pres~ure cobalt
catalyst contains l-n-olefins as the major type of olefins snd is derived
from the pstroleum residua by FlexLcoking or an equivalent high temperature
thermal cracking process. Starting with this feed, the present process
provides aldehydes and/or alcohols of a highly linear character having less
than one alkyl branch per molecule on an average. This feed and product
are also preferred for the other catalysts.
The preferred thermally cracked distillate feeds have a further
increased l-n olefin content and a reduced aromatic hydrocarbon and sulfur
content. In the C6 to Clo feed range this is advanta~eously achieved by a
process additionally comprising the fractional distillation of cracked
naphtha separating narrow faed frac~ions containing mainly linear aliphatic
hydrocarbons from fractions containing ma;or amounts of aromatic compounds
including thiophene3.
Th~ preferred high pressure cobalt cataly~ed process of the
present hytroformylation process i5 partlcularly suitable for the
conversion of the olefins of the pressnt fesd to novel se~ilinear aldehydes
having one carbon more than the parent olefins. The structure of the
aldehyde~ contQining less than one alkyl branch per molecule refleces the
unique mixture of the starting olefins. The major components of tha
preferred aldehyde compo3itions are n-aldehydes, 2-methyl-aldehydes and
3-mdthyl-aldehydes derived from the major l-n-olefin and l-methyl-l-olefin
components of the feed.
The invention is also concerned with tha derivatives of che
primary aldehyde products. These aldehydes can be hydrogenated during
- 14 ~ 3
and/or after the hydroformylation process to provide the corresponding
mixture of semilinear alcohols. Elther the aldehydes or the alcohols can
bs converted to ths corresponding amines and quaternary ammonium compounds
The novel alcohol compositions can be converted to valuable ester
plasticizers and ethoxylated surfactants. Polyvinylchloride plasticized
with ~he phthalate esters shows a unique combination of low temperature
flexibility, high temperature stability and reduced volatility attributable
to present semilinear alcohol intermedia~e Similarly, the sthoxylated
and propoxylated surfactant deri~atives of these alcohols show a desirable
combination of biodegradability and wetting properties. Such surfactants
will generally contain about 1 to 30 mole3 of ethylene oxide or propylenP
oxide per mole of semilinear alcohol.
D~_C~IPTI0~ 0~ ~HE PR~F~R~D ~M~OPIM~NTS
This in~ention describes a hydrofor~ylatlon process for the
production of aldehydes and/or alcohols of a largely linear character,
i.e., prod~cts stream having preferably less than on0 alkyl branch per mole
on the average, from a cracked petroleum distillate feedstock containing
substantial amounts of l-n-olefin~ and sulfur co~pounds. The process
comprises reacting the distillate with C0/H2 in the presence of a Group
VIII transition metal complex catalyst.
As such, the present hydroformylation process comprises reacting
with hydrogen and carbon monoxide an olefinic cracked petroleum distillate
feed, particularly in the C8 to C3s carbon range, preferably produced fro~
petroleum residua by high temparature thermal cracking, and coneaining
l-n-olefins as the ma~or type of olefin components, the percentage of Type
I olefins being preferably more than 30X, said feeds also containing
organic sulfur compounds in concentrations preferably exceeding O.lZ, more
preferably exceeding lX.
The hydrofor~ylation reaction is carried out at temperatures
between about 50 and 250~C and pressures in the range of S0 and 6000 psi
~3.4 and 408 atm) dependent on the particular catalyst employed.
The reaction takes place in the presence of affective a~ounts of
a Group VIII transition metal carbonyl complex catalyst preferably selected
from the ~roup of Fe, Co, Rh, Ru, Ir and 03, more preferably Rh, Co, Ru and
~r, most preferably Co or Rh, a preferred gro~p of complexes being modified
by a trivalent phosphorus ligand, preferably triorgano-phosphine or
phosphite ester.
-15- ~2~a~3
Such hydroformylations produce aldehydes and/or alcohols,
preferably aldehydes of a semilinear character, preferably having an
average of less than one alkyl branch per molecule. These products more
preferably contain n-aldehydes, 2-methyl and 3-methyl branched aldehydes as
the major products, most of the rest being mainly various 2-ethyl or higher
2-n-alkyl branched aldehydes. The reduction of these aldehydes by hydrogen
to the corresponding alcohols is preferably carrled out in a separate step
in the presence of a sulfur insensitive catalyst, preferably based on Co,
Mo, Ni, W in a sulfided form.
Thu~, according to another aspect of the invention, a
hydroformylation-hydrogenation process comprises reacting the above
described olefinic cracked petroleum distillaee fzed with carbon monoxide
and hydrogen under the conditions already defined to produce said aldehyde
products and ~han reacting said aldehydes and temperatures bet~een 100 and
220C in the presence of a catalyst in effective a~ou~ts to produce the
corresponding alcohols of a semilinear character having an average of less
than one alkyl branch per molecule.
According to a further aspect of the invention, the novel
aldehyde and alcohol compositions prepared via the present process are
dsscribed. These isomeric aldehyde compositionq comprise C7 to C21 mostly
saturated aliphatic aldehyde mixtures of a semilinear character having an
average of less than one branch per ~olecule. They contain more than 30X
normal alkanal and ma~or amounts of 2-methylalkanals and 3-methylalkanals
and minor amounts of 2-ethyl and higher 2-n-alkylalkanals. Similarly, the
isomeric alcohol compositions comprise C7 to C21 saturated aliphatic
alcohol mi~tures of a semilinear charac~er having an average of less ehan
one branch per molecule. These alcohols contain more than ~OX, preferably
more th~n 30X, normal alkanols, ma~or amounts of 2-methylalkanols and
3-methylalkanols and minor amounts of 2-ethyl and higher 2-n-alkylalkanols.
Dist~ eo Ye~ts
The cracked petroleum distillate feeds of the present
hydroformylation procass arz preferably derived via ther~al cracking.
Thermal cracking processes produco hydrocarbons of more linear olefinic
character than catalytlc cracking. Thz presence of linear olefin
components, partlcularly l-n-olefins, in the cracked dlstillates is
important for the production of normal, non-branched aldehydes and
mono-branched aldehydas using hydroformylation. For example, the
~l2~ 73
-16-
hydroformylation of l-hexene can produce n-heptanal as the maln n-aldehyde
product and 2-methylhexanal as the minor iso-aldehyde product. These in
turn can be hydrogenated to the corresponding alcohols:
CH3(cH2)3cH~cH2 ~ CO ~ H2 ~ CH3(CH2)sCHO + CH3(CH2)3CHCHO
c~3
~ H2
CH3(CH2)5CH20H ~ C~l3(cH2)3cHcH2oH
CH3
The llnear nor~al aldehyde and alcohol products sre generally more desired
than ehe branched iso-compounds as intermediates for the production of high
quality plastici~ers and surfactants. Among the iso compounds, the
2-methyl branched products have the least adverss effect on product
quality.
The percentage of 1-n-olefin components of thermally cracked
peeroleu~ distillates generally increases with the temperature of cracking.
Therefore, the distillate products of high temperature thermal cracking
processes such as Fluid-coking and Flexicoking are preferred feeds for the
present process. Delayed coking, which is normally operated at a lower
temperature, can also produce suitable feeds for the present process when
operated at sufflciently high temperature. Other less preferred, milder
cracking processea such as the thermal cracking of gas oils and the
visbreaking of vacuum residues can also produce distillate feeds for the
present process. Sultable distillate feeds can also be prepared in thermal
proce~es e~ploying a plurality of cracking zones at different
tempera~ures. Such a proc~ss is described in U.S. patents 4,477,334 and
4,487,686. Eacb of these thermal cracking processes can be ad~usted to
increase the olefin contents of their distillate products. Higher
distillate fractions of steam cracking can also be used as a feed in the
present process.
The olefin content of the cracked distillate feeds of the present
invention is above 20X, pre~erably above 30X, more preferably abo~e 40X.
The l-n-oleflns are preferably the major type of olefin components.
In the high pressure operation of the present process, using
cobalt ~arbonyl co~plexes without any added phosphine ligand, the feeds
-17-
should be thermally cracked distillates containing l-n-olefins as the major
olef$n type. These feedstocks are preferably produced by the FLEXICOKINC
process or FLUID-COKING process and slmilar high temperature coking
processes.
Distillate fractions of cracking processes can be hydroformylated
without prior purification. However, ehe cracker distillate feeds may be
treated to reduce the concentration of certain sulfur and nitrogen
compounds prior to the hydroformylation process. These impurities,
particularly the mercaptans, can act as inhibitors to the hydroformylation
step. The disclosed process is operable in the presence of the impurities
but adjustments to the catalyst level and/or to the reactant gas partial
pressure (notably the CO pressure) are preferably made to compensate for
the inhibition by the sulfur compound~.
One method for the removal of mercaptans, is selective
extraction. Most of the extractive processes employ basic solvents.
Examples o~ such processes include the use of aqueous and meehanolic sodium
hydroxide, sodium carboxylats (isobutyrate, naphthenate) sodium phenolate
(cresolste) and tripotassium phosphate. Sulfuric acid of carefully
controlled concentration and temperature can be also used although it is
less selective than caustic. For example, a 30 minute treatment with 12X
H2SO4 between 10 and 15 can be used.
The preferred cracked dLstillates of the present feed contain
relatlvely high amounts of organic sulfur compounds. The sulfur
concentration is preferably greater than O.lX (1000 ppm), more preferably
greater than lX (10000 ppm). The prevalent sulfur compounds in these feeds
are aromatic, mainly thiophenic. Most preferably the aromatic sulfur
compounds reprasant more than 90X of the total. This finding is important
for the present process since thiophenes, benzothiophenes and similar
aromatic sulfur compounds do not inhibit hydroformylation.
~ or the removal of sulfur, as well as nitrogen compounds,
adsorption on columns packed polar solids, such as silica, fuller's earch,
bauxite, can also be used. ~reating columns containing such adsorptive
solids can bs regenerated, e.g., by steam. Alternatively, ~eolites can be
used to enrich the present feed~ in l-n-olefins and n-paraffins.
The aromatic hydrocarbon components of the feed can also be
removed together with tha aromatic sulfur co~pounds, preferably by methods
ba~ed on the Increased polarity of aromatics compared to ths aliphatic
components. Selective solvent extraction methods usin~ a polar solvsn~
-18- 4 ~ ~ ~
such as acetonftrils ~ay be Pmployed for extracting the polar components.
As a feed for extraction, preferably narrow distillate fractions of up to 3
carbon ran~e are used.
Finally, sulfur compounds can also be converted to easily
removable hydrogen sulfide by pasqin~ the cracked distillate through a high
temperture fixed bed of either bauxite or fuller's earth or clay,
preferably between 700 to 750~C. Ona disadvantage of this catalytic
desulfurization method is the concurrent isomerization of olefin.
The cracked refinery distillata feed is prsferably separated into
various fractions prior to hydroformylation. Fractional distillation is
the preferred method of separation. The different distillate fractions
contain different ratfos of the various types of olefin reactants and have
different inhibitor concentrations. The preferred carbon range of the
thermally cracked feeds is Cs to C3s. The C8 to C2s range is more
preferred. The most preferred r~nge is Cll to C20. It is desirable to
limit the carbon number range of any given distillate feed by efficient
fractional distilLation to 5 carbons, preferably three carbons, more
preferably one carbon, to allow efficient separation of the products from
tha unreacted feedstock.
For example, a cracked distillata feadstock fraction might
contain hydrocarbons in the C7 eo Cg ranga. The maln components of such a
fraction would be C8 hydrocarbons. Upon hydroformylating the olefinic
components of such a fraction, C8 to Clo (mainly Cg) aldehydes and alcohols
would be obtained. These oxygenated products all boil higher than the
starting C7 to Cg hydrocarbons. The products could therefore be separated
by distillation from the unreacted feed fraction.
For the pr~paration of plasticizer alcohols, olefin feeds
containing fron 5 to 12 carbon atoms ara prsferred. These can be convarted
to C6 to C13 aldehydes and in turn to C6 to C13 alcohols. The more
proferred feQda contain C8 to C12 olefins and as such provide Cg to C13
~lcoholq. Tha mo~t preferred feeds are Clo to C12 olafin-Q. The alcohols
may be reacted with phthalic anhydride to produce dialkyl phchalate
pla3elcizers of appropriate volatility. The more linear the character of
the alcohol employed, tha better are the low tempera~ure properties of the
plasticized products, e.g., plasticizad PVC. The praferred feeds of the
present invantion are unlquely advantageou-~ in providing low cost olefins
for the darivation of high val~e plasticizers.
12~ ,3
-19-
For the preparation of surfactants, higher molecular ~eight
olsfins are usually preferred. Their carbon numbers per molecule range
from Cg to C3s. These feeds can be used for the derivation of Cg to C36
aldehydes, C12 to C20 olefin feeds leading to C13 to C21 surfactant
alcohols are more preferred. These aldehydes can be either reduced by
hydrog~n to the corresponding alcohols or oxidized by oxygen to the
corresponding carboxyl~c acids. The alcohols can then be converted to
nonionic surfactants, e.g., by ethoxylation; anionlc surfactants, e.g., by
sulfonation and cationic surfactants, e.g., by amination or cyanoethylation
followed by hydrogenation.
Ol~fln R~acean~C~ und~
The main olefin reactant componan~s of the pre~snt feed are
nonbranched Types I and II or mono-branched Types III and IV as indicated
by the follo~ing for~ulas (R - hydrocarbyl, preferably non-branched alkyl):
R-CH~CH2 R-CH-CH-R R-C-CH2 R-C-CH-R
R R
I II III IV
non-branched linearmono-branchedmono-branched
termLnal internal terminal internal
The concentration of Type I olefins is preferably greater than
30X of the total olefin concentration. The percentage of Type II olefins
is greater than 15X. Type V olefins of the formula R2C~CR2 are essentially
absent.
The n-alkyl sub~tituted Type I olefins, i.e., l-n-olefins, are
generally present at the highest concentration in thermally cracked
distillateq a~ong the YariOus olefinic species. The main product of
l-n-olsfin hydroformylation is the corresponding n-aldehyde having one
carbon mor~ than the reactant. The hydrofor~ylation of Type II linear
inte m al olefin~ ant Type III mono-branched terminal olefins provides
mono-branched aldehydes and in turn to alcohols:
-20- ~Z~ 3
R-CH-CH-R CO/H2 E~CH2CHCHO H2 ~ RCH2CHCH20H
R R
II
R-C-CH2 CO/H2 ~, RCHCH2CHO H~2 .. RcHcH2cH2oH
R R R
III
The hydroformylation of Type IV mono-branched olef~ns leads to
dibranchet products.
R-C CHR CO/H2 RCH-CHCH0 H2 RCH-CHCH20H
R R R - R R
Characteristically, the alkyl branches of the Type III and IV
olefins are mostly mathyl groups. The absence of long alkyl branches is
important in determining the properties of the oxo-derivatives of these
feed components. Types I, Il, III and IV olefins have a decreasing
reactivity in this order. Thus it Ls possible, using the selective
catalytic process of the present invention, to convert either to Type I, or
the Types I and II, or the Types I to III olefins, selectively to products
containing ton an av0rage) less than one branch per molecule. Of course,
the most lin0ar products can be derived by hydroformylating only the Type I
olefin.
Type II linear internal olefins can also be converted to
non-branchod ald~hyde~ and alcohols via the present process. To achieve
this conversion, combined isomerization-hydrofor~ylation may be carried
out. This process uses an intern~l-to-terminal olRfin isomeri7ation step
followed by a selective hydroformylation of the ~ore reaceive ter~inal
olefin isomer. For example, in: ~he case of 3-hexene, the following
reactions are involved: `
,
CH3CH2CH-CHCH2CH3 ~ CH2CH2CH2CH-CHCH3
~CH3CH~CH2CH2CH2CU2CHO /~2 CH3cH2cH2cH2cH-cu2
:~ :
:
-21- ~2~ 3
Due to lts much greater reactiYity, the terminal olefLn is selectively
hydroformylated even though its equilibrium concentration is smaller than
those of the internal olefin isomers. The cobalt-phosphine~complex-based
catalyst systems are particularly effective for coupling the isomerization
and hydroformylation reactions.
C~2 S~nqu,~g~
As a reactant gas for hydroformylating the olefin components of
the pre~ent feed, mixturcs of H2 and CO, preferably in ratios ranging from
1- 2 to 10-1, can be used. Ratios between 1 and 2 are preferred. When
reacting higher oiefins, most of the total reactor pressure is that of H2
and CO. High H2/CO pressures, particularly high CO partial pressures,
usually stabilize the catalyst system. The CO as a ligand competes with
the sulfur compound ligands for coordination to the transition metal to
form the metal carbonyl complex catalyst. The partial pressure of carbon
monoxide affects the equilibria among catalyst complexes of different
stability and selectivity. Thus, it also affects the ratio of linear to
branched products (n~i) and the extent of side reactions such as
hydrogenation.
High CO partial pressures are particularly important in forming
and stabillzing the desired carbonyl complq~ catalysts of high pressur
cobalt hydroformylation. They stabilizs the catalyst complex against
deactivation by the sulfur compound components of the feed. In a preferred
operation, the active catalyst system is produced at a lo~ H2/CO ratio.
Thereafter, the cstalyst is operated at incraasing H2/CO ratios.
The effect of CO partial pressure on the n/i ratio of aldehydes
and alcohol products is particularly important in the presence of rhodium
complexes of tri~alent phosphorus ligands, particularly phosphines.
Phosphine ligands increase the strength of CO coordination to rhodium.
Th~us, the need for increased CO partial pressures to stabilize the catalyst
complex i9 reduced. Increa~ed CO partial pressuras result in increased
sub~titution of the pho~phlne ligands by CO; i.e.~ rhodium catalyst
complexes leading to reduced n/i rAtios. To produce products of high n/i
ratios rhodiu~ complex~s containing only one CO per Rh are preferred. Thus
in this case, the partial pre~sure of CO is preferably below 500 psi.
-22- 12~73
C~t~l~st Comple3es and Select~ve Feed Conversion3
Catalysts suitable for use in this hydroformylation process
include transition metal carbonyl complexes preferably selected from ehe
group of Fe, Co, Rh, Ir and Os. The more preferred transition metals are
rhodium, cobalt, ruthenium and iridium. Rhodium and cobalt complexes are
most preferred. A preferred group of catalysts consists of transition
metal carbonyl hydrides. Some of the carbonyl llgands of these complexes
may be replaced by ligands such as trivalent phosphorus, trivalent
nitrogen, tr~org~noarsine and divalent Yulfur compounds. Trivalent
phosphorus ligands, and particularly triorganophosphines and phosphite
ester~ are preferred.
~ he preferred triorganophosphine ligands include substituted and
unsubstituted triaryl phosphines, diaryl alkyl phosphines, dialkyl aryl
phosphines and trialkyl phosphines. These phosphines may be partially or
fully open Chain or cyclic, straight chain or branched. They may have
various substituents, such as those disclosed in U.S. Patent 4,668,809 by
Oswald et al.
In general, the stable but not directly active catalyst complexes
of the pxesent invention are coordinatively saturated transition metal
carbonyl hydrides. They include metal carbonyl cluster hydrides. In the
case of Co, Rh and Ir they are preferably of the formula
LpM(CO)qH
wherein L is a ligand, preferably P, N or As ligand, M is transition metal,
p is O to 3 and q is 1 to 4, with the proviso ehat p + q - 4. These
complexes lead to catalytically active coordinatively unsaturatea compounds
via L and/or CO ligand dissociation
~ (C0)qH ~ ~ (C0))qH ~~ LpN(co)q-lH.
In the presence of the sulfur containing olefinic feeds of the
pres~nt invention some of the CO and/or other ligands can be exchanged for
appropriate sulfur ligands during hydroformylation.
~ preferred subgenus of complex catalysts consists of
penta-coordinate trialkyl phosphine rhodiu~ carbonyl hydrides of the
general fornula
(R3p)xRh~co)yH
wherein ~ is a Cl to C30 unsubstituted or substituted alkyl; x is 2 or 3
and y is 1 or 2, with the proviso that x + y is 4. The alkyl groups can be
the same or different; straight chain or ~yclic, substituted or
unsubstituted. The trialkyl phosphine rhod~um carbonyl complex subgenus of
~r
',,~.
~Z~ /3
catalyst co~plexes show~ outstanding thermal stabillty in the presence of
exc~ss erialkyl phosphine ligand even at low pressure. Thus, it can be
advantageously employed at temperatures between 140-200C under pressures
ranging from 100 to 1000 psi. Tri-n-alkyl phosphine complexes of this type
can be employed for the selective hydroformylation of Type I olefins.
In general, phosphoru~ ligands of low steric demand, such as
tri-n-alkyl phosphinss and n-alkyl diaryl diphenyl phosphines, can lead to
high n/i product ratios derived fro~ Type I olsfins in rhodium cataly~ed
hydrofor~lation. this requires a hlgh P/Rh ratio in the catalyst system
and a low partial pressure of C0.
Trialkyl phosphine complexes having branching on their ~-or/and
~- carbons have increased steric demand. They tend to form catalyst
complexe~ of struceures which have lncreased reactivity toward Type II and
Type III olefins. For example, the ~- branched tricyclohexyl phosphine and
the p- branched tri-i-butyl phosphine
' CH2 - CH2 -
CH CH2 and p 1c~2-cH-cH3i
CH2-CH2 3 CH3 3
are attractive catalyst ligands of thia type. These catalysts, while
highly active, do not provide high n/i product ratios.
Another pref~rred type of phosphorus lignnd for rhodium consists
of alkyl diaryl phosphines of low steric demand. The tris-phosphine
rhodiu~ carbonyl hydride complexes of these ligands show a desired
co~bination of operational hydroiormylation catalyst stability and
selectivity to producs hi~h n/i product ratios.
In general, tha hydrogenation activity of phosphine rhodium
carbonyl complexes i3 relatively low. Thuc~ in the presence of these
complexes, aldehyde protuces of hydroformylation can be produced in high
s~lectivity without ~uch alcohol and/or paraffin formation, particularly at
low temperaturo~.
Another subgenu3 of suitable catalyst complexes is that of
p~ntacoordinate trialkyl phosphins cobalt carbonyl hydrides of the formula:
(R3P)u~o(c3~v~
wherein R is preferably a Cl to C3D alkyl as above, u is 1 or 2, v is 2 or
3 with the provi~o that u + v is 4. Tri-n-alkyl phosphine ligands are
-24- ~2~ ,3
particularly advantageous in these cobalt phosphine catalysts since they
provide high selectivity in the production of normal alcohol products when
hydrofor~ylating the l-n-olefin and linear internal olefin components of
the present cracked feeds. Tri-n-alkyl phosphine ligands include those
wherein the n-alkyl substituents ~re part of a cyclic structure including
the phosphorus, ~.g.,
CH2 -CH2
CH3(CH2)20CH2 ~ P\
CH2 - CH2
Using theqe cat21ysts, it ~s pref~rred to operate at high temperatures.
Thus, the preierable te~perature3 are beeween 160 and 200-C at pressures of
500 to 4500 p9i. The more preferabls pr2ssure range is irom 1000 to 3000
p9i. Low medium pressurss ranging from 1000 to 2000 ps~ are most
pr~ferred.
Another subgenus of catalysts is reprssented by cobalt carbonyl
complexe~ free from phosphorus ligands. These catalysts include dicobalt
octacarbonyl and teeracarbonyl cobalt hydride.
Co2(CO)g and Co(C0)4H
The latter compound i9 assumQd to be an immed~ate precursor of
catalytically active specie~. Cobalt carbonyl catalysts are stabillzed by
bigh CO/H2 pressures ranging from 2000 to 6000 psi (136 to 408 atm) during
hydroformylation. They are preferably used in th0 lO0 to 180~C temperature
range. For a sel~ctive conversion of Type I olefins, lower temperatures up
to 145C are used.
The above cobalt carbonyl complex can be generated by reacting
cobalt or cobalt salt3 with C0 and H2. It is particularly adv~ntageous to
e~ploy cobalt carboxylates as reactants for ths generation of cob~lt
cArbonyl catalyst precursors.
When the cobalt catalyzed hydrofor~ylation ls completed, the
cobalt carbonyl complex is con~ert2d into Co, i.e. metallic cobale or
Co2~, e.g. cob~lt formate or acetate. The conv0rsion to cobalc acetate can
be advantag~ously carri~d oue with hot aqueous aceeic acid and molecular
oxygcn (air~. This allows the recovery of cobalt in the aqueous phase.
The cobalt acstate can then be conver~ed to an oil soluble higher molecular
weight carboxylate and recovered. ~or more sxtensive description of the
.
-25-
various method3 of cobalt recovery and recycle see pages 162 to 165 of the
Falbe reference.
In the hi~h pres~ure cobalt ca~lyzed reaction of the present
process uslng high sulfur feeds, dicobalt octacarbonyl is converted to
partially sulfur ligand sub3tituted components as it is indicated by the
following schemes.
C2(C)8 ~ ~ Co4tCO)7(sR)3 + C3(CO)6(S)SR
R2S~ ~
Co2tCO)7SR2 ~ [Co2(CO)sS~ + Co3(CO)gS
These and similar complexes and their hydride derivative~ form equilibria
with dicobalt octacarbonyl and tetracarbonyl cobalt hydride. The resulting
catalyst system provides active catalyst species with or without sulfur.
The sulfur containing species may also iead to insoluble and thus inactive
CoS. The conditions of the present proce g, particularly the CO partial
pressure, are set to suppress CoS for~ation.
In general, the transition metal complex hydroformylation
catalysts of th~ present invention are employed in effective amounts to
achieve the dasired olefin conversion to aldehyes and/or alcohols. The
catalyst concentratlon is typically higher in the present process using
feeds of high sulfur content than in other similar processes using pure
olefin feeds. The transition metal concentration can range from 0.001 to
5X. The more preferred concentrations primarily depend on the ~etal
employed. Cobalt concentrations range from 0.01 to 5~, preferably from
O.01 to 5X, more pref~rably from O.05 to lX. Rhodium concentrations range
fro~ about 0.001 to 0.5X. Other factors determining the optimwm catalyst
concentration are the concentration and types of olefin in the feed and the
desired olefin conversion. l-n-Olefins are generally t,he most reactive.
For a complete conversion of branched olefins, higher catalyst
concentrations sre needed.
The phosphorus, nitrogen and ~rsenlc containing catalyst ligands
are employed in excess. High excess llgand concentrations have a
stabilizing effect on the catalyst complsx. Particularly in the case of
the phosphoru3 llgands, it is preferred to employ a mlnimum of 3 to
ligand to transition metal ratio. In the case of the phosphine rhodiu~
complexes, the mLnimu~ P/Rh ratio is preferably greater than 10. P/Rh
-26- ~qa~$~
ratio~ can be as high a~ 1000. The sulfur-containing ligands may be
provided in the feed.
The use of P-, N- and As-containing ligands, particularly
phosphine ligands, leads to increased catalyst stability and selectivity
for linear product formation. At the same time activity is usually
decreased. Thus, the choice of metal to ligand ratio depends on the
desired balance of catalyst stability, selectivity and activity. The
S-containin~ ands can improve the aldehyde selectivity of the present
process.
~ig~ P~su~e Low_Femp~at ~ Hvdrofo~mYl~tion
The high pressure cobalt catalyzed hydroformylation in the
absence of stabilizing added ligands such ~s phosphines is preferably
carried out at low te~peratures below 180C where the reduct$on of aldehyde
products to alcohols and the aldol dimerization of aldehydes during
hydroformylation is reduced.
The aldehyde primary products are generally of a semilinear
character. The linear n-aldehydes are the largest single aldehyde type
pxesent in the products. The linearity of the alcohol products of
hydrogenation is of course determlned by that of the parent aldehyde
mixture. The linearity of the aldehyde products In turn is mainly
dependent on the unique feed of the present process and the catalyst and
conditions of the conversion. In the following the aldehyde product
mixtures are further characterized particularly for the cobalt catalyzed
hydroformylation.
Ihe maJor types of aldehydes are the n-aldehydes, the 2-~ethyl
branched aldehydes and 3-methyl branched aldehydes. Much of the rest of
the aldehyda~ are 2-ethyl or higher n-alkyl branched aldehydes. In
general, the normal, the 2-methyl and 3-methyl branched products preferably
represent mora than 40Z of the totai.
At the lowar temperatures, between 100 and 145C, the Type
olefins, ma~or conponents of the present feeds, are not effectively
Isomerized to the internal, Type II olefins of lesser reactivity. Thus a
high concentration of the most reactive, terminal, Type I olefins is
maintained. In addition, the low temperatures favor a higher n/i ratio of
the hydroformylation products of Type I olefiDs:
/3
-27-
RCH-CH2 . ! 2~ RCH2CH2CHO + RCHCHO
CH3
R-C3 to C33 alkyl n- i-(2-methyl)
Thus, the use of low temperatures maximized the selectivity of the present
process to the desired n-aldehyda and the 2-methyl substituted i-aldehyde
products. For tha Type II, linear $nternal olafins, 2-methyl, 2-ethyl,
2-propyl, etc. substituted aldehyde~ are formed in decreasing
concentrations as indicated by the following scheme (R - Cl to C31 alkyl):
RCH2CH2CH'CH2 ~ RCH2CH-CHCH3 , ~ RCH-CHCH2CH3
.1 \~ ~ \ 1~
R(CH2)4CHO R(CH2)2CHCH0 RCH2CHCHO RCHCHO
CH3 C2H5 C3H7
It was established by combined GC/MS studies that this product distribution
of normal and 2-alkyl substituted i-aldehydes i9 a feature of the present
process.
The 3-methyl substituted aldehydes are derived from
2-methyl-1-olefins which constitute most of the Type III olefin components
of the feed. Some of the 2-methyl-1-olefins are isomeri2ed to internal,
methyl-branched Type IV olefins and lead to other isomeric methyI branched
aldehydes, a.g.
R'CH2CH2C-CH2 CO/H2 ~ R'CH2CH2CHCH2CHO
I R-Cl to C31 alkyl
CH3 CH3
R'CH2CH-C-CH3 CO/H2 R'CH2-CH-CH(CH3)2
CH3 CHO
R'CH-CHCH-CH3 CO/H2 R'CH-CH2CH(CH3)2
C~3 C~O
~29~i3
-28-
The low temperature cobalt catalyzed process results in high
selectivity to aldehydes having one carbon more than their olefin
precursors. Little aldol addition of the aldehyde products occurs during
such hydroformylations. Thus, the so-called dimer by-products, consisting
mainly of aldol condensaticn products are minimal. Similarly, the amounts
of trimars, largely consisting of acetals and products of the Tischenko
reaction of aldol adducts, Is reduced.
A potential disadvantags of tha low temperature operation is the
relatively low reactivity of the Types II and III and particularly the Type
III olefins. This can be overcome in a staged operation which involves the
hydroformylation of Type I olefins Ln the low t0mperature regime and the
hydrofo~ylation of Type III olefinq in the high temperature regime,
between 145 and 180C.
The low temperature operation can be effectively used for the
selective conversion of Type I olefins to highly linear aldehydes. At low
te~peratures, tha hydrogenation of the pri~ary aldehyde products to ~he
corresponding secondary alcohol products is insignificant. Thus, the
aldehydes can be separated and utilized as versatile chemical intermediates
in various reactions.
Under the conditions of the present process, the desired
hydrofor~ylation of the olefinic components of the feed occurs selectively
witbout any significant conversion of the thiophenic aromatic sulfur
compounds. ~le aliphatic sulfur compounds, particularly the thiol and
disulfide components undergo a series of conversions, presu~ably via
hydrogen sulfide. It was shown by sulfur specific gas chro~atography (S
GC) of the reaction mixturc using a nonpolar capillary GC column that most
of the trace sulfur compound~ for~ed wera beyond the aldehyde product
boiling range. It was found by GC/MS that these sulfur compounds were
thiol esters and alkyl sulfides. Their alkyl groups had one carbon more
than the olefin reactants. This indicated that they were probably derived
from the aldehyde products via the following reactions with thiol and H~S
respectively.
2 RCHO ~ RSH ~ RCOSR + RCH20H
2 RCHO + H2S ~ 2H2 - (R~H2)2S
The hydroformylation reaction mixtures did undergo fur~her
reactions on prolonged standlng. This resulted in the formation of
-29-
si~nificant amounts oi` higher boiling sulfur compounds, Lncluding some
boiling in the aldehyde range. To obtain aldehydes and derivatives oi low
sulfur content, it is preferred to distill the reaction mixture without
much delay after cobalt removal.
~vdro~or~ylation-Acetalizatio~ in $ho i~#uYq__~of Cobalt
Low temperature, high pressure, cobalt catalyzed hydroformylation
can be advantageously carried out in the presence of added Cl to C6
monoalcohols, diols or triols such as methanol, ethanol, 1,6-hexanediol,
glycerol. In the presence of these lower alcohols, preferably employed in
excess, ths aldehyde products of hydroformylation undergo diacetal
formation catalyzed by cobalt carbonyl complexes. Using higher molecular
weight alcohols, higher boiling acetals are formed. After the removal of
the cobalt catalyst, these are readily separated from the reacted
components of the cracked distillate feed by fractional distillation.
Thereafter, the acetals are hydrogenated in the presence of added water to
produce the corresponding alcohols as indicated by the general reaction
scheme:
RCHO R _H RCH(OR')2 H2 ~ R'CH20H ~ 2R'OH
H20
The added lower alcohols form water soluble cobalt complexes and thus also
facilitate the removal of the cobalt catalyst after such combined
hydroformylation acetalization reactions.
In an alternate sequence of operation, the hydroformylaeion can
be carried out in the absence of added alcohol or in the presence of less
than stoichiometric amounts to minimize reactor volume. Additional amounts
of alcohol are then added to the reaction mixture after hydroformylation eo
compl~te the acetalization.
The use of added alcohols increases the stabllity of the catalyst
syste~ and the reaction raee. Due to rapid acetal formatlon, other
secondary reactions of the aldehyde reaction products such as aldoli2ation
are suppressed. Another ma~or advanta~e of producin~ the acetal
derivatives is their ease of separation. In contrast to ehe aldehydes,
which aldolize on heating durin~ distillation, the acetals of the present
invent~on can be separat~d without any significant yield loss by fractional
distillation.
2~73
-30-
The hydroformylation-acetalization process of the present
invention comprises reacting the previously described feed at first with C0
and H2 under hydroformylation conditions as described. The aldehyde
products are then reacted with a Cl to C6 alcohol at temperatures between
15 and 250C, pressure~ between 15 and 250C and pressures between 0 and
5000 psig durin~ and/or after 3aid hydroformylation. If the acetalization
is carried out or completed after hydroformylation, the conditions are
milder, preferably ranging from ambient temperature to 100C at atmospheric
pressure.
Hyd~f~L~LL~ion~- HYt~o~na~lo~
The aldehyde and aldehyde plus alcohol products of
hydroformyl~tion are usually reduced to alcohols substantLally free from
aldehydes by hydrogenation. The hydrogenation catalysts are preferably
sulfur resistant heterogeneous composltlons based on Group VIII metals,
particularly cobalt, molybdenum, nickel and tungsten. Cobalt sulfide and
molybdenum sulfide are specifically preferred. They are preferably
employed in the liquid phase at temperatures between about 50 and 250C,
preferably, 120 to 220C, and pressures in the range of 50 and 6000 psi
(3.4 and 408 atm), preferably 300 and 4000 p9i t204 and 272 atm).
The hydrogenation of the aldehyde mixtures of the present
invention can be advantageously carrled out at variable temperatures,
wherein the n-aldehydos are reduced to alcohols at first at lower
temperatures thsn those needed for i-aldehydes. The n-aldehyde components
are highly reactlve and sub~ect to conversion at high temperature to low
value n-paraffin by-product~ and aldol condensation-hydrogenatlon products.
The 2-alkyl branched aldehydes require higher temperatures for their
reduction to the de3ired aldehydes but have less tendency for paraffin and
aldol by-product formation. Thus, a preferred selecti~e hydrogenation
process for the present aldehydes in the presence of a CoS/MoS2 based
catalyst comprises hydrogenation of mo3t of the n-aldehyde components in
the temperature range of 130 to 190C followed by the hydrogenation of the
r~st of the aldehydes between 170 and 2205C. The temperatures employed of
course will also depend on ths catalysts used and the reaction time. Since
most hydrogenations are carried out in a contlnuous manner, liquid hourly
space velocities are another important factor in hydrogenation.
To increase the yield of the deqired alcohol products, the
hydrogenations are carried out in the presence of mlnor a~ounts of water,
-31-
preferably 1 to lOX based on the aldehyde reactant. The upper level of the
water i3 limited by the sensitlvity of the catalyst. The water suppresses
the formation of the aldehyde dimers during hydrogenation and facilitates
the conversion of the dimer, trimer and formate by-products of
hydroformylation to alcohols.
The hydrogenation of the present aldehydic feeds is preferably
carried out under conditions not affecting the aromatic sulfur compounds,
thiophenes and benzothiophenes. In a preferred operation, the cobalt
hydrofornylation catalyst is removed and the cobalt free hydroformylation
mixture is distilled to separate the unreacted hydrocarbons and aromatic
sulfur compounds. The resulting aldehyde distillate or aldehyde
distillation residue is then hydrogenated.
It was surprisingly found by sulfur specific GC analyses of the
reaction mixtures that most of the sulfur compound components of the
aldehyde boiling range are converted during hydrogenation to less volatile
derivatives of the aldehyde dimar derivative range. Thus, essentially
sulfur free alcohols could be obtained by a subsequent fractional
distillation.
Dependent on the sulfur content of the aldehyde products,
catalysts of varying sulfur sensitivity can be used. Such catalyst
compositions include CuO and ZnO reduced by H2 or CO. For the reduction of
the low carbon number Cs to Clo aldehydes, a vapor phase rather than liquid
phase hydrogenation process can be used.
Contl~uous H~drofor~ylation
The preferred mode of operating the present process is obviously
continuoui rnthqr than batchwise. The reaction conditions of continuous
and batchwise operation are nevertheless slmilar. Continuous
hydroformylation can be carried out in a single reactor or in a saries of
reactors using various method~ of ~eparating the cataly3t from the products
and unreacted feed components. S~irred, pncked and plug flow reactors can
be employed. Re~c~ants are continuously introduced. ~
When added stabilizing ligands (such as non-volatile phospbines)
are used, ths products and unreacted feed may be separated from the
catalyst qystem by flash distillatIon. In low pressure hydroformylation,
direct product flash-off from the reactlon vessel can be employed. At
increased pressures, a recirculation flash-off mode of operation is
preferred. This latter ~athod would includ~ a continuous removal of liquid
-32-
reaction mixture from the reactor. This liquid is then depressurized and
flash distilled at atmospheric pressure or in vacuo. The residual solution
of the catalyst may then be continuously returned to the reactor.
Stabilizing ligands of hydrophilic character may also be employed to make
the transition metal complex water, rather than hydrocarbon, soluble. This
allows b~phase ¢atalysis in a stirred water-hydrocarbon feed mixture and a
subsequent separation and return of the aqueous catalyst solution to the
reaction mixture.
In the absence of stabilizing ligands, the reaction mixture may
be continuously withdrawn from the reactor and the transition metal
carbonyl complex catalyst chemically converted to a water soluble, usually
inactive form. After separa~ion of the aqueous solution, the transition
metal compound is reconverted to the precur~o~ of the active catalyst which
i5 then recycled to the reactor.
A vsriety of reactor schem0s can be used for the optimum
conversion of ehe olefIn reactants in a continuous reactor. For instance,
interconnected reactors may employ different catalyst systems. The first
reactor may employ a phosphine-rhodium complex catalyst which selectively
converts l-n-olefins and employs direct product flash-off. This might be
connected to a second reactor containin~ a phosphine cobalt complex
catalyst which converts the linear internal olefins via
isomerization-hydroformylation. Aleernatively, cobalt alone may be used in
the first reactor followed by a phosphine cobale complex.
~x~o~o~ at~n-~ tion
A further variation of the present process is the aldolization of
the product ald~hydes. A hydroformylation plus aldolization step in the
pres~nce of a base followed by A hydrogenation step converts a Cn+2 olefin
to C2n+6 aldehydss and alcohols. This i9 indicated in the following
g~n-ral~ch-u- by th- exa~pl-s of ~yp- I o~-f~=-.
.
73
-33-
2 CnH2nllcH-cH2 / 2 ~ 2 CnH2n+lCH2cH2-cHO
n-al
1 Base
CnH2n+lCH2CH2CH-C-cHO ~ CnHzn~lCH2CH2CH2CH-CH-CHO
CH2CnH2n~l OH CH2CnH2n+1
n,n-enal n,n-hydroxyanal
¦ H2
CnH2n+lcH2cH2cH2-cH-cHo 2 CnH2ncH2cH2cH2-cH-cH2-oH
CH2cnH2n+l CH2CnH2n~1
n,n-anal n,n-anol
wherein the slmpla n-aldehyde product of hydroformylation is "n-al", the
therm~lly unstable primary product of aldolization is "n-hydroxyanal", the
unsaturated aldehyde resulting from aldolization is "n,n-enal", the
selectively hydrogenated saturated alcohol is "n,n-anal~ and the final
hydrogenated saturated alcohol is "n,n-anoln. The n,n-prefixes indicate
that both segm~nts of the aldol compounds are derived from the terminal,
i.e., normal, product of hydrogenation.
The hydrogenated saturatsd alcohol products of hydroformylation
can be also derived by ths Guerbet reaction of tho alcohols produced from
the primary aldehyde products of hydroformylation, ~.g.
CnH2n+lCH2CHO ~ CnH2n~lCH2CH20H
CnH2n+lcH2cN2cHcH20H
nH2n+l
~ I The Guerbet reaction is also a base and metal cataly~ed
conversion It is carried out at elevated temperatures concurrent with the
removal of the water condensation product.
~ ~ Minor iso-aldehyde components of the aldehyde product mixture can
also be converted in a so-called crosc-aldolization reaction with che
normal aldahyde:
.
73
-34
CnH2n+lCHCH0 + CnH2n+lcH2cH2cHo
CH3
i-al n-al
r Base
CnH2n~lcHcH-c-cHO
CH3 C~2cnH2n+
i, n-enal
H2~
CnH2n+lcHcH2-cH-cHO
CH3 CH2cnH2n*
i,n-anal
The rate of the above cross-aldolization process is slower than that of the
simple aldoliza~ion. However, the relative rate of cross-aldolization
increases with increasing temperature and decreasing n/i aldehyde ratios.
The latter can be achieved by the addition of extra i-aldehyde to the
reaction mlxture.
The aldolization step can be carried out separately by condensing
tha aldehyde product intsrmediates in the presence of a base catalyst.
Hydroformylation and aldolization plus hydrogenation r.an be combined by
carrying out the hydroformylation in the presence of ~he above-described
transition metal complex based catalysts plus a base aldolization catalyst.
A preferred mode of combined hydroformylation-aldolization is
carried out in the presence of a trialkyl phosphine rhodium carbonyl
hydride plus excess trialkyl phosphine hydroformylation catalyst system
plus a base aldalization catalyst such as potassium hydroxide.
To carry out tho present combined hydroformylation-aldolization
proca s in the preferred homogeneous, liquid phase, solvent selection is
important. The preferred solvent will dissolYe all the widsly different
components of the reaction system. Solvency for the nonpolar olefin
reactant and polar caustic catalyst and water by-product is therefore a
compromiSe. Alcohols, partlcularly hydrecarbyIoxyethyl alcohols are
excellent choices. They may be of the formula
J(oc~2c~{2)~oH
~2~4~ ~3
-35-
whsrein J - Cl to C4 alkyl, preferably primary alkyl, most preferably
methyl, C6 to Clo substituted or unsubstituted phenyl, preferably phenyl, j
is 1 to 8, preferably 3 to 8. Desirable solvents include methoxytriglycol,
CH3(0CH2CH2)30H, and phenoxyethanol, PhOC~2H20H. In general, the weight
proportion of the relatively nonpolar hydrocarbyl segment J to that of the
highly polar oligo (-oxyethyl) alcohol segment determines the relative
solvent power for the nonpolar versus polar co~ponents of the reaction
mixture. As such, this type of a solvent can be readily optimized for any
special application of the present proces3.
In ~ cont~nuous combined hydroformylation-aldolization process,
product flash-off is more difficult to real~ze because of the high boiling
points of the aldol condensation products. Therefore, direct produce
flash-off is not generally feasible. Rec~rculation flash-off, aqueous
catalyst separation and chemical catalyst recovery are preferred. Due to
the high boiling point of the aldol condeDsation products, separation from
the unreacted components of the distillate feed by fractional distillation
is facilitated. Thus, broader carbon range distillate feeds can provide
reaction mixtures suitable for aldol aldehyde or aldol alcohol separation
by fractional distillation.
Since high aldolization rates can be readily achieved in the
combined process, the reaction parameters can be readily adJusted to
provide either ths unsaturated or saturated aldehydes as the major
products. Short reaction times, and low olefin conversions, preferably
below 50%, plus high base concentration, favor the unsaturated aldehyde.
However, mostly the saturated aldol condensation product is desired. This
is, of course, the favored high conversion product.
Due to the improved thermal stabililty of the present trialkyl
phosphine rhodlu~ complex hydroformylation catalyst, the aldol condensation
products can be flashed off or distllled without affecting the catalyst.
However, strong bases have an adverse effect on the thermal stability of
the system. These can be either removed before distillation or replacsd
with weaker base aldolization cat lystq such as amines and Schiff bases.
For example, basic ion exchange resins can be filtered off. For known,
applicable aldolization catalysts, reference is made to Volume 16, Chapter
1 of the monograph ~Organ~c Reactions~, edited by A. C. Cope et al.,
published by J. Wiley ~ Sons, Inc., New York, N.Y., 1968.
-36- ~ 73
The preierred concentration of the strong organlc base, i.e ,
alkali hydroxide, aldolization catalyst is low, between about 0.~1 and lZ,
preferably between 0.05 and 0.5~. Of course, small caustic concentrations
have less adverse effect on the stability of the reaction system.
Aldehxde p~od~ an~ Per$v~ti~es
The present hydroformylation process, particularly the high
pressure cobalt catalyzed reaction, leads to unique semilinear mixtures of
aldehydes. Due to the specific mixture of 012fins found in the
hydroformylation feed, it is now possible to obtain a mixture of aldehydes
which cannot be economically produced in any other way. The aldehyde
products of the present invention are versat~ile chemical intermediates.
They can be readily converted to alcohols, acetals, carboxylic acids and
amines. The properties of thess compounds and of their ester plasticizer
and ethoxylated surfactant derivatives are distinct and desired. They
reflect the semilinaar character of their aldehyde precursors.
The semilinear aldehyde compositions have less than one branch
per molecule. They have preferably Cs to C21, more preferably C7 to C21,
most preferably Cg to Clg carbon atoms per molecule. They comprise 15 to
50X by weight of normal aldehyde which is preferably their major
constituent. Other significant components are 3 to 20X of 3-methyl
branched aldehyde and 3 to 20X of 2-methyl branched aldehydes. These
components constitute preferably more than 40X, more preferably more than
50X of the eotal. The higher semilinear C7 to C21 aldehydes preferably
also contain ~ to 20X of 2-ethyl and higher n-alkyl branched components.
The mixtures of semilinear Cs to Cls aldehydes possess alkyl
moieties which make them suitable intermediates for the preparation of
ester plasticizers having advantageous low temperature` properties.
Similarly mixtures of the semilinear Clo to C21 aldehydes have alkyl
moietiea which makes ehem sultable intermediates for surfactants having
appropriate blodegradability.
The reactions leading eo the formatlon of the present aldehyde
mixtures were previously described. The struceural for~ulas and
perc~ntag~s of ths key aldehyde constituent~ are shown by ~he following
tabulation:
-37-
CH3(cH2)ncHo CH3(CH2)mCHCHO CH3(CH2)pCHC112CHO
CH3 CH3
15 to 50X3 to 20X 3 to 20X
n ~ 3-19m ~ 1-17 p - 0-16
CH3(CH2~pCHCH0 and CH3(CH2)qCHCH0
C2H5 ( CH2 ) rCH3
p - 0-16 q + r - 6 - 21
q ~ 2 ; r ~ 2
3 to 20%
An exemplary aldehyde mixture is a semilinear isomeric C
aldehyde having less than one branch per molecule and comprising 15 to 50X
of normal undecanal, 3 to 20X of 3-methylundecanal and 3 to 20Z of
2-methylundecanal, said Cll aldehydes togother constituting 40Z or more of
the total. Another exemplary composition iq a semilinear isomeric C13
aldehyde having less than one branch per molecule and comprising 15 to 50X
of normal tridecanal, 3 to 20Z of 3-methyl-dodecanal, and 3 to 20Z of
2-methyldodecanal, said C13 aldehydes together constituting 40X or more of
the total. Percentages are by weight.
In spite of the high sulfur content of their olefinic feed
precursors, the present aldehyde mixtures are preferably of low sulfur
content. They have less than 1000 pp~, more preferably less than 200 ppm
sulfur. ~istilled aldehyde mixtures of narrow boiling range, containing
mostly isomeric aldehydes of the same carbon nu~ber are preferred low
sulfur compositions.
A preferret type of derivatives of the present aldehyde mixtures
are the correspond~ng primary alcohol mixtures. They comprise semilinear
Cs to C21 alcohol mixtures having less than one branch per molecule and
comprising 15 ~o 50X of normal alcohol, 3 to 20X of 3-methyl branched
alcohol and 3 to 20X of 2-methyl branched alcohol. The C7 to C21 alcohols
preferably also contain 3 to 20X 2 eehyl and higher 2-alkyl branched
alcohols. Thesa alcohol constituents and thsir percentages by weight are
defined by formulas oi the following tabulation:
-38- ~2~ 73
CH3(CH2)nCH20H CH3(CH~)mCHCH20H CH3(CH2)pCHCH2CH20H
CH3 CH3
15 to 50~ 3 to 20X3 to 20X
n - 3-19 m ~ 1-17p - 0-16
CH3(CH2)pCHcH2~H and CH3(CH2)qcHcH20~
C2H5 ( CH2 ) rCH3
p - 0-16 q ~ r 6 ~ 21
q 2 2 ; r 2 2
v
3 to 20X
A The preferred subgroups of these alcohol mixture~ are the same as
those of their aldahyde precursors. The above 3 eypes of components
prefsrably constitute more than 40X, preferably more than 50X of the total.
The semilinear Cs to Cls primary alcohol mlxtures provide ester
plasticizers with advantageous low temperatur0 properties. Similarly, the
Clo to C21 alcohols are intermsdiates for biodegradable surfactants.
An exemplary alcohol mixture is an isomeric primary Cg alcohol
having less than one branch per molecule comprising 15 to 60% of normal
nonanol, 3 to 20X of 3-msthyloctanol, and 3 to 20X 2-methyloctanol said Cg
alcohols constituting 40X or more of the total alkyl groups. Similarly, a
mixture of isomeric primary C7 alcohols has less than one alkyl branch per
~oleculs and comprises 15 to 60Z of normal heptanol, 3 to 20~ of
3-methylhexanol and 3 to 20X 2-methylhexanol. Said C7 alcohols also
constituting 40X or mora of the total.
The plasticizer e~ters based on the present alcohols are neutral
alkyl esters of mono-, di- and tribasic carboxylic acids and phosphorus
acid~ such as phosphoric, phosphorus and phosphonic acids. On an avsrage
their alkyl groups have less than one alkyl branch and compxise 15 to 50Z
of normal alkyl, 3 to 20Z 3-methyl branched alkyl and 3 to 20X 2-methyl
branched alkyl group~ and together they pref~rably repreqent more than 40X
of the total.
Exemplary and preferred types of the prssent plastici~er
compositions are alkyl b~nzoates, dlal~yl phchalates, dialkyl adipates,
trialkyl trimellitates, trialkyl phosphates, trialkyl phosphites, dialkyl
benzenephosphonates.
39 ~z~5~3
Th9 moqt preferred plasticizer ester derivatives of the present
alcohols are the dialkyl phthalate ester~. They are prepared by reacting
the Cs to Cls alcohol mixtures with phthalic anhydride according to known
methods. The two alkyl groups of these esters each have an average of less
than one alkyl branch and comprise 15 to 50X normal alkyl, 3 to 20Z
3-methyl branched alkyl, 3 to 20X 2-methyl branched alkyl moieties.
Tog~ther they preferably represent 40X or more of the total.
A preferred exemplary phthalate ester of the present invention is
ditridecyl phthalate having tridacyl groups with an averags of less than
one alkyl branch and co~prlsing 15 to 50X normal tridecyl 3 to 20X
3-methyldodecyl and 3 to 20X 2-mathyldodecyl groups, said tridecyl groups
together rspresenting 40X or more of ~he total.
The plast~cizer esters of the semilinear alcohols of this
invention may be employed to plasticize thermoplastic resins, sspecially
the vinyl resins. Suitable resins includ~ PVC resins derived from vinyl
chloride monomer as well as copolymer~ of vinyl chloride and other mono-
and di- olefinically unsaturated mono~ers copolymerizable therewith. The
plastici~ers may also be used in con~unction with other polymers or
mixtures thereof including, for example, polyvinyl alcohol, polyvinyl
acetate, polyvinyl butyral, polyvinylidene chloride, polyethyl acrylate,
polymethyl acrylate and poly~ethyl methacrylate. Preferred are vinyl
halides such as polyvinyl chloride and copolymers of vinyl halides such as
those containing at least 70 wt. ~ vinyl halide, e.g., vinyl chloride. The
plastici~ers are employed in effective pla~ticizing amounts and generally
from about 1 to 200 pArts of plastici2er per hundred pArts oi resin by
weight (phr) and preferably 10 to 100 phr. Plasticized resins containing
the esters of this invention exhibit excellent low temperature flexibility,
high te2p~rature stability and reduced volatility.
Some of the esters of monocarboxylic acids, especially the acetic
acid acid esters of the present semilinear C6 to C12 alcohols are also
useful as solvents. The alkyl groups of these ester3 also possess less
than one branch per molecule and co~prise 15 to 50X nor~l alkyl, 3 to 20
3-methyl branched alkyl and 3 to 20X 2-~athyl branched alkyl groups.
The semilinear C8 to C21 primary alcohols of the present
invention are attract~ve intsr~ed$ates for e~hoxylated and/or propoxylated
nonionic ~uriactants. Sulfated or sulfonated surfa tants derived from
either the present alcohols or from thelr ethoxylated and/or propoxylated
derivatives are of an anionic character. The preferred cationic surfactant
?73
-40-
derivatives af these alcohols, are primary, secondary and tsrtiary amines,
ethoxylated and/or propoxylated tertiary amines and their quaternary
ammonium deriva~ives, especially in their ammonium salt form. The
semilinear alkyl moiety of the alcohol pr~cursors advantageously affects
the biodegradability of all three classes of surfactants. Besides the
hydrophilic-lipophilic balance, the properties of nonionic, anionic and
cationic surfactant mixtures of the present invention depend on the
presence of semilinear Clo to C21 isomeric primary alkyl groups derived
from the present alcohols
The nonionic, anionic and cationic surfartant derivatives of the
present semilinear alcohols are derived via known methods, Their
derivation is exemplified by the following reaction schemes wherein the
symbol of the C8 to C21 alcohol reactan~s is RCH2OH.
RCH20CH2CH2S03Na _ RCH20il `~ - RCH20S03Na
RCH20H ~ n CH2-CH2 - ~ RCH2(OCH2CH2)nOH n - 1-30
~t/ ~
RCH2(0CH2CH2)nS03Na RCH2(0CH2CH2)nOS03Na
RCH20H + NH3 ~ ~D RCH2NH2 + (RcH2)2N~l + (RCH2)3N
x+y CHz-CH2
,(cH2cH2o)xH
RC~2N
(cH2cH2o)yH
H2
RCH20H ~ CH2-CHCN -~ RCH20CH2CH2CH2NH2
x + y - 2-30¦~ x + y CH2-CH2
,(CH2CH20)XH
RCH20CH2CH2CH2N ~
(CH2CH20)yH
As indicatad by the product formulas oi` the above scheme, the
.preferred semilinear surfacta~ts are selected from the group of nonionic
suriactants consisting of ethoxylated andjor propoxylated alcohols; the
~2~4~73
-41-
group of anionic surfPctants consisting of alkyl sulfates, ethoxylated
and/or propoxylated alkyl sulfates or alkanesulfonates; the group of
cationic surfactants consisting of alkylamines, ethoxylated and/or
propoxylated alkylamines, ethoxylated and/or propoxylated alkyloxypropyl
amines and quaternary salts of said alkylamines and alkyloxypropyl amines,
wherein the isomeric Ca to C21, alkyl groups of said surfactants each have
on an average less than one branch and comprise 15 to 50X normal alkyl, 3
to 20~ 3-methylalkyl, 3 to 20X 2-methylalkyl and 3 to 20Z 2-ethyl and
highar n-alkyl groups together representing more than 50Z of the total.
These compounds preferably do not contain any completely substituted, i e.
quaternary carbon.
A preferred subclass of the present surfactants is that of the
ethoxylated higher C8 to C21, preferably higher C12 to C16 alcohols wherein
the alkyl groups are semilinear and defined as above and the ethoxylated
moiety contains from 1 to 30 ethoxy units. These ethoxylated semilinear
alcohols compare well with the corresponding ethoxylated branched and
linear alcohols. They are better wettin~ agents than the linear
derivatives. From the practical point of view, their biodegradability is
of the same order as that of the more expensive linear compounds.
As specifically preferred, nonionic surfactant is a semilinear,
isomeric ethoxylated tridecyl alcohol containing from 1 to 30 ethoxy units
wherein the isomeric tridecyl groups are defined as above.
The semilinear C8 to C21 aldehydes of the present invention can
be also advantageously used for the preparation of surfactants. Carboxylic
acid surfactants of the anionic type can be produced by the oxidation of
these aldehydes or their aldol aldehyde derivatives by molecular oxygen in
the presence of a base. For exampla, with the normal aldehyde components,
the following conversions are carried out:
.
RCH2CHORCH2CH-CCHO
2 ¦ NaOH2 ~NaoH
RCH2C02NaRCH2CH-CC02Na
R
73
-42-
Cationic surfactants can be also derived from the semilinear
aldehydes via reductive amination.
RCH0 NH3~ RCH2NH2 ~ (RcH2)2NH
H2
Amines can be also produced directly from the thermally cracked definic
stre~ms via hydroamination in the pre~nce of rhodium complex catalysts,
e.g.,
RCH--CH2 ~ RCH2CH2CH2NR 2
HNR'2
Wherein R' is Cl to C8 alkyl and substituted alkyl such as 2-hydroxyethyl.
EW~
In the following, examples are provided to illustrate the claimed
hydroformylation process, but not to limit the invention. Prior to the
examples the cracked distillate feedstocks are described. The description
of the feedstocks details the structural types and amounts of reactive
olefins present, this information being a key component of the invention.
Thereafter, the low and high pre3sure hydroformylation procedures used and
the product workup are outlined. Thsn the examples of the actual
hydroformylation experiments are given in groups according to the feeds and
catalysts employed. The summarized reqults of these experi~ents are also
provided in tables.
The cobalt catalyzed high pressure hydroformylation of cracked
distillate fractions is described in particular detail. The semilinear
aldehyde product~ of varying carbon number are characterized. Their
hydrogenation to the corresponding alcohols is also outlined. Finally, the
conversion of the alcohols to phthalate ester plasticizers and ethoxylate
surfactants ic discussed. Some comparative data on plasticizer and
surfactant properties are also provided.
Feedstock~
The feedstocks used in the following examples were fractions of
liquid distillates produced by Fluid-coking and Flexi-coklng in the
temperature range of 482 to 538C (90Q to 1000F). As hi8h temperature
43 ~2~73
thermal cracking processes, Fluid-coking and Flexi-coking produce
distillate llquids and residual coke from vacuum residua. In Fluid-coking
only the distillate products are utilized. The vacuum residue feeds and
the thermal cracking step of Fluid-coking and Flexicoking are identical.
However, the Flexicoking process is further integrated into the refinery by
virtue of using the coke to manufaceure low thermal value gas. Flexicoking
is disclosed in U.S. Patents 2,905,629; ~,905,733 and 2,813,916 which were
previously discussed. Flexicokin~ ls described ln U. S. Patents 3,661,543;
3,816,084; 4,055,484 and 4,497,705.
The key factor in producing the present highly olefinic feed is
the high temperature ther~al cracking. However, ~nother important factor
i9 the origin and prior treatment of the petroleum residua to be cracked.
Th~ presence is desired, major l-n-olefin components of the present feed
depend on the presence of n-alkyl groups in the feed. These olefins are
formed by the cracking and dehydroganation of n-alkyl aromatics and
paraffins. In the past the molecular structure of higher boiling coker
distillates was not k~ow~. Thus the desired feeds of the present invention
were not recognized.
The Fluid-coker distillate feeds were derived from a Northwesc
American crude. The Flexicoker distilla~es were produced from mixed crudes
of Southwest American and Mideastern origin. Their compositions and those
of o~her cracked distillates of different origins were remarkably similar.
An important step of the present inventlon was the structural
analysis and recognition of the preferred distillate feeds. Since these
feeds are extraortinar~ly complex, several analytical techniques were
employed. The feed~ were analyzed using pac~ed column and capillary gas
chromatographs (GC). The capillary GC was equipped with 50m or 30m fused
silica columns coaeed with methyl silicones to determine the individual
components. The sulfur compound components ware also analyzed by capillary
GC, using a dual detection system. The colu~n effluent was equally divided
and directed to a flame ionization detector (FID) and sulfur specific
detector. Sulfur was detected either by a HallTM Electrolytic Conductivity
Detector ~iving a linear response to sulfur or a Hewlett-Packard Flame
Photometric Detector with a close to square dependenca on sulfur
concentration.
A high resolution, 40Q MHz, proton resonance spectrometer (NMR)
was used to estimate the various types of hydrocarbons, particularly
olefins.
;~
37~
-44-
The structures of key feed components and products were
determined by combined gas chromatography/msss spectrometry, GC/MS A
Finnigan TSQ-46B triple stage quadrupole GC/MS/MS was used in a single
stage mode. Both electron impact ionlzation (EI) and chemical ionization
(CI) were used for the identification of the components. EI provided
informatlon on the structura of the molecular frag~ents. It was
particularly successful ln determining the structure of the 2-alkyl
branched aldehydes bassd on the fragments resulting from the McLafferty
rearrangement. CI, using a~monia and deuterated ammonia as reagent gases,
was used in determining the molecu~ar weight and compound class of
components.
Th2 sulfur containing ions ~ere recognized on the basis of the
appearance of assoc~ated isotopic peak3. The natural abundance of the 34S
isotope is about 4X of the 32S isotope. Therefore, besides the peak for
the 32S fragmene, an appropriate weaker peak having a higher m/z value by 2
is exhibited for the isotopic 34S moiety.
Elemental and group analysis techniques were used to determine
total sulfur, mercaptan sulfur and total nitrogen contents.
Co~er ~E~L~h~
The compo3ition of several coker naphtha distillates was analyzed
by capillary GC, using temperature programmed 30 and 50m columns. They key
componants of the mixture were identified by GC/MS with the help of
standards as required.
The capillary gas chromatograms of Fig~Q_l were obtained using a
30m coluwn with FID and S detectors to show the distribution of hydrocarbon
and sulfur compounds in a Flexicoker naphtha.
The GC of they hydrocarbons ~and organic compounds in general) in
the bottom of the figure shows that the largest s~ngle types of components
in the C6 to Clo range are the l-n-olefins (Cn) followed by the n-paraffins
(Cn). This ratio is about 1.3. This ratio is very sensitive to the
cracking conditions, particularly temperature. Among the aro~atic
compounds, toluene, xylene and trimethyl-b~n7enes are ehe main components
in ehis carbon range.
The upper sulfur specific chromatogram shows that the major
sulfur compounds prssent were aromaeic: thiophene, mono- di- and
trimethylth~ophsnes. The minor suliur compounds wero aliphatic thiols.
1~ 73
Figure 1 indicates that the GC retention times and the boiling
point~ of the thiophenic sulfur compounds and those of the aromatic
hydrocarbon co~ponents largely coincide. Both differ from the boiling
range of the ma~or olefins present.
Thus, it is possible to separate highly olefinic C6, C7 and C8
distillate fractions essentially free from-aromatic sulfur compounds as it
is shown by the shaded portions of the figure. The minor thiol components
of these fractions can be removed by caustic wash or by converting them by
oxidati~e methods to higher boiling compounds which can be then readily
separated by distillation.
The hydrocarbon composition of the Fluid-coker naphtha was
analyzed with a capillary GC equipped with a 50~ column which provided a
higher resolution of the co~ponents. The l-n-olefins and n-olefins were
again the main types of components in that order. The complete
chromatogra~ is shown by Figure 1 of the parent application.
The corresponding l-n-olefin to n-paraffin ratios of the
Fluid-coker naphtha are shown by Table I. In the C6 to Cl2 range chese
ratios range from about 1.1 to 2.1. In general, the l-n-olefin to paraffin
ratio increases with increasing carbon nu~ber.
l-n-Olefin Versus n-Paraffin Components
of Fluid-Coker Naphtha
Com~onent. GC~
Ratlo,
Carbon l-n n- Olefia_
No. Ql~ Paraffin Paraffin
3 0.120 0.169 0.7101 --
4 0.193 0.307 0.6287
0.418 0.523 0.7992
6 1.298 0.924 1.4048
7 1.807 1.496 1.2079
8 2.223 1.960 1.1342
9 2.164 1.651 1.3107
2.215 1.483 1.4936
11 1.534 0.989 1.5Sll
12 0.623 0.299~ 2.0836
3-12 12.295 9,801 1.2545
73
-46-
As summarized by Table I, in the C3 to C12 range, the naphtha
contalned 12.3X l-n-olefins and 9.8X n-paraffins. Thus, the overall
l-n-olefin to n-paraffin ratio was 1.25.
The ratio of l-n-olefins to n-paraffins is a main factor
indicating whethsr or not a given thermally cracked distillate is suitable
feed in the present process, particularly in the case of the cobalt based
catalysts. The ratio should be above 1, praferably above 1.2.
Lower cracking temperatures result in decreased olefin/paraffin
ratios. For example, delayed coking which is carried out at a lower
temperature than Fluid-coking give~ distillates of lower ratios. An
analysis of a naphtha fraction irom a delayed coker gave an average of 0.3
l-n-olefin/n-paraffin ratio as it is shown by Tab~e I~.
Table II
l-n-Olefin versu~ n-Paraffin Co~ponents
of Delayed Coker Napheha
Com~onent GC~ ~
Ratio,
Carbon l-n n- Olefi~
No~ Olefin Paraffi~Par~in
6 1.9565.008 0.3850
7 2.3447.352 0.3188
8 1.8796.707 0.2802
9 1.4924.148 0.3596
0.3740.994 0.3763
6-10 8.04524.209 0.3323
A comparison of the olefin/paraffin ratios of Table I and Table
II indicates that Fluid-coking provides an about 4 times greater
olefin/parafiin ratio than delayed coking.
~ any of the other components of ~he naphtha were also identified.
Some of the illustrative detalls will be given in a discussion of certain
distillate fractions.
The broad C13 to C12 coker naphth~ fraction was fractionally
distilled, using a column equivalene to 15 theoretical plates wieh reflux
rativ o f 10, to produce distillates rich in olefins and p~raffins of a
particular carbon number. The bolling ranges and amounts of the distillate
fractions obtained ondistilling th~ naphtha are shown by rab~es ~I and IV.
The l n-olefin and n-paraffin components and a few kay aromatic
4~ 3
cn tG
C`~ S o ~ In ~ N O C~
L S ~ O O O O O ~ O
C~ Z
C o o I r~ o o o
- aJ ~
al O O
1: ~ ~ O ~ ~ _ r~ W ~ I~
~ o ~ O ~
~ o o
Q G C In oo 01 l~ ~ C~l
C.~ _ o _ ~ ~ ~ r~ ~ ~
c E
LL '- C~ ~oO~ r~ O
O ~ ~ ~ 0_~00
~ ~ ~ o n C`J~
'P' ~ ~- ~ UO~ C~ ~
L~_
~ ~ o~ ~ ¦ . . .
-- LL --I --' O
--
~ t l -N~ , e
,~ O O T O~ O O L~) O .D ~ ~ ~
I_ ~t o ,s~ , o _ cn u) C~J E
o o O Z
(n .~ _ o O c~ I _ o c~ O
~ O C~ O O ~ ~ ~ O ~C
o E 00 ~0 ol _ O _ ~ O _ ~
~ S ~ I --I O-- --= 00 0 E
~ a~ ~ ~, ~ o~ O I ~ O. ~ . ~D o
~I 3 ~ U~ O c~
C~
~: _ I
.~ U~ I I I .--O r~
~ ~ o o U~
C~ ~ O ~ ~t _ ~ r~ O
__ C~l__ c
.. ~.. , _ ~
z o~ o~ ~ E~ O
:n o ~D _
D~r~
Cl~ ~_ ~ ~ X _ r-~
-- 48 --
'J
" 1 o ~ o N
L u I_~ ~I N ~ N CO O D
~ U
~ ~ 1~ 5~ ~D ~ N C~) ~ CJ
., _ O O . .. . . . L .
L~ O ~ . C~l O ~ ~ ~
O V~ Oæ
~3J t~ o ~ o a~ C O
._ U O~ ~ ~ ~ . . .. . . . _
1~ ~ _ N _ t'~ O O CO 0~ O O O
O ~ ~ C
LL ' '`'~ c ~
2~ Q r~ C 1~ ol CO r~ ~ E ~ o
m ' 0 3~
Cil O ~ 0
~o u ~O ~ I~ - C .~,
r~ _~ O ~1~0 I~J_ ',~ U~
a~
~e e U ~ ~ o l ~ o ~ ~
~3 ~Q ~11 r~ I o (13
C 'C o CV3
, el~ $ ~ O Oo~ 1~ N ~ _
3 ~ L~ I C
I~ aJ-O
0 u~ oI ~ ~ t ~ ,u ,~,
O _ N~ ~ C0 l~o N O v) ~_ 3
C _ I I IV 2 Q G
3J ~ ~/7 C U
O C ~1
I= o E IU ~ I" _ ~c~v
C ~ llCo C 1~ 0 0 ~ _I ~ ~ CU
o . C_~ o ~ o C C~ ~
E a _ c_~ x _ o ~-- _ v ~ _ ~ z _ v
-` ~2~4~ ~3
-49-
hydrocarbons present are also shown. The results indicate that in the Cs
to Clo range, distillates containing about 15.1 to 29.6X of individual
l-n-olefins could be produced. In the case of the higher boiling
fractions, separation was more difficult and thus the maxlmum l-n-olefin
percentage in the case of l-dodecene was 12.7X. The separa~ion of Clo, Cll
and C12 fractions was adversely affected by the presence of water in the
distillation vessel. This effect could be eliminated by removing the water
in vacuo.
The C4 to C12 naphtha and selected distillate fractions thereof
were also studied by proton NMR using a JEOL GX 400 ~Hz spectrometer.
Figure 2 shows the NMR spectrum of the olefinic region of the naphtha with
an indication of the chemical shift regions assigned to the vinylic protons
of various eypes of olefins. A quantitative dete~mination of the olefinic
protons of the various types of olefins w8s used to estimate olefin
linearity. The relative mole percentage~ of olefins of varying carbon
number were calculated on the basis of amounts of the different types of
olefinic protons. The results of these calculations are shown in Table V.
The data of Table V show that the Type I olefins, i.e.,
monosubstituted ethylenes, are the maJor type of olefins in all the
distillate fractions as well as in the starting C4 to C12 n~phtha. The
percentage of Type I olefins in the distillation residue is, however,
reduced to less thsn half of the original. It is assumed that this result
is due to l n-olefin conversion during the high temperature distillation.
Minor variations, between 32 and 50Z, are also observed in Type I olefin
content of distlllate cuts. Ths reasons for thi.~ variation are unknown.
The only Type I olafins indic~ted in the C8 and higher carbon fractions are
l-n-olefins.
The second largest olefin type present in the naphtha and its
dlstillate consists of 1,2-diqubstituted ethylenes. The percentags oE
these Type II olefins varies between 18 and 26~. Most, if not all, of
these olefins are linear internal olefins.
Type III olefins, i.e., l,l-disubstituted ethylenes were found to
be present in amounts ranging from 12 to 17X. The ma~or olefins of this
type were 2-methyl substituted terminal olefins. On the basis of MS
studies of aldehydes deri~ed from these olefins, it appears that their
branching occurs mostly at the vinylic carbon.
Type IV olefins, i.e. trisubstituted ethylenes, were the smallest
monoolefin components of these distillates. Their relative ~olar
~Z~ 7;~
-- 50 --
~ o
._ ~ ~ ~
l~- .
C~J o ~
. ~ ~ ~ I ~ N
_~ ~ ol
~1 ~ ~ ~ ~D
~1 . O 1~) Cr ~ N ~
~ ~ o ~ n ~C~
_ e ~ ~ o ~ o N
_ ~- ~
:~O ~ O I C~ ~ D ~I~
~ O ~ ~_ ~ ~ J O
I_ ~ e O ~ ~ ~ ¦ ~ N
o ~ V O _ N ¦ e~ N . __
aJ ~ o o l o co u- o c~ Q
4 ~ c~
l --I~ ~'1 N _ e
l ~ r~
~ a~
a!: OT ~ ~ O O
,~ ~~ ~ ~
C_~ ~-- ............ ~ .~
~__ _. ~ ~ ~ ~ C
,c C ~ ,C ~ 3 ~0~
S ~ ~ ~cV
Il~ O _ o
2 a~ O
37~ 1
-51-
concentration is in the 6 to 12X range. Interestlngly, the C8 fractions
contained the least of these olefins among the fractions examined.
Type V olefins, i.e., tetrasubstituted ethylenes, could not be
deter~ined by proton N~R. They are of little interest in the present
invention since they are apparently unreactive in hydroformylation.
Finally, Table V also lists small but significant quantltiies (8
to 16Z) of con~ugated diolePins. The amounts listed for these olefins are
approximate because conjugated olefins may have a different number of
vinylic hydrogens per molecule dependent OD the site of conJugation and the
presence of branching at vinylic sites.
The NMR spectra of naphtha fractions w~re also analyzed in the
area of aro~atic and paraffinic protons to esti~te tho amounts of olefins.
Ta~le VI summarized the results. It shows the percentage distribution of
various types of hydrogens. From this distribution and the elemental
analyses of these fractions, th~ weight percentage of various types of
compounds was ssti~ated.
The Type I olefins, mostly l-n olefins were estimated to be
present in these fractions in the range of 18.7 to 28.3X. These
percenta~es depend on both the carbon nu~ber and the particular usually
narrow boilin~ range of the olefinic fractions studied. In the C6 to Clo
range these values for the Type I olefins approximately correspond to the
values obtained for l-n-olefin by GC.
The total olefin content of these fractions is in the 47 to 62X
range as deter~ined by NMR. It is noted that the con~ugated diolefins are
included in this p~rcentage since they ~re converted to monoolefins under
hydroforDylation conditlons or by a prior mild hydrogenation. The amounts
of paraffins are g~nerally decreasing with increasing csrbon numbers while
the amounts of the aromatics are generally increasing.
To illustrate the detailed composition of the presen~ naphtha
feeds, more detalled data are pro~idsd on the C8 and Clo fractions on che
basis of GC and GG~S analyses.
The compositlon of a heart cut C6 Fluid-coker distillate fraction
is shown by Table VI~. This frac~ion was obtained by the redistillation
using a 15 pla~ column and a lO to 1 rePlux ra~io (15/10) of a broad C6
cut It distlll~d between 56 and 65C (133 - 149F). Table VII shows the
compo~tion of the broad cut ~eed and the heart cut product of
distillation.
~$~3
-- 52 --
C ~
, ._ ~o ~ I_ o o~ ~ _
o ~ ~ ~t ~ ~ ~ U~
l- - o
e ~1 _ ~ ~ ~O ~ ~O c~.
O_ _ ~ ~ ~ r_
_ _ C~
I ~C I 00 r~
~ L 4--c~J ~J 'D ~ ~
e CL ~ ~ ."
a~
U~ r~ ~ _ ~ U7 _ 2 U7 0
I-J C ~11 ~r ~O
~IJ
.C I_ ' U ~0 ~ CO _
~ ~
a e ~ ~ ~ o co
~? ~
U ~ ~ ~ o
~Z ' ~
~` ~
a~ d' O 1~ ~ r~
8-U ~ Ct) tr~ ~ I` t~ O C~J 3
:2 aL V O _ C~i ~ ~ ~ ~0 11 el~
-
~o 2 ~ L ~ ~ . ~ r` O O~ O n _
e ~ c a~ _ ~ ~ ,~ r~ O ~ ~
o 3~ o ~ o, ~n " ~ O. _.
o~? ~
~ ~ .0 er ~ 00 CO ~ ~ e~O
3, ~ , ~ r~ _ ~ ~ _ ~~ ~
'- ~ C l _ o o o o o _ o o o
aJ u~ C~l ~ ~ O G
,, ~ aJ--' I ~ C~J t~> O ~` C~J ~ C~l
,~ ~ -1 - -' - -
C CO ~ I~ L~
~ ~ ~ ~ - - ~ - ~
I ~ a~
I ~O 1~ O
,c ~ ~ ~t '` ~ a~
_ ~:n ~ D r _ _ _
o ~q V ~O O~
a~ ~ o ~ o o~
0 ~ ,_ _ _ _ ~ ~ ~
O C L
~L ' ~O 1~ O = C~ J +
~ ~ et --
~L ~ .
Table VII
CO~ ITS 0~ THE C6 DISTILI~TE CUT OF
A FLUID-COKRR N~P~THA BE~ORE AND AFT~ R~DISTILL~TION
Seq. Componçnt Boiling Point Componen~ GC Re-
No, ~ erature)GC, Z tention
Abbre- -F C Feed Heart Time
_ Namç _ vint~,o~ a~ Cut Min
1 l-Pentene 112 44,2422.30 - 6.79
2 n-Pentane 97 36.0653.06 - 7.17
3 2-Methylbutene-2 10138.5683.30 0.10 7.94
4 Cyclopentene CP~ 11244.2422.33 0.37 9.40
4-Methylpentene-1 4MeP- 12953.8652.45 2.44 9.65
6 3-Methylpentene-1 3MeP~ 13054.1781.84 1.60 9.71
7 Cyclopentane CP 12149.2621.91 0.81 9.97
8 2,3-Dimathylbutane 2,3-Di~eB 13657.9880.17 0.27 10.15
9 2,3-Dimethylbutene-1 2,3-DiMeB~ 132 55.6160.68 0.78 10.20
cis-4-Methylp~ntene-2 c-4MeP~2 13356.3870.34 0.44 10.33
11 2-Methylpentane 2MeP 14160.2713.28 5.53 10.40
12 trans-4-Methylpentene-2 t-4MeP~2 13958.612 1.71 2.37 10.48
13 3-Methylpentane 3MeP 14663.2821.76 3.58 11.22
14a 2-Methylpentsn2-l 2MeP~ 14462;113
l-n-Hexçne n-H~ 146.5 63.48521.13 42.00 11.65
16 3-Methylcyclopentene 3MçCP-149 64.910.24 0.50 12.06
17 n-Hexane n-H 15668.73610.6113.71 12.38
18 cis-3-Hçxene c-3H- 15266.450l.S0 2.45 12.52
19 trans-3-Hexene t-3H- 15367.0883.15 4.25 12.69
trans-2-Hexene t-2H- 15467,8845.18 8,38 12.86
21 trans-3-Methylpentene-2 t-3MeP~2 lS970.438 1.12 1.46 13.04
22 4-Methylcyclopentene 4MeCP~ 150 65.67 1,OS 1.93 13.11
23 cis-2-Hexene c-2H- 15668.8911.64 1.64 13.31
24 2,3-Dimethylbutadiene 2,3-DiMeB - 154 67.78 0,16 0.20 13.46
cis-3-Methylpentene-2 c-2MeP~2 15467.7072.16 1.12 13.76
26 Methylcyclopentane MCP 16171.8124.26 2.04 14.14
27b l,l,l-Trichloroethane C13CCH3 165 74.10 - 0,05 15.02
28 Methylcyclopentatiene MeCP~- O.S9 0.12 15.02
29 l-Methylcyclop~ntena l-MeCP~ 168 75.49 0.54 15.79
Benzene Bz 17680.1008.38 1.26 15.92
31 Thiophene S 18484.16 0.10 0.06 16.22
Total Identified 86.94C99.46
a) 2-Methylpentene-l was not separat~d from l-n-hexene on the column used, I~ amounted
to about 2X. b) Trichloroethane was present as an impurity as a result of using it as a
solvçnt for cleaning the distillation apparatus, c) Thç feed cont~ined significant
amounts of higher boiling components,
~Z~4~
-54-
Table VII shows that the largest components of both the feed and
the heart cut were l-n-hexene (n-H~) and n-hexane (n-H). There were also
significant amounts of linear internal hexenes (16.7Z) and methylpentenes
~9.4X plu8 2-methylpentene-1) in the heart cut. In addition, l.9Z of
4-methylcyclopentene and 0.5X of 3-methylcyclopentene wsre identified.
Thus the amount of linear internal and monobranched olefins is about 28.5X.
Only 0.8Z of a dibranched olefin, 2, 3-dimethylbutene was found.
The composieion of the heart cut is illustrated by the gas
chromatogra~ oX Fi~u~e 3. The co~ponents are id0ntified by the sy~bols
explained in Table VII. Figure 3 also shows ths chromatogram of
unconverted hydrocarbons remaining a~ter tha hydroformylation of the heart
cut. The m2~or unconverted components were n-hexane, methylpentanes and
benzene as expected. The comparison of th~ chromatogra~s of the
hydrocarbon components of the hydroformylation feed and the final reaction
mixture greatly helped in the identificstion of ehe feed components.
Tab~ VI~ shows the composition of two C8 fractions of a
Fluid-coker naphtha. It is apparent that beside the major l-octene
component, there are significant quantities of all the linaar internal
octene isomers. The trans-isomers of octene-2,-3, and 4 were identified.
2-Methylheptene-l was also identified as the largest single branched
octene. Toluene, ethylbenzene and xylenes were al90 present.
One fraction is richer in l-n~octene, the other ln n-octane. The
sum of identified olefins in the3e fra¢tion~ is 33.lX and 20.1%,
respectivoly. Some of the octene isomers wera not identified. The first
fraction richer in olefins was used as the feed in the C8 naphtha
hydrofor~ylation exp~ri~nts.
Ths composition of C8 Flexicoker naphtha fractions was also
studied in some detail. At first a broad C8 cut was obtained by a 15/10
fractional distillation between 110 and 135~C (230 - 275~C). Part of this
broat cut was then redistillad with a 36 plate~ column using a reflux ratio
20 ~2h/20). Fractions of the 36/20 distillation boiling betwesn 117 and
124C (243 - 255F) were combined to provide a narrow cut in about 42X
yi~
~ a~ shows the composition oi th0 above broad and narrow Cg
Flexicoker naphtha fractions. A comparison of the capillary GO data of
Tables VIII and IX indicates that the composition of these Fluid-coker and
Flexicoker naphthas is similar in spite of their different crude sources.
The narrow cut Flexicoker naphtha fe0d con~ains hi~her amountc of linear
73
-55-
T~ble VIII
~Jor Olefln, Par~ffin and Arom~tic ~ydroc-rbon Components of
Dlstill~t2 Fr~ctlons o~ Fluld Cokor N~phth- in th~ C8 ~ange
Wei~ht % Co~QsLtion bv GC
Designation of Fraction l-Octene R~ch n-Oct~ne Ri~h
Fraction No. 11 12
Quantity, g 2072 1034
~oiling Point Range, ~F 245-254 254-262
C 118-123 123-128
OthersOl~flns Olefins Others
X ~ X X
Toluene 4.3 1.3
2-Methylheptene-1 6.3 3.2
Oceene-l 18.5 10.3
trans-Octena-4 1.0 0.6
trans-Octen~-3 2.1 1.3
n-Octana19.9 16.3
trans-Octene-2 3.6 2.8
cis-Octene-2 1.6 1.8
Ethylbsnz~ne 0.6 6.1
m-Xylene 0.1 5.1
p-Xylene 1.8
o-Xylene 0.8
Nonena - 1
Su~ of Identi~ied Compounds 24.9 33.1 20.1 31.4
-56- ~ 2~73
Table IX
Re~ Co~pon~nts oi the CB Bayto~n Flc~icoker Naphtha Feeds
Concentration of Components, %
Broad Narrow
__Component Identificationa _ _ Bp. Bp.
Boi~in~ Po~lt 110-135C 117-124C
_ _Name C _~E~ 2~Q-27$F 243-255F
l-n-Heptene 94 201 0.14
n-Heptane 98 208 0.32
Methylcyclohexane 101 214 0.57
3-Methylcyclohexeneb~C 104 219 0.3~ 0.15
Toluened 111 232 6.39 O.lS
4-Methyl-l-Heptene 113 235 2.47 0.49
2-Methylheptane 117 243 2.94 3.67
6-Methyl-l-Hepteneb 1.38 1.53
1,3-cis-Dimethylcyclohexaneb 120 248 2.02 3.31
2-Methyl-l-Heptenee 118 244 4.08 7.ô2
l-n-Octene 121 250 11.07 28.12
4-Octene 0.97 2.62
3-Octene 123 253 0.98 3.09
n-Octane 126 259 9.98 20.01
trans-2-Octene 125 257 1.82 2.86
Dimethylhexadieneb 1.78 4.28
cis-2-Octene 126 259 1.25 1.76
Dimethylcyclohexeneb 1.72 1.22
Ethylbenzene 136 277 3.2.2 0.09
2,6-Dimethyl-l-Hepteneb 2.18
m,p-Xylenes 138 280 6.03
o-Xylane 144 291 1.02
l-n-Nonene 0.57
n-Nonane 151 304 0.23
,
a)Identification based on GC, GC~MS and boLling polnt correlations.
b)The identification ls tentative.
C)l-Methyl-cyclohexene is also indicated.
d)2,4-Dimethyl-l-hexene is also indicated.
e)3 Methyl-l-heptene is also indicated.
73
-57-
octenes than the broad fraction (36.45 versus 16.09). Most significantly,
the percentage of l-n-octene in the narrow cut i5 28.12X while it is only
11.07~ in the broad cut.
The broad cut naphtha is richer in branched olefins including C7
and Cg compounds of an open chain and branched character. In consrast to
the narrow fraction, the broad cut had significant amounts of aromatic
compounds: 6.39Z toluene, 3.22X ethylbenzene, 7.05X xylenes.
In the broad cut naphtha the pre~ence in small aMounts of a high
number of monobranched olefins was indicated. The largest of these
2-methyl-l heptene is present in both the broad and narrow cuts in
concentrations of 4.08 and 7.82X, respectively. There are also other
methyl branched, mainly terminal, msthylheptenes present. However, the
exact structures of these compounds are not known with certainty. In
addition, there are branched, cyclic ole~ins present, particularly
methylcyclohexene and dimethycyclohexene.
Fi~ure 4 illustrates the composition of the narro~ cut C8
Flexicoker naphtha. It is noted that most of the olefin components are
linear or monobranched compounds. The cyclic olefins are largely excluded
from this fractLon.
The sulfur content of the broad C8 fraction is lX while that of
the narrow C8 fraction is 0.2X. The concentration of the main sulfur
containing compounds, i.e. methylthiophenes and dimethylthiophenes is
drastically cut in the narrow fraction. The distribution of the sulfur
compounds in the two fractions is indicated by the sulfur specific gas
chromato~rams of Flgu~e S. Althou~h the sulfur response of the detector is
close to quadratic rather than being linear, the figure shows that the
thiophenic sulfur was largely removed by fractionation from the narrow
fraction.
~ xtraction of the narrow cut with 30X KOH solution in methanol
containing 2X water reculted in a fuxther reduction of the sulfur content.
It was specifically shown by sulfur GC that the pentanethiol co~ponent was
completely remo~ed.
Fi~u~e 6 illustrates the composition of the Clo naphtha fraction.
As it is indicated, besides the main l-n-decene component several of the
linear decenes and 2-methyl nonene-l were identified. It was also shown
that indene, a reactive, aromatic cycloolefin, is also present in this
fraction. The main aromatic hydrocarbon components are trimethylbenzenes
and indane.
~l~9'~ 3
-58-
The naphtha and its distillate fractions were also analyzed for
sulfur and nitrogen compounds. Table X shows the carbon, hydrogen
mercaptan and total sulfur plus total nitrogen contents.
The ~ercaptan content of the C8 and higher fractions is
surprisingly low compared to the hlgh total sulfur content when determined
by mercaptan tieration by silver nitrate. It is believed that this is in
part due to the facile cooxidation of mercaptans and activated olefins.
The total sulfur content generally increased with the carbon number of the
di tillates from the C6 fraction upward. Assuming the sulfur compounds of
the various fractions had two fewer carbons per molecule than the
corresponding hydrocarbon compounds, it was calculated that in the Cs to
C12 range the approximate percentage of sulfur compounds has increased from
0.4 to 7~. In contrast to sulfur, the total nitrogen content of the C4 to
C12 fractions was generally less than 160 ppm.
The mercaptan content of the two combined C8 fractions ~shown in
Table X) was also determined by difference. At first, the tatal sulfur was
determined by sulfur specific GC. Thsn the mercaptans ~ere removed by
prscipitating them as silver mercaptldes. Based on such an analysis, the
following ppm concentrations were obtained for the various sulfur compounds
in the order of their retention times: 2 methyl- and 3-methyl thiophenes,
962 and 612; n-pentane and n-hexanethiols, 105 and 78; C6 branched
thioether, 200; l-hexanethiol, 384; 2,5-, 2,4-, 2,3 , 3,4-dimethylthio-
phenes, 1245, 945, 728, 289 unknown sulfur compounds, 11. Thus, this
analysis provided a total suifur content of 5560 ppm and a mercaptan
content of 568. The main group of sulfur compounds were thiophenes in a
concentration of 3781 ppm.
Cok~ Ga~ Oi~
Similar characterizations were performed on a light coker gas oil
produced by the same Fluid-coking unit from which the coker naphtha was
taken.
Fi~ure 7 shows the capillAry GC of the light gas oil in the Cg to
C16 range. About 90X of the components are in the Clo to Cls carbon range.
The Cll eO C13 components are pareicularly large. Obviously, there is some
overlap between this composition and that of the broad cut naphtha.
As it is indicated by the symbols of the figure, the ~ain
component~ are the l-n-olefins and the n-paraffins. In general, the
~2~ f3
-- 59 --
~ l 1~ 0 N O
'`'~` I"' ~ o ~ u o .e
~' ~ Q~ o 0~
I~ 'o ~ - ~ ~
o ~oo I ~ ~o
.; ~ U C
~
~o I ~ o ~ oo ~ ~ o ~u
U o ~o U ~ ~ D v ~
~ CO ~ O O O V ~
~ ~ ~ 70 C~ ~ ~U
_ _ e ~
_ e I~ E ~ v
73
-60-
concentrations of the l-n-olefLns are greater than those of the
corresponding paraffins. The l-n-olefins to n-paraffin ratio is apparently
maintained with increasing carbon numbers.
The light gas oil fraction was fractionally distilled to produce
narrow cut distillates of a particular carbon number. The fractions
obtained were then an~lyzed by GC. The data are summarized in Tables XI
and XII. The tables show the a~ounts of the individual cuts, the
percentage concentration of the main paraffln and olefin components and
separately list tha heart cuts of particularly high content of a l-n-olefin
of a certain carbon number. These heart cuts were utllized in subsequent
hydroformylation experiments.
The data of the tables show that 54X ~44,439 g) of the
distillates were in the C12 to Cls olefln range. It is noted that the
percentage values for the l-n-olefin and n-paraffin components are
relative. Absolute values could not be deter~ined. Wieh the increasing
molecular weight of these fractions, the number of isomers is sharply
increasing. Thus, the GC resolution is decreased and absolute accuracy
decreased. Nevertheless, it appears at least in a qualitative sense that
the l-n-olefin concentrations are maintained.
The Cg to C16 gas oil and selected distillate fractions were also
studied by proton NMR. The results are illustrated by the spectrum of
Figure 8 which shows the aromatic, olafinic and paxaffinic hydrogens. A
quantitative analysis of the spectru~ showed that this gas oLl is highly
olefinic with a strong aliphatic character in that 88.2X of the hydrogens
in the ~ixture are on satursted carbons, 6.2X on olefinically unsaturated
carbons and only 5.6Z on aromatic rings. Overall, the gas oil has a
significantly hlgher percentage of linear olefins than does the coker
naphtha ag is shown by the following tabulation:
73
-- 61 --
, ~2
0 cl c~ v
C0
0~ O ~ CO V`
L C C _ _ _ _
-r C L
8~ E co O~ _ --
= l_~Z
E c ,~ ", ~ o
>~
~ ~o O
~ ~ CO r` , ,_
_ _ ~7 o o ~ C
cn C~
c
--~1 '`
c _ ~
C ~ C 0 ~ _ ~ o
X _ ~ 0 o o o o o o o o o oO oO ,o o ,_
~1 ~~ ~ c~
U C
g c cl~
c ~ ~ _~ c~ _ o c, ~n ~ ~ ~ ~o _
_ O 11 ~1 0 ~ I ~ ~I 'I
~ I
1~~ O ~ O ~0 ~ ~ ~ r~
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~_
o o
-- -- ~ O C~ _ ~ ~ _ ~ ~ ~.~
o E ~,¦ o ~ ~
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~1: _ O O O O O O O C~
C ~ V ~ ~ .~7 ~ U- ,~ ,~ ~ ,~
_ C_ ~0 ~ ~ ~ ~ ~ ~ ~ ~ ~ I
~ ~ ~ 1~ ~ ~ 0 ~7 ~ er U7 ~O r~ ~ ~`7
E 0 u7 0 c~ r~
c ~ ~ ~ ~ 2 ~
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,. .
~2Q~$`7 ;3
-- 62 --
¦ e~ N 00 N
L _ _ _ N
C
V~ ~
C ~ ~ O~ O'
_ _ _ N N
I O
I E
~ 1 Z N ~1 ~ ~s)
0
O o C~ ~, O
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., , ~ , ~--¦ , e, o ~o
o c
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X O ~ ~ r _ ~ _
~J ~ C ~ ~ _ (J N N ~ C~ ~n N 1~ N ~ V:~ ~) N ~ I~
~0 ~ _ ~ O '~:t O ~O N D ~ N N ~ N ~ ~) N N
1~ 0 ~ ~OO O o o o ~ o o o o o o o o o o o o o o o
1~ E _ _ _
~el c ~ ~ Il ~ ~ co o ~1 o _ N N 1~ O ~0 Ot Ln ~ O N O
._ C ~ U~ N t~ IrJ O ~ 1~1 ~ ) N ~) O t~ _ ~ O U- ~> ~
._ ~. C ~ _ N N _ _ N ~ ~ _ N ~ N _
Vl I ~J N N N N N N ~) ~ ) ~ ~ er ~ G ~r ~ ~ 3
C~ __
U~
_I C ~ O o ~0 ~ ~o ~D o r~ ~ ~D ~r O ~ ~ _ O~ Co O = _ ~ ~
~ V ~ ¦ ~ _ ~ æ _ r~ _ ~ N ~) N ~ N N N r~ _ N ~
3 q_ _ ~1 0 N ~ _ CO N 1~ _ N O ~ ) ~ O r~
O 1~ ~ ~ 1~ ~1 ~D N C~ O CO ~D 1~ a~ O-- 1~ t~ N ~D C0 1~ Ol 0') ~O
~ ~1 ~O~_~N~~tO~Iq_~7~)NO~_ CO
L._ E ~ o ~ N N O ~ ~ N O _ ~ O 14 ) r~ ~ r~ U-
o V~l N_~N~er,_NN~~ererln~err~~
: ~ ~ C ~ ~ N N N N ~ N N N N r~J N N N ~ N ~.
c O ~---- N N ~'I ~ ~ ~1 . ~ ~ N N ~ ~ ~ er N Næ N er N _
~ V~ ~ ~
_ ,_ _ ~ In r~ ~ N ~ N ~ a~ n ~ N Ln ~ ~ L~ n N
3 v~ V _ _ N ~ r r C er ~ ~ u~ ~ ~ r~ ~ o7 _
E ~3 u N ~ n ~n N n N r> a~ ~ in ~ ~ In . In ~ U~ r~
~ o o _ _ N N r ~ ~r ~r er U~ e e`r ~` ct) ~ ~ u7 ~ u~ -- ~
c v a
LL~ ~ ~ X X X ~ = X X X --X X X X _ ~ X X
O r~ ~ x x ~e X x X X X X x x x 3 xx
t73
-63-
Mole X Unsaturation
VinylicGas OilNaphtha*
Type SegmentC10-C15 C4-C12
_
I -CH-CH2 42 37
II -CH~CH- 22 20
III -C CH2 16 17
IV -C-CH- 7 12
Con~. Diolefin -C-C-C-C- 14 14
~From Table IV.
Type I olefins represent about 42X of the total olefin content in
the gas oil and about 37X in the naphtha. Most of thç Type L olefins are
l-n-olefins which do not have branching anywhere on their hydrocarbon
chain. Tha mass spectrometry data indicated that branching is mostly by
methyl groups on the vinylic doubla bonds.
Selected distillate cuts of the light gas oil were also analyzed
by NMR in a similar manner. The distribution of their vinylic hydrogens
was particularly studied to determine the relative amounts of the various
types of olefins present. The results are summarized in T~ç XIII.
The data of Table XIII show that the relatlve olefin percentages
of the distillete cuts vary. However, the percentages of tha Type
olefins, including the dssired l-n-olefins, is generally more than a third
of the total. The Type I and II olefins combined, which includes all che
linear olefins represent more than 55X of the total. The vinylically
branched olefins are present in le-~s than 35X~amounts. The percentages of
the con~ugated diolefins are included in ehe table since they are converted
to ~onoolefins during hydroformylation. However, the diene structures are
uncertain and as such of approximata ~alues.
~ Table XIII also shows the distribueion of olefin types in the
case~of four narrow cut Cl2 distilIate fractions. As expected, varying
a~ounts of the diffcrent types of olefins of different boiling points were
iound to be present. Thus, the proportion of the Type I olefins chan~ed
from 45.5 to 33.8X.
~2~ 73
-- 64 --
4',
C~J N
U) ~ ~:t ~) N r
C~ U ~ O O
~1 _ N I N O
et ~ I et C~
~ ~ U
O C~J U . . . O~
._ ~ _ ~ L171~ N
er (D
v~ ~1 ~n ,
a~ ''
` I u7 u~l ` ~' ~
~~ ~ ~ 1
at U~ l
^
O If) O ~ N
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J O L~
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In O _I In U~ . . = o
,~,~ ~ r~O ~ O
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c~.l I O O ~I~
a~_ ~ ON O C~J ~ ~ _
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~ ~o ~ ~ ~~ ~
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-65- ~2~73
The percentages of various typ8s of olefinic hydrogens, are shown
by Table XIV. From the hydrogen distributions, the weight percentages of
the various types of olefins were estimated. As it is shown by Table XII,
the estimate of total olefins including dienss is between 50.4 and 61.7X.
It is noted that the 61.7X value is for the C16 fraction which was
distilled with decomposit$on. As a result of cracking this fraction
contained not only C16 but lower molecular weight olefins as w811. In the
case of the C12 range, four narrow cut fractions were analyzed to determine
changes in the proportion of different types of compounds. Only moderate
changes were found in total olefiD concentration (45.5 to 54.4X).
To illustrate the detailed composition of ths present gas oil
feeds, more detailed data are provided on a narrow Cl2 fraction on the
basis of GC/MS analyses. Such a cut cannot be separated on a nonpolar
(boilin& point) methylsilicone GC column. However, it was found that a
highly polar type CP Sil 88 column (with a cyanopropylated silicone
stationary phase) separated the various types of components according to
their polarity. [This column is particularly suitable for the analysis of
high boiling fractions since it has a high use temperature limit (about
275C)]. These components could then be largely identified via GC/MS
studies. Two capillary GC traces with the groups of components identified
are shown by Fi&uxe 9.
The effluent of the above polar capillary column was splLt and
led to a flame ionization and a sulfur specific detector. The chromato~ram
of the flame ionization detector shows tha distribution of the organic
compounds according to polarity in the lower part of the Figure. The upper
chromato~ra~ produced by the sulfur specific detector shows the elution of
the sulfur compounds in the order of their polarity.
The lo~er GC of Figure 9 shows good separation of ehe aliphatic,
monoaromatic and diaromatic hydrocarbon components of the Cl2 fraction.
With the help of GC/MS the aliphatic components could be broken down eo
paraffins, olefins plus diolefins. Their percentages were 18.6 and 50.5X,
respectively. The monoaromatics included alkylbenzenes, naphthenobenzenes
and trace ~mounts of alkylthiophenes. The total a~ount of monoaromatics
was 28.2X. The main diaromatic compounds were indene, nephthalene and
benzothiophen~. Surprisingly, trace amounts of trimethyl phenols were also
found.
The upper, sulfur specific GC of Figure 6 shows th~t essentlally
all ehe sulfur compounds of che C12 fraction were aroma~ic. The ma~ority
~4~ ~
-- 66 --
~ O e~ ~ ~ ~ I_ ~ ~ o~ _
v ~ r~ ~ ~ o 1~ et O
~o
~ ~ o o d- ~ ~ ~
' ~'1
o~ cn cn ~ e~ a~ co ~ o _
a~
C:l
V~
~ ~ C O CO 0 1~ 0~ 1~ It~ _ r~ 0 ~ i~
~ I co ~ O 1~ O cr~
~ 8 ~ _. ~ ol N CO O Cl~ O ~ O~ O
,Co I _ _ _ __
O ~ N ~ Q
L
vl 4 e:t O et :) O 1~ r~ N O ~`J
o OU C ~r ~r OD _ e~ n CS ~) N U~ _-
.v U L ~ U~ 0 a~ ~ CO O 0 ~ cr~ O
~ L j~ 2_ 1~ CO CO Ct) 00 1:~ O~ 00 CO CO C~t ~
X O ~ ~ --~ C ¦ N 0~ ~) N N ~)
3~ ~, ~ ,,. o ',1 -
O N Ir) Ir~ ~D Cl~ ~r ~ ~ C~ ':t
0 ~ C~J ~7 _ C~J ~ ~t ~ ~ ~
~_ O o O O O o o o o o o
~:L L
~ 3~ a~ -- ~ ~ a) ~`J ~ oo u:~
0~11 I--_ .- O O O O O O O O O O
' dl _ _ o ~ ~ o o Cll ~1 a~ ~ 0 ~
L T O -- -- O _ O O O O O O O
V~ .Y
a ~3 ~o _ ~ co ~ ~ ~o ~ J ~ 1~
e ~ _, r~ r_ _ ~ I~ ~ ~ a~ Ln o
Vl a ~ ~ ~ c~
L LL
~ 0:
C ~ ~ ~ O U> o o o o
.-- ~ E ~ ~C ~ O _ Lrl C~ C~
e O O ~ ~ ~ _ ~ co
~ U7 u~ o ~ ~ ~ _ O O c~J ~
o _ _ o
c~
~ O L
_ ~L n
~ ~ E
~2~ 3
-67-
wers alkyl thiophenes. Benzothiophene was also present in significant
amounts.
A similar analysis of the C14 fraction showed an even better
separation of the components according to their polarity. In this case the
distribution of the aliphatic components was similar but the ma~or aromatic
componsnts were dinuclear: methylnaphthalenes and methylbenzothiophenes.
The dlstillate fractions of light gas oil were also analyzed for
elemental composition, particularly for sulfur and nitrogen compounds and
mercaptans. The data obtained are summarized in Table XV.
The percantages of carbon and hydrogen were rather well
maintained with increasing molecular weights. They indicate that the
aliphatic character of the gas oil was f~irly maintained. The total sulfur
contant remained at about lX in the Cg to C12 range. Thereafter, thers was
a rapid increase of sulfur up to 2.82X in the Cl6 fraction. It is noted
that ehere was increas~ng decomposition during the distillatLon of these
fractions. When the C16 fraction was red~stilled a broad molecular weight
range of l-n-olefins was found in the distillates. This suggests the
breakdown of nonvolatile aliphatic sulfur compounds to generate olefins and
mercaptans.
The total nitrogen contents of the distillates were more than an
order less than that of the total sulfur. The mercaptan content is
generally even lower. However, both the nltrogen and mercaptan contents
rose sharply in the Cls and C16 fractions.
Exp~rlmental proç~e~ures
Except as otherwise specified in the examples, the processes
found in those examples were carried out using the following experimental
procedure~.
Low ~d 4Odlum P~es~urs Hy~o~o~myla-tio~
The low and medium pressure hydroformylation experiments employed
300 ml and 150 ~1 ste~l autocla~es, resp~ctively. Both autoclaves ~ere
equipped with impeller type stirrers operating at 1500 rpm. The co~al
liquid feed was 100 g and 50 g, respectively.
In a standard hydroformylation experiment, 80Z of the feed was
placed into the autoclave and deoxygenated with repeated pressuriæation
with nitrogen. The solution, now at atmospheric nitrogen pressure, was
then seal-d and pressured with 1:1 H2/C0 to 50~ of the reaction pressure.
-` ~2~7~
-- 68 --
u~ ~n r~ c~ c
U~ 1~ ~r~ ~I OD O _ N ~
J O1~ ~ --
C~.~
u~
U7 O C~J U~ D O O ~ ~ g
~ u7 U~ d ~
::~ ,o
e~ u~ ~ ~ ~ O O c~
d- ~r OD= ~ -- ~ O
U~ ~o ,C _,
C~ ~ ~ ~ ~ O 0 1
~ ~t ~ CO~
-- 1~ ~1 _ co ~ o o (O ~ -~
~
U~ -- C~l
~ o ~
a- ~1~o ~ ~ _ v
U- o~
~ ~ n= ~~ o o e~ ~ ~c
~ ~I _ _a~ N _ ,~ o ~
J O _ ¦ . q O
~1 - ~ _ _ W C ~a~
t~
O æ _ N _ _ O 11'~
._ ~ ~ ~ _ O ~ n~ L
~ N _ ~O U _
~o co ~ o o o co o
~tl C~
~L~ O ~ . ~ ~ ~
_ ~ ~N O o o ~ O O
tJ-o
s_~ a~ c~--~ o o o _ _
N ~ U~ C
O
~ _ O
V ~
8 , W' , ~
_ ~~ o V~ E ~ ~D
v~ 2 ~1 ~ 3 ~ O
O ~_ ~O 0~ ~ ' ~ ~_
.~ ~ ~ " ' ~
73
-69-
The catalyst precursors, l.e., rhodium carbonyl acetylacetonate,
dicobalt tstracarbonyl or dicobalt octacarbonyl plus the appropriate
phosphorus ligand, were dissolved in 20~ of the feed and placed into a
pressure vessel connected to the initial H2/~0 feed line and the autoclave.
The autoclave was then heated to the reaction temperature.
Thereafter the catalyst solution, about 40 or 80 ml dependent on the volume
of the autoclave, was pressured into the autoclave by the inltial feed gas
and ths d2sirsd reaction pressure was established without stlrring.
Thereafter, a switch wa~ made to the feed Bas pressure vessel of
known volume which contained an appropriate mixture of H2/C0 at higher
initial pressure. Then the stirring of the reactlon mixture started. This
resulted in efficiant contact of the gaseous H2/CO with the liquid reaction
mixture. As ths reaction proceeded, the reactor pressure dropped due to
the H2/CO reactant gas consu~ption. In r~sponse, feed gas was
automatically p~ovided as needed to maintain the pressure in the reactor.
The feed gas had an appropriately hi~h H2/C0 ratio above ons so as to
provide H2 not only for the main hydroformylation reaction but the
hydro~enation side reactions as well.
The progreqs of the hydrofor~ylation was followed on the basis of
the C0 and H2 consumed. The latter was calculated on the basis of the
pressure drop in the l liter H2/C0 cylinder. Reactant conversion was
estimated by plotting the C0 consumption against the reaction time. In
soma cases, reaction rates were also estimated in spite of the complexity
of the feads and were expressed ns ~he fraction of the theoretical H2/C0
consumed per minute. Reaction rate constants were normalized for lM
transition metal concentration, assuming a first order rate dependence on
the metal concsntration.
When the reaction was discontinued, the H2/C0 valve was shut and
the autoclave immediately cooled by water The synthesis gas in the head
space of the autoclave was analyzed to determine the H2 to C0 ratio. After
the release of excess H~/C0, the residual liqu~d reaction mixture was also
analyzed to determine conversion selactivity. For these analyses a
capillary gas chromatograph with a 50 m fused silica colu~n was used.
Reactant conversions an~ product selectivities were also
estimated on the basis of ths gas chromatograms of the reaction mixture.
The conversion of l-n-olefins could be usually determined on the basis of
the reduction o~ their peak intensities compared to those of the inert
paxaffins. These conversions could be correlated with the formation of che
~26~4~ 3
-70-
correspondin~ n-aldehyde and 2-methyl branched aldehyde products. When
comparing hydrocarbon slgnal intensities with those of aldehydes and
alcohols, a correction factor of 0.7 was assumed for the oxygenated
compounds.
When the ma~or products of the present hydroformylation process
were alcohols, e.g. in cobalt-phosphine catalyzed reactions, samples of the
reaction mixtures were silylated prior to GC analyses. An excess of
N-methyl-O-trimethylsilyl-trifluoroacetamide wa~ ussd to convert the
alcohol! to trimethylsilyl derivatives:
NCH3
RCH20H CF3COSi(CH3)3 RCH20Si(CH3)3
These derivatives of increased retention time are easier to
chromatographically resolve and determine than their alcohol precursors.
High ~
In the high pressure hydroformylation experLments, a 1 liter and
a 1 gallon stirred autoclave were used. In these experiments, the amounts
of synthesis gas consumed were not monitored quantitatively. However, the
liquid reaction mixture was sa~pled, usually after 10, 30, 120 and 180
minutes, and analyzed to determine ol~fin conversions and product
selectivities, Also, the relative reaction rates were estimated by
periodically shutting off the synthesis ~as reactant supply and determining
the rate of pressure drop per minute in the reactor.
In the one liter autoclave, the thermally cracked distillate was
usually dilut~d with an equal amount of n-hexane, to provide a
hydroformylation feed for standard experiments. However, about 20X of the
diluent was employed to dissolve the catalyst, usually dicobalt
octacarbonyl. In the one gallon autoclave, the cracked distillate was
placed as such without solvent. The catalyst was usually dissolved in
toluene solvent a~ounting to about 5X of the distillate reactant.
The high pressure experiments were carried out in a manner
basically similar to those employ~d in the low pressure experiments~. The
distillate reactant was typically preheated to the reaction temperaeure
with stirr$ng under an initial H2/CO pressure equally about 3/4 of the
final rsaction presiure. The catalyst solution was then pressured into
-71- ~2~C~3
stirred mixture using the in~tial H2/C0 at reaction pressure and the
pressure waq ma~ntained with additional, ~2/C0 feed gas as the reaction
proceeded. During the periodical sampling of the liquid mixture,
significant losses of H2/C0 occurred, thus the H2/C0 ratio thereafter was
that of the feed gas rather than the initial gas. At the completion of the
experiment tha reaction mixture was rapidly cooled under H2/C0 pressure and
discharged when cold.
For a more detalled study of some of the products of high
pressure cobalt hydroformylation, particularly those prepared in the one
gallon reactor, the reaction mixtures were fractionally distilled. To
avoid decomposition, the cobalt was removed as cobalt acetate by hot
aqueous acetic acid plus air treatment. In a typical procedure, a 200X
excess of acetic acid is used aa an about 6X aqueous solution. As a
reaction vessel a three necked glass vessel equipped with a mechanical
stirrer, sintered glass bubbler, reflux condenser and a bottom valve for
liquid takeoff, was used.
The stirred mixture of the cobalt hydroformylation reaction
mixture and the theoretical amount of aqueous acetic acid was heated to
reflux temparature while introducing air. Thereafter, stirring and
aeration were continusd for 20 minutes while refluxing. As indicated by
the lightening of the color of the reAction mixture, cobalt conversion was
usuall~ substantially complete by the tima refluxing started. The mixture
was then allowad to cool and settle. Theraafter, the bottom pink aqueous
phase was separated. The organic phase then was treated the same way
again. After ths qacond acid wash, tha mixture was filtered if there were
any solids present. Thereaftar, two washed with distilled water followed.
Lack of color of the aqueous washings indicated a complete prior removal of
cobalt.
The cobalt free orgsnic phase was fractionally distilled in vacuo
using a l to 2 ft. long, glass beads packed column or an Oldershaw column
with 22 theore~ical plates. The composition of distillate fractions was
monitored by capillary GC to halp appropriate fractionation. Many of the
fractions were also analyzed by a sulfur specific GC detector. Selected
fractions were also analy~ed by a combined gas chromatography/~ass
spectrometry ~GC/MS).
.
125~73
-72-
~dsh~d~ H~dro~en~on,~o Produc~ ALcoh~ls
Typically, the aldehyde hydrogenation~ were carried out at 3000
p~i (206 atm) pressure in a 1 gallon (about 3.8 liter) rocking aucoclave
using about 1800 g reactant. The aldehyde rsactant was used as such or in
a hydrocarbon solutlon. Five per cent by weight of water was added to the
aldehyde to inhibit the formation of dimesic and trimeric by-products
durin~ hydrogenation.
A~ a preferred hydrogenation catalyst, cobalt sulfide
molybdenum sulfide on alu~ina was used. Alternatively, molybdenum sulfide
on carbon support was employed. Ten percent by weight of catalyst was
used. In the presencs of the CoS/MoS bascd catalyst, the hydrogenations
could be carried at lower temperatureQ in tha ran8e of 130 to 170C. The
low temperatures are important for avoidin~ the undssired conversion of
aldehydes to paraffins and sulfur transfer from the metal sulfides co form
sulfur containing by-products. In the presence of molybdenum sulfide the
hydrogsnations were carried oue a~ 232C (450F). At this temperature,
paraffln formation was significant (10 to 30~).
The hydrogenations were substantially compleeed in five hours.
However, they were gen~rally continued for a total period of 20 to 24 hours
to assure a completa conversion of ths aldehydes. Ihe alcohol products
were usually colorless or very light in color. They were characterized by
GC and GC/MS and fractionally distilled in vacuo to provide colorless
liquids. Som~ of the alcohols were washed with 10~ aqueous sodium
hydroxide to remove hydrogen sulfide and other potential acidic impurities.
~ Q~ Pr~ Llbob3a~Q~ ation of C4-C12Naphtha Frace~,,o~s
i~ tbo ~ u~Lsa~_~b:~phln~-ahQdium Com~le~es ~xamplc3 1-12~
Tho previoucly described C4 to C12 Fluid-coker naphtha and its
di3tillate fractions were hydroformylated without prior treating in th~
pre~ence of rhodium co~plexes of various phosphines under varying low
pressure conditions.
The rhodium catalyse systam~ employed and the reaction conditions
used are u~arized togethar with som2 r~ults for orientation in Table
~21- In general, in the presence of sufficient a~ounts of
phosphine-rhodium cstalyst complexes, rapLd and selective hydroformylation
occurs ae low pressure. Very little hydroesnation occurs. CC analysis
provideq a quantitative measure of tha two ~a~or aldehyde produces and a
more qualitative estimate of the toeal a1dehyde products. At low pressure,
~Z~ 3
- 73 -
~7 cl
o
,~ ,~ E ~ ~ o ~oO o O co o ~D o
ccl c~ _~ ~ ~ I ~ r~ o~ ~ ~ Q
C O
_ ~ V
_ E ._
n l O C 2r~ 00 ~ o _~ o ~ a a~
c~lo ~ c~ _ _ o o
lel ~: O C~ l r~ ~ C~l C`J cr~ N C~J ~ I
~ CJ
al ~ ~7 ~ n c
o a~ ~ n o
~:L O ~ ._ I~ CO C~ D O aJ
1~ ~ C~ ~ ~
~:3 rn O C
,9, L. 1~ ~ o a) la _
~2~ o v~ ~ _ _ a~ o 1-- o o c~
Ecc ~ o ~ __ __ _ __ ~ c c
C~~E ~ ~ ~ "
tU~ 3 t_ --
~ c~ ~I ~ ~ ~ ~7~c~ ~ ~oLI~ .~
C ¦ t _ N _ N C~J C~ 0 _ o _ O
H ~: O . U'l 0~:) Ln ~ 1~. LO I ~ C ~ e ..... ~c O~ 0OO ~ O _.~0 _ c,
~ c ~_ . ... . . . ... , ._ ~
OJ J~ T Ll_ _ _ _ ~ _ ~ O _ Ir~ ') _ r~ O C
,1 o E c o o o oN O O ~1 o O o
CL C 1~ O ~O ~ r.~l ~O _~O ~ ~O
O U
V~ ._
O,J r_ n OO O O O O O O OO O O
O ~_ t_ ~ o o 1~7 0 0 0 00 01~ Ln O O
Q ----~-- ------ ~
~ ~ C
'~ ~ C C
E~ I O O O O O o O o o o Ln o
~ ~ ~ c~ o ~ co o ~ ~ o
O ~ o -- -------- E s '- s
G c~ c I o
c~ ~ a~ c~. c~ ~ ~ ~ ~ ~ _
'-- C t-- c~ ~ t~c~ ~ c~. ~~ I--
el Jl ~ ~ ~ o c c ~
--~ _.1 ~ X T I oT ~-- :~ TI Q L7 ~ ~ ~ Q
~ ~ ~ .) ~ S ~_ 5) 0 0 ~t)
. C ~ ~ Q `_ L ~J
o ~ . e ~ U- S~
~n r,~ ~ ~ S ~~ ~ e~ ~ o
t_ O~ _ ___ _ _ O oo_
C~ O O O O O O O O r O_ _ O ~ C C
~:: O O
~IJ
C I Q
~y ~ O ~ ~~ ~ ~ C o o
C . ~
q~ ~o o ~ ~ ~ ~ o
a~ ~ z _- o o o 1--1~ 1~ o o o o o
-- --.~__ O O
L-I ~ CS 1-
~ Z~ 3
-74-
the total aldehyda products could be more reliably estlmated, on the basis
of the H2/C0 consumed, by comparing the found values with the amounts
calculated for converting the l-n-olefin component. Based on the initial
rates of H2/C0 consumption (0-1 minute) the hydroformylation rates of t'ne
most reacti~e l-n-olefin components were also compared in the presence of
different catalyst complexes.
Comparative l-n-decene hydroformylation experiments with the Clo
naphtha fraction as a feed showed that the activity and selectivity of
rhodium complex catalysts could be controlled by the chemical structure and
excess concentration of the phosphine ligand added, as it will be discussed
in the individual examples.
Ex~mple 1
~ydroformyl~tion of ~ C4-C12 Naphth~ ~ith
a Tr~butyl Phosphlno Rhodlu~ Complo~
A broad naphtha cut previousiy dascribed was hydroformylated in
the presence of a catalyst system containing 10 ~M rhodium, employed as
dlcarbonyl acetylacetonate, and 0.14~ tri-n-butyl phosphine. The reaction
was run at 180 under 1000 psi (6900 kPa) pressure for 40 minutes. The
inltial H2/C0 ratio was 1, the H2/C0 feed ratio employed during the run
1.22 and the final head space ratio 1.95. The increase of the H2/C0 ratio
during the run indicated that very littl0 hydrogenaeion side reaction
occurred.
The final roaction mixture was analyzed by GC. The chromatogram
showed no l-n-olefin components, indicating their complete conversion. The
main products were the n-aldehydes. Among the minor aldehyde products,
thos~ of the 2-methyl substituted aldehydes were readily recognizable.
i~L~YII shows the signal intensities of these two types of aldehyde
products and those of the n-paraff~n components. The paraffin components
repres~nt ~ultiple internal 3tandards which were present in the starting
reactants in amount~ comparable to the l-n-olefin reactants of
corresponding carbon nu~bers. The data of the table qualitatively show
that the convsrsion of the l-n-olefins resulted in the formation of the
expectsd normal aldehyde and 2-methyl branched aldehyde products:
CnH2n+lcH-cH2 /i2~ CnH2n~1CH2CH2CHO + CnH2n~lCHCHO
CH3
~2~
-75-
~able XVI~
Ma~or Aldahyte Product~ snt n-Paraffin Components
of ~luid Coker Naph~h-
Alkyl GC Sign~l ~ntensltv. X
Carbon Normal2-Methyl Normal
No, B~ Aldehyde ~3E~ LB
1.104 0.926 0.798
6 1.837 1.468
7 1.796 2.927
8 2.259 1.586 3.064
g 2.0~7 1.350 2.208
2.182 1.115 2.043
ll 1.~23 0.715 1.409
12 0.514 0.239 0.393
5-12 13.162 14.310
The n/i ratlo of these linear versus branched aldehydes is about
2. Using the present cataly3t system and conditlon~, this ratio is in the
ran~e oi n/i values obtained on the hydroformylation of pure l-n-olefins
and Type I olefins, in general. As eh~ l-n-olefins were converted, the
reaction rate d&creased and the reaction was discontinued. Thus, the
results of this example indicate that the l-n-olefin components of the
diqtillate ieed can be selectively hydrofor~ylated in the presence of
phosphine rhodium complex based catalysts.
E~ample 2
Hyd~ofor~ylation of Clo N~phth~ ~ith a
Tri-n-octyl Phosphine Rhodlu~ Co~pls~ at 1000 p~i
The pr~viously described Clo fraction of the Fluid coker-naphtha
was hydroformylated at 180C under 1000 psi, using the low pressure
procadure. The catalyst system was derivad from 2mM rhodium dicarbonyl
acetylacetonate and 0.14M tri-n-octyl phosphine. The reaction period was
60 minutes. The ratio of the initial H2/C0 wa~ 1; the H2/C0 feed was of 51
to 49 ratio. The final H2/C0 ratio of the head space was 52 to 48,
indicating a virtual absence oi hydrogenation.~
The reactio~ was very fast during the initial period of about 5
minute~, then the reaction became slower and slower. Apparently, the
l-n-decene component of the feed was rapidly hydroformylated while the
isomQriC Type II and Typs III deoenea ~ere more sluggish to react.
-76- ~2~ 7~
A GC analysis of the final reaction mixture showed that
l-n-decene was absent. Apparently, it reacted to form n-undecanal and
2-methyl decanal. The latter compounds constituted about 69X of the total
aldehydes fsr~ed. The ratio of the normal to the iso aldehyde produced ~as
1.88.
On the basis of the origlnal conceneration of l-n-decene in the
feed, the theoretical amount of Cll aldehydes was calculated. The total
aldehydes were 171X of the amount which could have been derived from
l-n-decene. Apparently ma~or amounts of the Type II decens components of
the feed were also hydroformylated On the other hand, the GC showed that
2-methylnonene was still substan~ially unconverted in the rPaction mixture.
This indlcated that the Type III olefins of tha feed are of low reactivity
in the presence of this catalyst system.
Example 3
Hydroform~lat~on of Clo Naphtha ~ith a
Tri-n-octyl Pho~phine Rhodiu~ Complex at 350 psi
The experiment of Example 2 was repeated-at 350 psi instead of
1000 psi pressure. Qualitativ~ly, the reaction was very similar. The
reaction rate was only slightly lower. The final H2/CO ratio in the head
space was 51/49.
The ratio of the two major products, n-undec~nal versus
2-methyldecanal was about 2. These two aldehydes represent ll9X of the
calculated yield based on the starting l-n-decene. The total aldehyde
yield Ls 187~ of the l-decene based value. Thus, the amount of the above
two aldehydes is about 62X of the total.
Example 4
Hydrofor~ylatlon o~ Clo Naph~ha With a
Tri-l-octyl Ph~sphine Rhodiu~ Comple~
Ex~mple 2 was repeated using the rhodium complex of tri-i-octyl
phosphine ~tris-(2,4,4-tri~ethyl-pentyl)pho~phine] as the catalyst instead
of that of tri-n-octyl phosphine. The reaction was very similar to that of
Example 2 except for the lower n/i ratio of the two maLn products. The
ratio of n-undecanal to 2-msthyl decanal was 1.64 in the present
experiments whila a ratio of 1.88 was found in Example 2. The reduced n/i
ratio wss apparently a result o the steric crowding effece of the bulky
tri-i-octyl phosphine ligand.
77 123~73
The two main aldehyde products represent 94X of the theoretical
yield based on the l-n-decene content of the feed. On the same basis, the
yield of the total aldehydes was fond to be 128Z. Thus, the two main
aldehydes amounted to about 74Z of the total aldehydes produced.
Example 5-7
Hydroformylation o~ C7 Naphtha ~ith
Tri-n-butyl Phosphin~ Rhodlum Comple~
The previously described C7 fraction of the Fluid coker naphtha
was hydroformylated at 180C uDder 1000 psi pressure with the standard low
pressure procedure using 1/1 H2/CO as reactant. Three hydroPormylation
experiments were carried out using different concentrations of rhodium in
the presence of excess tri-n-butyl phosphine at 0.14M concentration. The
rhodium was provided as a dicarbonyl acetylacetonate derivative in 1,2 and
lOmM concantration. Reasonably fast reaction occurred with 2mM rhodium.
The results of ~his experiment (Example 5) will be discussed at first.
Gas consumption data indicate thae initially the reaction rate
was very high, but started to drop in 2 minutes. When the reaction was
discontinued after 12 minutes, gas absorption was minimal. The H2~CO ratio
remained close to 1 during the reaction.
Gas chromatography showed that 42X of the l-n-heptene component
of the faed was reacted. The l-n-heptene derived component of the product
was mostly n-octanal and 2-methylheptanal. The n/i ratLo of these products
was 2.3. The amount of the two compounds was 115X of the calculated value
based on the converted n-l-heptene. The total aldehyde products correspond
to 133X of that value. Apparently, minor amounts of other heptene isomers
besides I-n-heptene were also raacted.
In another experimant (Example 6) the same reaction was run in
the presence of lOmM rhodium. This resulted in an extremely fast reaction.
About 0.645 moles of H2/CO mixture wa~ consumed within the one minute
reaction time. The run gas used had a 52/48 ratio. The final ratio of
H2/CO was 1.47, a substantial increasa over the initial H2JCO ratio of 1.
Apparently, no significant hydrogenation occurred.
The gas chromatogram of the reaction mixture showed that all the
l-n-heptene was converted. The two main products were again n-octanal and
l-methyl heptanal, in a ratio of 2.15. The sum of these two corresponds to
18% more than the 2~ount which could ha~e been theoretically derived from
l-heptene. The total amount of aldehyde product is 165X of the amoun.
~2~ 3
-78-
derivable from l-heptene. Thus, the n-octanal formed equals to 48~ of the
total aldehydes formed.
In a third expariment (Example 7) only lmM rhodium was employed.
At ehis low catalyse concentration, little reaction occurred. In 20
minutes only 15Z of the l-n-heptene wa~ consumed. The n/i ratio of the two
main products was 2.3.
Example 8
~ydrofor~yl~tion of Clo Naphtha with Rhodiu~ Co~ple~
in tha Presence of 1~ Trlb~tyl Phosphina
The Clo fraction of the coker naphtha was hydroformylated under
the conditions of Example 2. Ho~ever, LM tri-n-butyl phosphine was used
insteat of 0.14~ tri-n-octyl phosphine to ascertain the effect of an
increased excess of phosphine ligand. Also, 4mM Lnstead of 2~M rhodium was
used to counteract the inhlbitory effect of the added ligand.
The initial reaction was very fast. All the l-n-decene was
converted in about 140 seconds. Thereafter, the internal decenes were
being converted at a much slower rate. At 60 minutes, the C0/H2
consumption rate was quite low. Tha reaction was discontinued after 60
minutes.
A GC analysis of the r0action mixtura showed that the two main
reaction products, n-undecanal and 2-mathylnonanal were formed at an
increased ratio. Due to the increased excess trialkyl phosphine ligand
concentration, the n/i value was significantly higher, 2.02. (In the
presance of the smaller ligand concentration Example 3t the n/i ratio was
1.88). The amount of ths two maJor products was 102X of the v~lue
calculated for the ~ounts derivable for l-n-decene. The total amount of
aldehyde product~ form~d was 130X of the theoretical value calculated for
l-n-dacene.
Example 9
~ydroPormylation of Clo Naphtha ~ith
Rhodiu~ Dicarbonyl Ac~tyl~cetona~a
The sam~ Clo naphtha was also hydroformylated under the
conditions of the previous example, but wlthout any phosphine catalyst
modifier. In this example, tha usual rhodiu~ catalyst precursor, rhodiu~
dicarbonyl acetylacetonate was used alone in amounts corresponding to 2~M
rhodiu~ conc~ntration~
., 73
79
Apparently due to the absence of phosphine modifying ligand, ehe
reaction was slow. Although the reaction time wa~ lncreased to 120
minutes, even the converstion of the most reacti~e olefin component of the
feed, l-n-decene, remained incomplete. Also, the amount of the C0/H2
reactant gas consumed WAS only about half of that of the previous example
(The 1/1 ratio of H2/CO wa8 well maintained during reaction).
The main products of the reaction were again undecanal and
2-methyldecanal derived from l-n-decene. They represented about 77X of the
aldehyde products. No alcohol product was observed. The n/l ratio of the
two main products was 1.93.
Exæmple lO
~ydro~orDylation o~ Clo ~nphth~ vleh T~i-n-butyl Phosphina
Rhotium Co~ple~ at 350 psi S/l ~2/GO ProQsur6
The Clo naphtha was hydroformylated under the conditions of
Example 8, but at reduced pressure, at 350 psi of 5/1 H2/C0. The amount of
rhodium was cut to 2mM. The trl-n-butyl phosphine concentration was ehe
sa~e, LM. The 5/1 H2/CO ratio wa_ maintained by a feed gas ratio of 53/47.
Tha sharply reduced C0 partial pressure of this reaction
signlficantly increased the n/i ratio of thc two ma~or aldehyde products
without a ma~or drop in the raaction rate.
Compared to Example 8, the n/i ratio of the two main products
increased from 2.02 to 3.2. These two products represented 68.5X of the
total aldehyde yield. No alcohols were formed during the 60 minutes
resction time. The yield based on l-decene was lOlX ~or the two main
aldehyd~s. The total aldehydes amounted eo 147X of the l-decene based
calculated yield, indicating a qigniflcant con~ersion of some of the other
olefin co~ponents of the feed. The amount of H2/CO needed to
hydroformylate all the l-decene was consumed during the first 7 minutes of
the experiment.
~xample 11
~ydroformrlation of Cl~ ~aphtha ~ith a ~hodium Compl~
of n-Oc~adsc~l Diph~n~l ~hosphln~ at 14S~C
The Clo naphtha fraction wa3 hydroformylated with the rhodium
complex of an alkyl diaryl phosphine ~o produce a higher ratio of normal
versus iso aldehyde products. To deri~e the catalyst system, 2mM rhodium
and lM n-octatecyl diphenyl phosphine were used. The reac~ion was run at
-80- ~2~ 3
145C und~r 350 psi 5/1 H2/C0 pressure. During the reaction a 53/47
mlxture of H2/C0 was fed. This feed gas more than maintained the initial
H2/C0 ratio during the 60 minutes run. The final H2/C0 ratio was 5.75,
indicating the absence of ma~or hydrogenation side reaction. Compared to
the previous example the difference is in the type of phosphine ligand used
and the reaction temperature.
The use of the alkyl diaryl phosphine ligand resulted in a much
increased selectivity of l-n-decene hydroformylation to n-undecanal. The
n/l ratio of the two main aldehyde products was 6.76. Also, in the
presence of this ligand a faster hydroformylation rate was observed. An
amount of H2/C0 sufficient to convert all the l-n-decene was consum~d
withln 3 minutes.
After the 60 minutes reaction time, GC analyses indicated that
the amount of the two main aldehyde products was 106X of the calculated
yield for l-n-decene. The total aldehyde product were 164X of this yield
and no alcohols were formed.
Example 12
Hydroformylation of Clo Naphth~ ~ith a
~hotiu~ Compler of Trl-i butyl Phosphine
Tha C7 naphtha fraction was hydroformylated under conditions
similar to those in Examples 2, i.e., at 180C under 1000 psi 1/1 H2/C0
pressure. However, instead of a tri-n-alkyl phosphine, a sterically
crowded tri-i-alkyl phosphine, tri-2-methylpropyl phosphine (tri-i-butyl
phosphino) was used. The phosphorus ligand concentration was 0.14M, the
rhodiu~ concentration 2mM. Feeding a 51/49 mixture of H2/CO as usual
maintained the equimolar synthesls ~as reactant mixture during the 60
minutes reaction tim~.
The use of the tri-i-butyl phosphine ligand resulted in a fast
resction of low n/i selectivity. Enough H2/C0 reactant was consumed during
th~ first minute of the reaction to convert all the l-n-decene in the
reaction mixture. The n/i ratio of the two main aldehyde products was
1.25. After the complete run, GC showed that the co~bined yield oi` the two
main products formed was 90~ of the value calculated for l-n-decene. The
total aldehyde yield corr~sponded to 161X of ehis valu~. In this reaction
~inor amounts of alcohols were also formed. Thus, the combined yield of
aldehydes and alcohols was 165% of the theoretical yield of the
hydrofor~ylation of the l-n-decene com?onent.
-81-
~xample 13
~ydrofor~ylation of C16-Cl~ Gas Oil with Tri-i-butyl
Pho~phine Rhodiu~ Comple~ st 180C and 1000 psi
A broad cut light gas oil from a Fluid coker was distilled in
vacuo to provids a C16-Clg fraction, having a bolling range of 74-82C at
0.lm~. A capillary GC analysis of this fraction showed that it contained
approximately the follo~ing percenta~es of l-n-olafins (Cn~) and
n-paraffins (Cn) : Cl~, 0.30; Cls, 0.28; Cl~, 10.06; C16,6.25; C17,
9.55; C17, 7.90; Cl~, 3.34; Clg, 3.10; Cl~, 0.78; Clg, 0.62.
About lOOg of the above distillate feed was hydroformylated using
the low pressur2 hydroformylation procedure under 1000 psi 1/1 H2/CO
pressure at 180C in the pres~nce of 2m~ rhodium and 140 ~M triisobutyl
phosphine.
The gas consumption data indicated a very fast initial reaction,
apparently a very effective conversion of the l-n-olefin components. After
this initial stage, the rate was steadily declining as the less reactive
olefins were being converted. At a gas consumption calculated for a 50X
conversion of a C17 feed of SOX olefin content, the reaction was
di3continued.
Capillary GC analysis of the reaction mixture showed a complete
conversion of the l-n-olefins and the formation of the corresponding l-n-
aldehydes and 2-methyl substituted aldehyd~s having one carbon more than
the parent olefin. The ratio of these n- and i-aldehyde products was 1.35.
Together, they represented 69X of ths total aldehydes formed. A comparison
of the intensities of the peaks of the two ma~or ~ypes of aldehyde products
and the n-paraffins showed that the yield of these aldehydes is about 61X
of the calculated value for the l-n-olefins. Thus a significant l-n-olefin
to int~rnal olefin isomerization occurred during hydroformylation. The
linear olefins formed were converted to 2-ethyl and higher alkyl
sub~tituted aldehydes which constitute moqt of the minor C17-Clg aldehyde
products.
The reaction mixture was distillsd in vacuo to separats the feed
from the products. About 15g of clsar yellow-greenish product was obtained
as a distillate, boiling in the range of 102 to 124G at O.OSm~.
129 L~97~
~etium Pressure HydroformYlation in the Pre~ence o~
Phosphlne-Cobalt ~9=~ uL ~ =e~e~ 14-18~
The previously described, untreated C4 to C12 Fluid coker naphtha
and i~s distillate fractions were also hydroformylated in the presence of
cobalt co~plexes of trialkyl phosphine complexes. The reaction conditions
used and results obtained are summarized in ~ LISYILI
In general, the substitution of cobalt for rhodium in these
phosphine complex catalyst systems changes the activity and the selectivity
of the system. The inherent activity of the cobalt systems is about 2
orders of magnituda smaller. In contrast to rhodium, the cobalt complexes
are multifunceional catalysts. Olefin isomerization is extensive; this
results in an increase of the n/i ratio of the products. Aldehyde to
alcohol hydrogenatlon is also extensiva. Since the ma~or products are
alcohols and the reactions are performed at medium rather than low
pres ure, syn gas consu~ption based olefin converstions are relative rather
than absolute values.
Example 14
Hydro~or~ylation of a C4 to C12 Naphtha With a
Tributyl Phosphine Cobalt Complex
About 93.8g of the broad cut naphtha feed previously described
was hydroformylated in the presenca of a catalyst system containing 80mM of
cobalt, added as dicobalt octacarbonyl, and 0.24M tri-n-butyl phosphine
tP/Co - 3). The reaction was run under the conditions of the first example
(180C, 1000 psi) but, for a longer period (60 minutes). While the initial
H2/C0 ratio was again 1/1, the synthesis gas added during the run had a
significantly higher H2/C0 ratio of 3/2. This higher run gas ratio was
amployed because cobalt phosphine complexes catalyze both olefin
hydroformylation to aldehydes and aldehyda reduction to alcohols.
During the reaction about 1 mole of H2~C0 mixture was consumed.
In contrast to the first example, no significant reduction in the reaction
rate W85 observed. The final hsad space ratio of H2/C0 dropped to 0~68,
indicating that hydrogenation took place to a major degree.
The final reaction mixture was again analy7ed by GC. The
chromatogra~ obtained showed an essentially complete converstion of the
l-n-olefin components and the formation of major amounts of the
corresponding n-aldehydes and alcohols.
73
-- 83 --
O o ~ ¦ '` .D O U ~
C a: ol _ ,o c
S ~ V ~
t`') O ~ 1-- C~J ) ~ N ~ O O
~ " ~ ~ ,c c E E
r E ~I o ~ -- O u~ ~ e
O _ _
~Co ~ VC~ ~ ~ ~ ,c
._, ~ o ~ ~ ~ oo u. ~ oC O 8
O L ._ I~ N ~ ~ L
~- a ~ ~ e v ~
. ~ CL~ ~ C
~ ~ .C~ ~ O C O O U~ ~ O ~ C
e~ :~ CO ~o _ ~0 ~
_ ~ V~
V (~- ~ O C
O ~ O C ~U~ lS~ O O _ ~ ~ o _ -~
O~ ~ r_ 3 ~ C
cl o o o o o >~
_ C C ._._
L ,~, O O ~ E ~) ~LI ~J ~ C
~ U~ O O O o o ~V~ C ~ ~ _C
oc ~ ~._ o o o c:~ o L,
~_ ~ O ~ V) 0 1~- 0 U~U~ O C ~_ O
O'~ ) ~ C!. _ ,~
LU~ ~') C ~ ~
o t ~ O cl o o ~. o c`J ~ o ~ O O
o~ ~J L 3 C
~ ~ ~ ~ l_ O O I e ~ U V
U~ O ~
X E ~ ~ ~ ~n ~D 1~ X C X C C
73
-84-
Example 15
~ydroformylatlon o~ Clo N~phths ~ith ~
Tri-n-oct~l Phosphlna Cobalt Co~plo~ at 1500 p~i
The Clo fraction of the Fluid-coker naphtha used in the pre~ious
examples was also hydroformylated using a catalyst system based on dicobalt
octacarbonyl and tri-n-octyl phosphine. The concentrations were 40mM
cobalt and 120~M phosphine ligand (P/Co - 6). The reaction was carried out
at 180C under 1500 psi for 2 hours. The initial H2/CO ratio was 1.
During the run an H2/C0 ratio of 60/40 W~9 used. The final H2/C0 ratio of
the head space was 48/50. Ther~ was no apparent decrease of
hydroformylation rate during the reaction. The maximu~ rate wa~ reached
after about 10 ~inutes. In 120 minutes, the H2/C0 feed consumed was about
155Z of tha a~ount theoretically required to convert the l-n-decene
component to undecyl alcohol.
The gas chromatogram of the final reaction mixture shows no
significant amount~ of l-n-decene present. However, other decene isomers
appear to be present in increased amounts as a consequence of concurrent
isomerization-hydroformylation.
The hydrofor~ylstion produccd tha expected two significant
aldehyde products derived from l-n-decene. However, thesa wera largely
hydroganated to the corresponding alcohols, as shown by the reaction
scheme:
iso~erization
CH3(CH2)xcH-cH(cH2)ycH3 ~ CH3(CH2)7CH-cH2
x+y - 6 ~ C0/H2
C8H17CH2CH2CHO + C8H17CHCHO
CH3
! H2
C8H17CH2CH2cH20H C8Hl7cHcH2oH
CH3
The a~ount of the above 4 products i9 about 75.5X of the
calculated yield for l-dacene.
-85~ $~3
The total yield of aldehydes plus alcohols was also estimated on
ehe basis of the capillary GC analysis of the final reactlon mixture. It
was 139X of the products calculated for a complete conversion of the
l-n-decene component. The n-aldehyde plus n-alcohol amounted to 52.lX of
the total products. Most of the products, 92.lX were alcohols. Only about
7.9X ware aldehydes. The n/i ratio of the 4 ma~or products, mostly derived
from l-n-decene was high, 7.62.
Example 16
Hydroformyl~ion of C7 ~aphtha ~ th a
~ributyl Phosph~ne Cob~lt Compl~
The C7 fraction of the Fluid-coker naphtha employed in Examples
5, 6 and 7 was also hydrofor~ylated with a catalyst system derived from
dicob~lt octacarbonyl and trioctyl phosphine. Forty mM cobalt and 0.12~M
l~gand were used tP/CO ~ 3). The reaction conditions were similar to those
in Example 6: 180C, 1500 psi and 1 hour using a 60/40 ratio of run gas.
The initial and final ratio of H2/CO in the reactor were both very close to
1. The H2/CO feed consumed was about 70X of the amount calculated for the
conversiton of the l-n-heptene component to octanols.
According to GC there was no unconverted l-n-heptene left in the
react~on mixture. Besldes hydroformylation, isomerization occurred. The
ma~or hydroformylation products prcsent were n-octanal, 2-methylheptanal
and tha corresponding alcohol hydrogenation products. The overall n/i
ratio of these products i9 about 10.06. These four products represent
about 56X of the total aldehyde and alcohol products. About 58.3X of the
total product.~ were alcohols. The significant percentage, 41.7%, of the
aldehydes present lndicatqd that the hydrogenation reaction was incomplete.
Examples 17 and 1~
~ydrofor~ylation of Clo ~aphtha ~ith a
Tr~-n-bueyl Phosphina Cobalt Co~ple~
The Clo fraction of the coker naphtha was hydrofor~ylated in the
presence of dicobalt octac2rbonyl plus tri-n-butyl phosphine catalyst
systems having a P~Co ratio of 3. The reactlons were run at 180C under
1500 p9i 1/1 H2/CO pressurq. The high H2/CO ratio was maintained by the
addition o~ a 60/40 feed gas mixturs during the reaction.
Th~ rate of absorption of the H2/CO reactant gas showed that the
reaction has an inital inhibition perlod, dependene on the concentration of
-8~
catalyst. At 40mM cobalt, this inhibition period is about S minutes; at
120mM Co, it is less than 1 min. At 40mM cobalt (Example 16), it takes
about 35 minutes to consume enough H2/CO for a complete converstion of the
l-n-decene component of the naphtha cut. At 120mM cobalt (Example 17),
only about 10 minutes are required to achieve thi~ conversion. The rate of
absorption indicate a first order reaction rate dependence on cobalt
concentration.
The first reaction with ~OmM cobalt (Example 16) was run for a
total of 1290 minutes. In that time 0.254 moles of H2/CO was consumed.
This is about two and a half fold of ths amount necessary to convert the
l-decene component to the corresponding aldehydes. However, most of the
primary aldehyde products were reduced to the cor~esponding alcohols. The
two main aldehyde products and the corresponding alcohols are derived from
l-decene via combined isomerization hydroformylation a~ described in
Exa~ple 14. Capillary GC indicated that the yield of the total oxygenated
products 63.2X of the value calculated for a complete conversion of the
l-decene component. About half of the products were of straight chain.
Most of the products, 91.2X were alcohols rather than aldehydes. The n/i
ratio of the four major products was 7.
The second reaction with 120 mM cobalt tExample 17) was run for a
total of 60 minutes and consumed 0.292 moles of H2/CO. This is almost 3
fold of the amount needed to convert l-decene to aldehydes. Again most of
the aldehydes formed were reduced to alcohols. Caplllary GC indicated that
the increased cat~lyst concentration resulted in approximaeely doubling the
total product yield to 129X of the cslculated value for the l-`n-decens feed
component. The yield of the ~our major products which could be derived
from l-n-decene was 64.8X. The n/i ratio of these product~ was 8.45.
About 44.8X of the total products was completely linear.
Examples 19 and 20
Hydroformylation of 2-Butene with a ~ri-n-Butyl
rho~phlne Cobalt Co~ple~ ant Adted Th{oL
Comparative hydroformylatlon experiments were carried out with
2-butene as a model olefin reactan~ under the conditions of Example 13 to
demonstrate that thiol inhibition can be overco~e by the use of cobalt
phosphino complex catalysts in the present process.
Two reactions were carried out, each starting with lOQg reaction
mixture coneaining 20g (0.1 mole) 2-butene, 2.43g (12 milimole)
-87- 12~
tri-n-butylphosphine and 0.68g (2 milimole) dicobalt octacarbonyl in
2-ethylhexyl acetate as a solvent. One of the reaction mixtures also
contained 38.8 mg (0.626 milimole) ethyl mercaptan to provide 200 ppm
mercaptan sulfur. Both reactant solutions were reacted with 1/1 H2/Co
undar 1000 psi pressure at 180C. An equimolar ratio of H2/CO was
maintained during the run by supplying addi~ional H2/CO in a 3/2 ratio
during the re~ction.
Both reaction mixtures were hydroformylated with simLlar
selectivity. The only slgnificant difference was in the reaction rates.
The 2-butene was more reactive in the absence of ethane~hiol. In the
absence of the thiol, 50X olefin conversion was achieved within 18 minutes.
In the presence of the thiol, a similar convsrsion took 36 minutes.
After the reaction, both m1xeuras were analyzed~ The most
signiiicant difference between the mlxtures was the selectivity to
l-butene; 10.5X in the absence of thiol versus 5.8X in its presence. This
indicated inhibition by the thiol of the isomerization of 2-butene to
produce the more reactive l-butene which is then hydroformylated to produce
n-valeraldehyde with high selectivity. The latter is largely converted by
hydrogenation to n-amyl alcohol.
CH3CH-CHCH3 ~ CH3cH2cH-cH2 COtH2 ~ CH3CH2CH2CH~CHO
~H2
CH3CH2CH2CH2cH20H
The selectivities toward the various oxygenated products were similar in
the absence and presonce of thiol: overall n/i 8.15 vs. 8.92;
alcohol/aldchyde 0.52 vs. 0.57; aldehyde n/i 6.81 vs. 7.34; alcohol n/i
12.6 v~. 13.8.
Example 21
~ytrofor~ylation of Cg-C16 Li8ht Gas Oil With
Trioctyl Phosphine Cobalt Co~ple~
Th9 previously described Cg-C16 light gas oil was hydroformylated
using a tri-n-octyl phosphine cobalt complex based catalyst system at 180C
under 1000 psi pressure and a 3~2 H2/CO reactane ratio. Cobalt carbonyl
was employed as a catalyst precursor; its concentration was 40~M, i.e.,
-88-
0.0472X cob~lt metal. The phosphine ligand was employed in 240mM
concsntration to provide a 3/1 P/Co ratio. It was added to stabilize the
cobalt and to obtain a more linear product.
The reaction was carried out without solvent. No induction
period was observed. The reaction was discontinued after 60 minutes,
although H2/CO uptake continued throughout the reaction period The amountof H2 and C0 consumed indicated that hydroformylation and hydrogenation
both occurred to a great extent. GC indicated that the products were
mainly alcohols. To enhance the analysis of the alcohol products in the
GC, the rsaction mixtures were treated with an excess of a silylating
reagen~ which acts to convert the -CH20H groups of the alcohols to
-CH20Si(CH3)3 ~roups. The retention time of the resulting capped alcohols
in the GC column is significantly increased. The shifts of retention times
by silylation confirmed that ~he main products were alcohols.
The GC of the final silylated reaction mixture is shown by Figure
10. The GC shows that none of the l-n-olefin componsnts of the feed remain
in the product stream. The capped alcohol products are mostly n-alcohol
derivatives. Although many branched alcohol derivatives are present, they
are mostly in minor amounts. Due to their increased retention time, the
peaks of most of the capped alcohols is beyond those of the hydrocarbon
feed.
A comparison of the peak heights of the capped n-alcohol products
derivad from gas oil indicated a distribution similar to that of the
starting l-n-olefins (and n-paraffins). Thus, the reactivity of the feed
l-n-olefins Ls essentially independent of the olefins' carbon number in the
presence of the phosphine cobalt complex catalyst.
Example 22
~ydroior~ylation of Clo Gs3 0$1 ~ith
Triethyl Pho~phine Gobalt Comple~
The hydroformylatlon of the previously described Clo coker gas
oil fraction was also attempted in the presence of a tri-n-alkyl phosphine
cobalt co~plex catalyst at hi8h pressure, i.e., 3000 p5i . Examples 14-18
have shown us that phosphine cobalt complexes catalyze coker naphtha
hydrofor~ylation under low pressure, i.e., 1000 psi at 180C and mediu~
pressure, i.e., 1500 psi at 180C. The purpose of the present experiments
wa~ to detemine the effect of pressure on the stability and selectivity of
the catalyst system.
~2~ 3
-89-
Triethyl phosphine was selected as the ligand because it is
potentially applicable in the present high temperature process. Triethyl
phosphine is fairly volatile (bp. 130lC), thus excess li~and can be removed
as a forerun by distillation if desired. Triethyl phosphine can be also
readily removsd from the reaction mixture by an aqueous acid wash and then
recovered by the addition of a base.
As a precursor for the phosphine complex, dicobalt oceacarbonyl
was employed. An amount equivalent to 0.472~ Co was used [0.04M Co2(CO)g]
The triethyl phosphine added was 2.9% (0.24~). Thus the P/Co ratio was 3.
The triethyl phosphine catalyst was dissolved in the naphtha feed which was
then heated under ~2/C0 pressure. Under tha reaction conditions, a
concantrated solution of the dicobalt octacarbonyl was added to the
reaction mixtura to preform the catalyst and start the reaction.
The reaction was followed by capillary GC analyses of samples
taken after 10, 30, 60, 120 and 180 mlnutes. Extensive isomerization of
l-n-decene to internal decenes occurred in 30 minutes. Hydroformylation
and hydrogenation of the aldehyde were rather slow. As expected, the
phosphine complex of the cobalt is a more stable, but less active,
hydroEormylation catalyst.
To increase the GC and GC/MS sensitivity for alcohols and to
increase their retention time, the reaction mixture was treated with a
silylating agent. The capillary GC of the resulting mixture is shown by
Fi~ e 11.
The GC/MS established that mose of the reaction products were
primary alcohols. The only detectable aldehyde components present were
minor a~ount~ of n-undecanal and 2-methyldecanal. They are present in
amounts le~9 than 5X of the total oxygenated products.
As it is apparant from the figure, the main product of the
reaction wa9 the n-Cll alcohol, undecanol. It represents 50X of the total
reaction mixture. Thus, only about 50% of the products have branching.
Significant a~ounts of 2-methyldecanol wera also formed. The n/i ratio of
these two products was about 10. This means that the hydroformylation of
l-decens was highly selective, sinc~ both of these compounds were derived
from it. The minor alcohol components could not be identifi2d because of
similariti~s in th~ir mass spectra. Baqed on the relatively short GC
ret2ntion time the isomeric C12 alcohols wer~ probably dibranched
compounds.
73
-so-
The reaction mixture was also analyzed using packed column CC to
estimate the amount of heavies formed. The heavies were only about 0.3X in
the residual product. The presence of the phosphine ligand apparently
inhibited the formation of the hea~y by-products.
The reaction was stopped after 1~0 minutes. Thereafter, the
remaining 1704g of the product catalyst mixture was worked up. The excess
phosphine and then the unreacted components were first removed in high
vacuo at room tempcrature. However, in the absence of excess phosphine,
the remaining product plus catalyst mixture was unstable when heated to
90C in vacuo. Ther~al decomposition was indLcated by a loss of vacuum.
Thersfore, th~ attempted distillation was discontinued and the catalyst was
removed fro~ the residue by aqueous acetic acid plus air treatment as
usual. The water-organic mlx~ure was diluted with he~ane to facilitate the
separation of the organic phase. After the removal of the solvent in
vacuo, the residual product weighed 420g. This is about 25 weight percent
of the crude reactant mixture. Disregarding the weighe increase of the
olefinic reaction mixture during the reaction, the above amount of total
oxygenated products corrasponds to the conversion of 25X of the gas oil
fraction employed as a feed.
The cobalt free residual product was distilled under 0.12mm
pressure. The isomeric undecyl alcohol products were obtained as a clear,
colorless liquid distillate between 80 and 90C. The dark residual heavy
by-products amounted to about 5X of the total oxygenates.
Examples 23-25
~ffect of Aging on the
~ytrofor~ylatlon of C16-Clg G~s Oil ~ith Triethyl
Pho-~phlno Cob~lt Comple~ at 140~C and 1500 psl
The broad cut light gas oil of the previous example was hydro-
formylated using the medium pressure procedure in the pxesence of 0.23M
cobalt and 0.72M triethyl phosphine. The reaction was carried out at 180C
using an initial 1/1 H2/CO reactant at a pressure of 1500 psi. The
pressure was maintained with a feed gas of 3/2 H2/C0 ratio.
In the first example (23), a rapid initial reaction too~ place.
GC analyses indica~ed that, assuming 50X olefin content for the feed, about
half of the Qlefins were hydroformylated in 12 minutes. The ma~or reaction
products were the C17-Clg n-aldehydes and 2-methyl aldehydes in a n/i ratio
of about 5.
~.2~ 73
-91-
In the second example (24), the same feed was used under the same
conditions, but after about a month's storage at room temperature, without
an antioxidant. No reaction occurred. The cobalt was precipitated.
Testing of the aged feed for peroxide was positive.
In the third example (25), the aged feed was disti.lled in vacuo
prior to being used in another hydroformylation experiment under the same
conditions. The re~ults with the redistllled feed were about the same as
those with the fresh feed of Example 23.
Hi~ Pre~ Hydrofo~YlA~ion o~ C4_to Cl~ N~phtha Fractions
in th~ Pr~sance of Cobalt Comple~s ~amples_26-472
The previously described C4 to C12 Tluid coker naphtha containing
l-n-olefins as the major type of olefin reactant was also hydroformylated
successfully in the presence of cobalt complexes withollt phosphine
modifiers at high pressure. Clo and C8 feeds were studied in detail. The
reaction conditions used and some of the results obtained are su~marized in
Table~
In general, the omission of the trialkyl phosphine modifying
ligand from these cobalt carbonyl complex catalysts resulted in greater
hydroformylation activity. However, the ratio of n-aldehydes to the
2-methyl branched aldehydes was drastically reduced to values between about
1.9 and 3.2. The cobalt catalysts could be used not only at high, but at
low temperatures as w~ll. In the low temperature region of 110 to 145C,
the process was selective for the production of these major aldehyde
isomers. The rata of olefin isomeri~ation was drastically reduced. The
n/i ratio of the products and the amount of aldehyde dimer and trimer
products w~re inversely proportional with the reaction temperature.
Example 26
Hydrofsrmylation of a C4 to C12 Naphtha by H2~CO ~lth
D~cobalt Octacarbonyl at 150C and 4500 psi
The previously described broad naphtha cut was hydroformylated as
a 1/1 mixtur~ with hexanc in the presence of 0.2X CO at 150C by an approx-
imat61y 55 to 45 miXturQ of H2 and CO at 4500 psi, using the high pressure
7~3
--92--
V-
_ ~ ~ ~ ~ o
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o ~ .~
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O I N O O C~J O O C~l O C~i O
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,
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-93-
procedure. The reaction mixture was sampled after 10, 30, 60, 120 and 180
minutes to follow th~ progress of the reaction by capillary GC analyses.
The GC data indicated a long induction period. Up to 30 minutes,
no n-l-olefin conversion was observed. For example, the ratio of
n-l-decene to n-decane component remai~ed the same. However, thereafter a
fast reaction occurred. The GC of the 120 minute sample showed that all
the l-n-olafin components were completely conYerted. The ma~or product
peaks of the GC are those o the correspondin~ n-aldehydes. The minor, but
distinct aldehyde products are 2-methyl substituted aldehydes. The n/i
ratio of these major products is about 2.8.
The GC of the final reaction mixture is shown by Fi~e 12. It
expressly shows the ma~or Cs to C13 aldehyde products formed and the Cs to
C12 n-paraffins. A comparison of the hydrocarbon reglon of the figure with
Figure 1 of th~ naphtha feed clearly indicates that on hydroformylation the
l-n-olein components were essentially completely converted to provide
mainly the n-aldehyde products. Figure 7 also shows that the peaks of the
hydrocarbon and sulfur compound components of the feed in the Cg to C12
n-paraffins region overlap with those of the C7 to Clo aldehyde products.
Since the GC retention times of components are approximately proportional
to their boiling points, this indicates that thc overlapping components
cannot be separated by fractional distilla~ion.
Examples 26 and 27
Hydroformylation of Cs Naph~ha by 1/1 H2/CO
~ lth 0.2X CobAlt at 130C and 3000 psi
a~d tha ~ydrogenation of tha C6 Aldehyde Product
About 2500g of a broad Cs Flexicoker naphtha fraction with a
boiling range (bp.~ of 24 to 34C was washed three times with 1250ml cold
25X agneous NaOH solution and once with distilled water to remo~e the thiol
components. Thereafeer it was fractionally distilled using a 22 plate
Oldershaw column to obtain hydroformylation feeds free from higher boiling
disulfides. The feed composit~ons and the results of two hydroformylation
experiments are shown in TablQ~ 9g~
A Cs f ed of bp. 25-28C, cont.aining about 33X l-pentene and 13X
n-pentane, was hydroformylated in the presence of 0.2X Co addPd as Co2(CO)g
at 130C by a 1/1 mixture of H2/CO at 3000 psi for 6 hours. The reaction
mixeure WaQ periodically sampled fcr packed column and capillary GC
analyses. A highe. boilinz Cs feed of bp. 28-32C,
- ~2~73
-94-
Table XX
~ydroformylation of Cs Olsfinic Fr~ction~ of Flexico~er Naphtha at 130~C
in the Prcsence of 0.2X Cobalt Catslyst Derived ~rom Co2(CO)g with
1/1 H2/CO at 3000 p3i
Components of Total Mixturç
Reaction Pressure mbY Packed Column GC. Z
Example Time Drop Un- Alde- Alcohols Dimers
__~Q~ B_reac~ hYdes Form~tes Trimers
26 60 21 92.4 6.2 0.3 1.1
120 160 78.2lg.5 0.3 2.0
180 32 28.965.9 1.2 4.0
240 12 22.568.5 3.8 5.2
27 60 94 93.5 4.8 0.4 1.3
120 188 66.329.0 0.5 4.2
180 20 29.861.8 2.9 5.5
240 8 25.963.5 4.2 6.4
-95- ~. 2~ 3
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'Yl ~ U , _~ O N Cl~ t 3 3 c c
~ ~ ~ 3C~ ~ ~ O O ,~ O _l o ~ r~ u~ C~
4 U~ ~ C`J t~ D N ~ ~C E~
.C . g . ~ ~ 3 S
Sb C~ C,
Z; O ~ :~ O O O O O O O C3 0 0 C~
E~ ~ L O O
C ~_1 _
$ ~3
-96~
ontaining about 31X l-n-pentene and 20X n-pentane was similarly converted.
The packed GC data of Table X~ show a selective conversion of the
olefinic components to aldehydes. The observed rates of pressure drop
indicate that maximum reaction rates were reached betweeen 1 and 3 hours.
By the end of the 4 hour reaction period, the hydroformylation was
practically complete and according to GC, the final reaction mixture
contained more than 60X C6 aldehydes.
The capillary GC data of Table XXI show the selectivity of the
olefin conversion and the isomer composition of the aldehyde products
formed.
The change in the distribution of the major hydrocarbon compon-
ents of the Cs fe~d indicate that l-pentene, 2-pentenes and the methyl
substitueed l-butenes are converted to n-hexanal and the corresponding 2-,
3-and 4-methyl branched pentanals. The 2-methyl-1-butene component is much
less reactive and as such is only partially converted under the reaction
conditions used.
The main aldehyde product is n-hexanal. According to capillary
GC, it is more than 45X of the C6 aldehyde products. The three methyl
branched C6 aldehydes, 2-, 3- and 4-methylpentanal, are present in compar-
able ~uantities and not completely separated by GC. n-Pentanal and these
monobranched aldehydes amount to more than 95X of the reaction mixture.
Slightly more than lX 2-ethylbutanal is present. Similar amounts of
2,3-dimethylbutanal are found.
Sulfur specific GC of the reaction mixture did not indicate any
sulfur containing impurities in the aldehyde range. However, there were
low boiling sulfur compounds includLng H2S in the feed range.
The reaction mixture was distilled to isolate the products. The
C6 aldehydes were obtained betwen 47 and 51C at about 50/mm pressure.
During the distillation, most of the cobalt complex catalyst decomposed and
precipitated. Significant aldehyde dimerization and trimerization occurred
during distillation as a side reaction. The recoYered Cs hydrocarbon feed
was free o~ sulfur indicating that desulfurization by cobalt also occurred
during the distillation.
The distilled aldehyde product contained 37.8X n-hexanal, 55.8X
isohexanals, 1.8X alcohols and 4.6X formates according to packed GC. The
~ t 3
-97-
reduced percentage of n-hexanal in the distillate compared to the reaction
mixture was due to its preferential aldolization over the isohexanals.
The distilled aldehyde washed with lOX aqueous sodium hydroxide
solution to remove the small amounts of HCo(CO)4 which codistilled during
the separation. The washed aldehyde (1730g) plus 5Z distilled water
(86.5g) was then hydrogenated in the presence of a 160g (270~1) CoS/MoS
based catalyst. The reaction mixture was presured to 1500 psi (103 atm)
with hydrogen and heated to 130C. The pressure was set to 3000 psi and
th~ temperature was increased by 10C every hour. Once the temperature
reached 160C, it was kept there for the total reaction time of 20 hours.
Subsequent capillary GC and 400 MHz lH NMR analyses indicated that
essentially all aldehydes were hydrogenated to the corresponding alcohols.
Capillary GC indicated that 38.4X of the C6 alcohols formed was n-hexanol.
According to packed GC, dimeric and trimeric by-products were formed in
comparabla amounts. They amounted to about 15X of the reaction mixture.
No paraffin by-products were observed. Sulfur specific GC detected no
sulfur.
A 2 to 1 mixture of the crude, C~ alcohol product was ~ashed with
a lOZ agneous solution of NaOH and then with water. After drying over
MgS04, the alcohol was distilled to recover the hexanols as a clear,
colorless liquid mixture between 109 and 115C at 200 mm. The n-hexanol
content of the distillate product was 35.8X The dimer by-product was
distilled at 12 mm. It was obtained as a colorless liquid between 103 and
113C. Capillary GC indicated that it contained isomeric C12 aldol
alcohols. The distillation residue was mostly the trimer presumably formed
from the aldol adduct of the aldehyde via the Tischenko reaction:
C4H9CH2CH-CHCH ~ C4HgCH2CHO ~ C4HgCH2CH-CH-02CCH2CH2C4Hg
OH R OH C4Hg
+ C4HgCH2CH-CHCH20H
C4HgCH2CH20CO C4Hg
Similar trimerization side reactions occur with the other aldehyde products
of the present process.
Examples 28 and 29
Hydroform~l~tion o~ C6 Naphtha by 1/1 H2~GO vith Cobalt at 130 and 150C
under 3000 psl ant the Hydrog~nat~on o~ tho C7 Aldehyd~ Pr~duct
-98-
A heart cut C6 Fluid-coker naphtha of bp. 56-65C fraction was
used as a feed for hydroformylation. It contained about 42X l-hexene. Its
detailed composition was previously discussed and given in
Figure 3. The reactions wsre carried out with an equimolar mixture of H2
and C0 at 3000 psi, (206 atm). About 2000g of the feed was used per run.
As a catalyst C02(CO)g was added in benzene solution. In the first run,
the cobalt equivalent of the catalyst was 0.4% and the reaction temperature
130C. In the second experiment, 0.2Z Co was used at 150C. Rapid olefin
conversion was observed in both experiments.
Analyses of periodic samples of the reaction mixtures by packed
colu~n GC are shown by Table XXII. The pressure drop data of the Table
indicate that the hydroformylations were essentially complete in both
experiments in 180 minutes. By that time, the percentage of unconverted
hydrocarbons in the reaction mixture was reduced close to the mini~um in
the 30X range. The combined percentages of aldeh~de plus some alcohol and
formate ester products reached a maximum in about 180 minutes. More
aldehydes (62.3X) were obtained at 130C than at 150C (53.6%). The
significantly reduced aldehyde concentration after 360 minutes (52.1 and
37.6X, respectively) is clearly due to dimer and trimer formation (19.4 and
33.4Z) respectively.
Capillary GC provlded an effective separation of the volatile
isomeric components o~ the reaction mixture. Most of the isomeric C7
aldehyde, C7 alcohol and C7 alkyl ~ormate ester products could be identi-
fied by a combination of capillary and mass spectrometry (~S). In the
capillary GC of the isomeric aldehydes product, shown by Figure_13, all the
aldehydeg which can be derived from linear hexenes and four of the
aldehyde-~ deri~ed from monobranched heptenes were separated and identified.
The reaction schemes of the presumed hydroformylations leading ~o the
various heptanol isomers are shown in the following:
CH3CH2CH2CH2CH-CH2 ~ CH3CH2CH2CH2CH2CH2CH0 : Normal
CH3CH2CH2CH-CHCH3 - ~ CH3CH2CH2CH2CHCH0 : 2-Me
CH3
-
CH3CH2CH-CHCH2CH3 - ~ CH3CH2CH2CHCHO : 2-Et
C2H5
~$~ 3
99
- Table XXII
COMPOSITION BY PACKED COLUMN GC OF PERIODIC SAMPLES OF REACTION MIXTURES
OF ~HE HYDROFORMYLATION OF A C6 OLEFINIC DISTILLATE FRACTION OF
FLUID-COKER NAPHTHA BY H2~CO AT 3000 PSI (20680 kPa)
Pressure _ _ GC Composition~ X Alde-
No. Dropa hydes,
Temp. Ti~e ~i Hydro Ald~hydes Dimers n/i
_Cat. Min. ~ carbonsb nC 1 Trimers Ratio
28 10 94 97.0 1.4 0.8 0.8 0.56
77 45.127.0 24.1 3.8 1.12
130C 60 32 39.729.6 27.8 2.g 1.06
0.4XCo 180 11 30.331.5 30.8 7.4 1.02
240 8 29.629.6 29.9 10.9 0.99
360 - 28.525.0 27.1 19.4 0.92
29 10 118 89.0 3.7 3.5 3.8 1.06
273 74.612.1 9.2 4.1 1.31
150C 60 201 42.526.4 ~4.4 6.7 1.08
0.2~Co 180 11 28.726.4 27.2 17.7 0.97
240 10 26.323.8 25.1 24.8 0 95
360 - 29.020.0 17.6 33.4 1.14
... . ~
aPressure drop while supply of additional H2/CO is shut.
bUncon~erted feed components.
CThe percentage of n-aldehydes also includes alcohols and formate esters.
-100-
CH3CH2CH2C-CH2 ~CH3CH2CH2CHCH2CHO : 3-Me
CH3 CH3
.,
CH3CH-CHCHCH3 ~CH3CHCH2CHCHO : 2,4-DiMe
CH3 CH3 CH3
CH3cH2cHcH-cH2 ~CH3CH2CHCH2CH2CHO : 4-Me
CH3 CH3
Capillary GC also indicated the presence of minor amounts heptyl
alcohol and heptyl formate secondary products. The main isomers were ehe
normal heptyl and 2-methylhexyl derivatives derived from normal heptanal
and 2-methylhexanal as indicated by the following reaction scheme:
CH3(CH2)5CH20M CH3tCH2)3CH(CH3)cH20H
. I H2
H2/CO
CH3(CH2)3CH--CH2 - ----~ CH3(CH2)5CH + CH3(cH2)3cH(cH3)cHo
~ H2/CO ¦ H2/CO
CH3(cH2)6ocH CH3(CH2)3cHcH20cH
Il 1 11
CH3 O
n-ROCH 2-MeCH20CH
Il li
O O
,
In case o the alcohol by-products only normal heptanol and
2-methylhexanol, the two main isomers, were identified. However, all ehe
significant isomeric heptyl formaee by-produces could be recognized since
73
-101-
their GC peak patterns werç the same as those of the corresponding
aldehydes.
Analyses by capillary GC of samples periodically taken from the
reaction mixtures of 130 and 150C hydroformylations provided detailed
~nformation on the progress of the reactions and side reactions. The data
obtained are sum~arized in Table XXIII.
In general, the capillary GC results also indicate that the
primary reaction, i.e. hydroformylation, was essentially complete in 180
mlnutes. In this period, the hydrocarbon content of the mixtures decreased
to about 35X. Deter~ination of the concentrations o f l-hexene and 3-hexene
reactants relative to that of the unreactive 3-methylpentane component
indlcated rapid olefin conversion. l-Hexene conversion was essentially
complete within one hour. 3-Hexenes convsrsion took about three hours. In
that period 2-methyl-1-pentene was also reaceed. The residual olefin
content of th~ hydrocarbon feed after 3 hours was about 5X. Thus the total
olefin conversion is about 92X.
Determinations of the 3-hexene concentrations in the 150C
reaction mixtures indicated a slight increase rather than decrease during
the first hour. This increase is apparently due to the isomerization of
l-hexene to internal hexenes concurrent with the hydroformylation. Olefin
isomerization is much reduced at 130C.
Hydroformylations were continued at both 130 and 150C for a
total reaction time of 6 hours (360 mln.). During the last 3 hours largely
secondary reactions took place. The concentration of formate esters more
than doubled. Formates were 7.1% of the oxygenated products at 130C and
8.2% at 150C. The alcohol concentraiton decreased from 3.2 to 1.7X during
the last 3 hours at 150C. This was apparently due to the ~ormation of
heavy by-products not observable by capillary GC.
Table XXIII also shows the percentage distribution of the main
aldehyde products in the reaction mixture. After 3 hours reaction time,
the maln aldahyde products amounted to 93.lX of the total oxygenates at
130C and 95.7X a~ 150C. The n-aldehyde component was 36.2 and 31.2~,
respectively. As sxpected the n-aldehyde conc0ntration decreased with
increasing reaction time. Mor2 and more of the internal and branched
olefin components reacted to form other branched aldehydes.
Table XXIII separately lists the percenta~e in the oxygenates of
ths three iso~eric heptanals, i.e. n-heptanal, 2-methylhexanal and
2-ethylpentanal. These aldehydes are derived from linear h2xenes as it was
-102-
~ ~ o~ ~ S
æ c:~ ~ s~ c~ o o _i , ~ ~ ~ U
o CO ~ ~
~i ~ ~ C I U~ O
o o ~ ~ ~ O o o
~ ~ 'O u~ I I ~ o
~, o æ~ C O O OO OC, O O O O
~o 0 u O o
3; ~ 3 I ` 1 ~ ~ ~ ~ ~ ~ ~
~ O a~ ~1,~ ~ ~ ~ ~ ~ ~
V ~ N 00 ;S ~ rf ~ ~d aJ
U ~ C
O C~
~X ~ ~ ~ O O C~ C
O ~ ~1. .C c~ D X
_l ~: co o o~ ~ ~ ~ n 1~ ~ ~ ~ 1
¢ ~ o . u~
~ ~ C7 ~
O ~ ~ I~ ~ X ~ ~ ~ ~ ~ ~ C
u~ u
3 ~ ~ ~ ~ 0 ~ ~ " , C
~ ~ X V~ ~C
O a~ ~
o ~ o~ I ~ o
~ Z ~ C
o o o
O O ~ _I ~ ~1 VD N ~1
~ . o C
Q.
E~~ h ~ . ~ ~ ~ O _~ o u
~a ~ o
Z C~
æ~ cl O ~ O O`~ ~oO O O O O O ~ O
O ~ ` O
X z ~ O U
-103 1~ 73
praviou~ly ~hown by the rea~tion schemes. Their combined percentage after
3 hou~ i9 57.3X at 130C and 52.6X at 150~C. It is noted that these per-
centaga~ are way balow the percentage of linear olefins in the total
identified olsflns of the feed (86X). This and particularly the lower than
expected perc~ntags of ehe n-aldehyde component are due to the presence of
signlficant amounes of unidentified methylcyclopentenes in the feed and the
preferential convçrsion of the primary normal aldehyde iso~er products to
higher boiling secondary by-products.
The percentage distribution of identlfied lower boilin~ oxygen-
ated compounds is shown in TablçL~ V It is noted that in this table the
su~ of the aldehydes derived from linear hexenes (Normal, 2-Me and 2-Et) in
180 mlnuta~ is 65.6X at 130~C and 61.lX at lSO'C. These increased percent-
age~ ~re due to the exclusion of cyclic C7-aldehyde products from the
calculations.
The primary C7 aldehyde products of the hydroformylation of C6
olefinic coker distillate feed and the secondary products derived ~ia ehe
condensation of these aldehydes were separated by distillation for further
studies. At first, the two reaction mixtures resulting from the
hydroformylation of the C6 olefinic naphtha fraction at 130 and 150C were
separately decobalted with aqueous acetic acid plu5 air treatment as usual.
Neither precipitation nor separation prob~ems were encountered. In case of
the 150C reaction mixeuro, the percentage of dimers plus trimers was
reduced from 33.4~ to 18.5Z duri.ng decobalting, probably due to acetal and
ester hydrolysis.
The decobalted yellow liquid reaction mixtures (1834 g and
2288 e) wero fractionally distilled under atmospheric pressure using a two
foot packod column.
Mose of the unconverted hydrocarbons were removed from the
reaction mixtures as colorless liquid distillates boiling between 55 and
65C, u~ing a heating bath of 120 to 130C. Thereafter, the aldehyde
produots were distilled at reduced pressure. Th~ aldehydes from ~he 130C
reaction were distilled at 29 to 31~C under 0.2mm. Those of the 140C
hydroform~lation were received between 30 and 50C at lOmm pr~ssure. The
heating, particularly during the at~ospheric distillation, resulted in the
formation of additional amounts of dimers and trimers. In the cas~ of the
130C reaction mix~ure, the heavy by-products increased by 60% (from 18.9
to 31.9X) during dlstillation. In tha case of the 150'C reaction mixture,
the incre~se was 82X (fro~ 18.5 to 33.6~).
-104- ~ 3
Table XXIV
SELECTIVITY OF THE HYDROFORMYIATION OF C6 OLEFINIC DISTILLATE FRACTION
OF BILI.INGS FLUID-COKER NAPHTHA TO VARIOUS ISOMERIC C7 ALDEHYDES
_ Capil~GC Con~osition of Mai~ Products and Bv-P~ducts. X
Aldehvdes Alcohols Formates
Temp. Timc 2,4- 2- 3- 2- 4- 5- Nor- 2- Nor- 2-Nor-
Cae, ~ ~ ~ Me Me Me Me mal ~ mal Memal
130C 10 0.9 4.39.0 17.3 6.4 4.857.3 - - - -
0.4X Co30 2.3 ~.29.1 20.9 7.5 4.047.4 0.3 0.40.3 0.6
2.2 6.99.9 19.8 8.2 4.646.1 0.4 0.60.5 0.8
180 2.5 6.511.9 17.6 9.0 5.941.5 0.6 1.01.4 2.1
240 2.4 6.412.2 17.3 8.9 5.940.:20.7 1.21.9 2.8
3~0 2.5 6.812.5 17 2 8.5 5.837.7 0.6 1.52.8 4.1
150C 10 2.0 7.57.5 24.2 6.0 4.047.2 - 1.0 - 0.6
0.2X Co30 2.2 7.66.9 24.8 6.6 3.547.1 0.2 0.7 - 0.4
2.4 7.38.5 21.7 7.9 4.345.4 0.6 0.90.4 0.6
180 2.7 6.611.0 17.8 9.0 5.83~.7 2.7 3.71.7 2.3
240 2.7 6.510.7 16.7 8.4 5.533.6 4.3 5.92.4 3.3
360 2.9 8.011.5 18.1 7.7 5.030.7 2.5 3.64.3 S.7
1 Z~4~373
-105-
The distilled C7 aldehyde products of the two hydroformylation
runs were combined to provide 1353 g (11.87 moles) aldehyde intermediate.
The composition of this combined aldehyde product with the distribution of
the various heptanal isomers i9 provided in Table XXV.
The heptyl formate rich distlllate fractions were also combined
to providc 396 g of another intermediate for hydrogenation. This colorless
liquid fraction contains about 50Z formate ester. Its boiling range is
from 43'to 65C at lOmm. The rest are aldehydes and alcohols and their
condensation products. Thus the product is equivalent to about 3 moles.
As such, it is the calculated amount for the hydroformylation of 252 g (3
moles) of hexene. The isomer composition of this formate rich product is
comparable to that of the aldehyde in Table XXV.
The aldehyde product consists of about 90X aldehydes, 9X formates
and l~ alcohol. Aboue 82.6Z of all the components of the aldehyde fraction
were specifically identified. Of the total identified aldehydes, 35.2X is
n-hep.tanal. The n/i ratio of aldehydes is 0.54. Most of the iso-aldehydes
are monobranched C7-aldehydes. Ony one dibranched aldehyde, 2,4-dimethyl-
pentanal, was found. On an average the aldehyde product mixture contained0.63 branches per molecule.
The higher boiling for~atc rich fractlon (E-7170-II) could be
only partially analyzed by capillary GC. The high boiling dimer and trimer
components were not eluted from che capillary column. According co packed
column GC, th~ formate fraction contained small a~ounts of dimers (about
2X), but large amounts of trimers (about 30X). The relative percentage of
formate.c among thes0 components is 60X. It is interesting to observe that
th~ alkyl carbon backbones of these isomeric heptyl formates correspond eo
those of the primary aldehyde products.
After distilling off mose of the aldehydes, the residual reaction
mixtures were combined and their fractional distillation continued at 10~
using an 18 in. packed column. Further distlllate fractions containing
increasing amoun~s of C7 alcohol and heptyl formate secondary reaction
products were obtained betwen 50 and 66C at lOmm. During the distilla-
tion, thermal decomposition of ;he formaee esters occurred to an increasing
degree as the temperature of the heaeing bath increased to 150C. Thus the
last small distillate fraction ~11 g) consiseed of 70X h~ptanols, 12X
dimers and 18X trimers.
.2~ 3
-106-
Table XXV
COMPOSITION OF THE C7 ALDEHYDE PRODUCTS AND FOR~ATE BY-PRODUCTS DERIVEDFRO~ A C6 OLEFINIC DISTILLATE FRACTION OF FLUID-COKER NAPHTHA
Compos~tion bv Ca~lllary CC
Aldehydes _Formates
~ of % of Z of
Seq. Nams Designatlon Total Listed Listed
~_ ~ ~~Qmpo~entP~--ÇQ~mg:~D~ Cm~, C~p~s. C~pds.
1 2,4-Dimethylpentanai 2,4-Di-Me-CH02.22 13.50 18.10
2 2-~hylpentanal 2-Et-CH0 8.07 9.77 0.68
3 3-Methylpentanal 3-Me-CH0 11.15 13 50 1 99
4 2-~&thylpentanal 2-He-CH0 15.50 18 76 2 53
5-Methylpentanal 5-Me-CH0 6.74 8.71 1.23
6 4-M~ehylpentanal 4-Me-CH0 4.55 5.52 0.90
7 n-Heptanal n-C6-CH0 26.20 31.72 8.98
8 2-Methylhexanol 2-Me-CH20H 0.45 5.39 10.82
9 n-Heptanol n-C6-CH20H 0.31 0.38 12.53
2-Ethylpentyl formate 2-Et formate0.10 0.12 0.67
11 3-Methylhexyl formate 3-Me formate0.51 0.62 2.88
12 2-~ethylhexyl for~ate 2-Me formate2.93 3.55 18.10
13 5-Methylhexyl formate 5-Me formate0.80 0.97 5.72
14 4-Methylhexyl formate 4-Me formateO.46 0.56 3.78
n-Heptyl formate n-C7 formate2.59 3.14 28.90
16 Total aldehydes R-CHO's 74.43 90.13 16.60
17 Total alcohols R-CH20H's 0.76 0.92 23.35
18 Total formates R-CH202CH's7.39 8.95 60.05
19 Sum Totsl 82.58 lOO.OO
aThe h~gh boLling ~dimer and trLmer" components were not eluted from the
capiIlary GC colu~n. According to packed column GC there were about 2i
~ b-u~ 301 ~rim-ri pre~en-
-107-
After the decomposition of the formate ester by-products, the
rest of the residue was distilled using a one foot column at O.lmm. About
640 g of a distillate consisting of about 70X dimer and 21Z alcohol was
obttained as a clear, pale yellow liquid boiling between 55 and 74C.
Thereafter, a trimer rich fraction (80X) and a tetramer rich fraction (58X)
were also obtained as yellow liquid distillates. The "trimer" fraction
distilled at 130 to 132C at O.lmm with decomposition.
The final distillation residue was only 116 g, i.e. 2.8Z of the
starting reaction mixtures. However, the recovery of pure distillate
products was poor, due to the concurrent decomposition of the ormates and
heavier by-products. The present results suggest the hydrogenation of the
comple~e reaction mixture immediately subsequent to cobalt removal. This
should result in much improved recovery of the desired hepanols.
The sulfur compound components of C6 olefinic coker naphtha feed
and the hydroformylation feed were also studied primarily to determine
sulfur distribution according to boiling point. The total sulfur contents
of feed plu~ selected product and by-product fractions is shown by the
fol~lowing tabulation:
Boiling Point Main Component Sulfur
Ç/mm ~X) ppm
56 - 65 ~760 Hydrocarbon Feed (100) 640
55 - 59 /760 Recovered Hydrocarbon (99) 575
31 /02 Aldehyde (85) and Higher 92
58 - 65 /10 Formate (46) and Lower 123
55 - 57 /0.1 Dimer (82) and Lower 1740
130 - 132 /0.1 Trimer (80) and Lower 3380
- DistillatIon Residue 596
The data indicate that some of the sulfur compounds of the feed are con-
verted to high boiling compounds. The aldehyde product has a relaeively
low sulfur content.
An investi~ation of the sulfur distribution by GC/MS showed that
the thiol components of the feed were lar~ely con~erted to H2S and to high
boiling sulfur compounds while the thiophene component remained mostly
unconverted. The main sulfur compound impurity in the aldehyde fraction
was thiophene, due to poor separation.
Thb sulfur containing compounds in the dimer fractions were
thiolheptanoic acid propyl and butyl esters. It is assumed that the propyl
ester was derived by the reactisn of the propanethiol component of the fesd
9~
-108-
with the C7 aldehyde product
2 C6H13CH0 + C3H7SH ~ C6H13cos~ + C6H13CH0
The corresponding butyl ester could have been derived via butadiene derived
from ~hiophene according to the following hypothetical set of reaction
equatLons:
S + 2H2 ~ CH2~CH-CH-CH2 + H2S
2 C6H13CHO ~ ~ C6Hl3C2H + C6H13CH2H
C6H13C2H + H2S ~ C6H13CSH ~ H20
C6H13CSH + CH-cH-cH-cH2 -- C6Hl3coscH2cH--cHcH3
l H2
C6Hl3coscH2GH2cH2cH3
The above hypothesis is supported by a model experiment. A 9 to
1 mixture of l-hexene and thiophene was hydroformylated under the pre-
viously used conditions Ln the presence of 0.02X cobalt in a highly
exothermic reaction between 140 and 185C. GCjMS studies indicated that 5X
of the thiophene was converted to bu~yl thiolheptanoate and propyl
thioheptanoate.
The main sulfur containing components of the trimer fraction were
found to be diheptyl sulfides. These were presumable derived from the
heptanal products as indicated by the following hypothetical sequence of
r2actions:
H2 S H2
C6H13CH0 ~ [c6Hl3cHs] '- C6H13CH2SH
C6H13CH
C6Hl~cH2sH - ~ C6H13CH(OH)Scx2c6Hl3
~ H2
C6Hl3cH2scH2c6Hl3
Whether the above hypotheses of the course of sulfur compound conversions
are right or wrong, the present exa~ple demonstrates tha~, in the present
process, the sulfur containing impurities of the feed are partially
- log- ~ 73
converted to high boiLing thiol esters and sulfides rather than sulfur com-
pounds of the aldehyde boilLng range. Thus aldehydes of low sulfur content
can be isolated by frational distillation.
The aldehyde product was hydrogenated as a 2 to 1 mixture with
toluene in the presence of 5X water and lOX CoS/MoS based catalyst at about
160C under 3000 psi for 20% hours. Probably as the result of the high
temperature employed, significant dimerization occurred. According to
packed colu~n GC, the distribution of the oxygenated components of the
final reaction mixture was the following: 56% alcohols 39% dimeric aldol
alcohols and 5Z trimers, Sulfur specific GC indicated no sulfur in the
alcohol range, but H2S and high boiling sulfur compounds in the dimer
range.
The crude alcohol product was further diluted with toluene to
produce a 1 to .1 mixture. This was washed with lOX aqueous sodium
hydroxida and then with water to remove the H2S and other acidic impuri-
ties. The resulting organic phase was then fractionally distilled using a
24 plate Oldershaw column. The heptanol product was obtained as a color-
less, pleasant smelling liquid between 98 and 103C at 55mm, The dimeric
aldol alcohol distilled in the 74 to 99C range at 3mm. The trimer
by-product remained as the distillation residue, No sulfur could be
detected by GC in the alcohol product, but minor sulfur impurities were
noted in the dimer,
Tha heart cut heptanol product containing 22X n-normal isomer was
converted to semilinear diheptyl phthalate which was evaluated as a
plasticizer.
Example 30
~ydroformylation of C7 Naphtha by 1/1 ~2~CO
with O.2X Cobalt at 13~C under 3000 psl
ant the Hytrogsnatlon of the CR Aldehyde Product
A broad cut C7 Fluid-coker naphtha was redistilled to provide an
olefin enriched oxo-feed, The narrow fraction of a 15~10 distillation,
boiling betwen 88 and 94C, was utilized, It contained about 6.5X
2-methylheptene, 30X l-n-heptene, 12X n-hepeane, 4.3X trans-2-heptene, 2,8X
cis-2-heptene. Only small amounts of aromatic hydrocarbon were present:
O,lX benzene and 0,5~ toluene, A sulfur specific GC of this distillate
prior to use as a feed indicated thae some of the sulfur containing
components were converted to hign boiling compounds,
73
-110-
The hydroformylation of the above feed was carried out using a
to 1 mlxture of H2/C0 under 3000 psi at 130C with 0.2~ Co catalyst, added
as a solution of Co2(CO)g in the feed, in the manner described in the
previous example. A maximum rate of pressure drop was observed about an
hour after the start of the reaction. The conversion of l-heptene was
essentially complete in two hours. The reaction was completed in four
hours. The reaction was highly selective to aldehydes. The distribution
of the various types of components of the final reaction mixture by packed
column GC was the following: 33.7X unconverted C7 hydrocarbons, 59.lX C8
aldehydes, 4.2X C7 alcohols and C7 alkylformates, plus 3X dimers and
trimers. Capillary GC provided the following isomer distribution of C7
aldehydes: 43.8Z n-octanal, 11.7X 2-methylheptanal, 8X 3-methylheptanal,
5.8X 2-ethylhexanal and 1.7X 2-propylpentanal. A sulfur specific GC of the
reaction mixture indicated the presence of H2S, some volatile sulfur
compounds in the C7 feed range and minor non-volatile sulfur compounds in
the dimer range. There were no measurable sulfur compounds in the aldehyde
range.
The hydroformylation reaction mixture was decobalted by aeration
with hot aqueous acetic acid. Thereafter, the cobalt free mixture was
hydrogenated without prior removal of the unreacted C7 hydrocarbons and
volatile sulfur compounds. Two hydrogenation experiments were performed in
the presence of lOX CoS/MoS based catalyst and 5X water under 300 psi (206
atm) pressure. The first experiment was carried oue at 150C. After 20
hours only about half of the aldehydes were reduced. Thus the reaction was
completed in 40 hours. The second experiment was carried out at
temperatures increasing from 130 to 160C in four hours in the manner
described in Exampla 26 and 27. After an additional 16 hours at 160C, the
hydrogenstion was complete.
Hydrogenation at 150C resulted in the formation of major amounts
of dimers. The ratio of C8 alcohols to the C16 aldol alcohols ln the
reaction mixture was 64 to 37. There was also significant C8 paraffin
formation as indicated by the 78/22 ratio of C7 and C8 hydrocarbons. In
contrast, the better controlled, variable temperature hydrofor~ylation was
highly selective: The ratio of C7 alcohols to dimer alcohols was 91 to 9
and the C7 to C8 hydrocarbon ratio 92 to 8. The n-aldehyde reactants were
preferably dimerized. Hydrogenation at 150C produced C8 alcohols coneain-
ing 36.4X n-octanol, while the more controlled variabls temperature
reaction gave a C8 alcohol con~aining 40.3X normal isomer.
~2~ 73
The crude C8 alcohols were washed with lOX aqueous NaOH and ~hen
with water. Thereafter, the mixture was fractionally distiled using a 22
plate Oldershaw column. The C8 alcohol product was obtained as a clear,
colorless liquid between 81 and 87C at 13mm. It contained 33X n-octanol
No sulfur could be detected by GC. The compound was converted to a
semilinear dioctyl phthalata plasticizer.
Examples 31 to 34
Hydrofor~ylation of Broat and Narro~ Cu~ C8 ~aphtha Fractions
With and U~thous ~rio~ Caustic Trea~ent in the Pro~enc~ of
Cobalt ~ith 1/1 H2/CO a~ 300~C and 3000 psi
The broad and narrow cut C~ Flexicoker naphtha distillate
fractions, described earlier by Table IX and Figures 4 and 4, were utilized
as oxo-feeds. Half of each of these feeds were extracted with a 30X KOH
solution in methanol containing 2X water to remove the thiol components.
The caustic treated fractions were then washed with water and
hydroformylated under the same conditions as the untreated fractions. The
synthesis gas reactant was a 1 to 1 CO/H2 mixture. The reactions were
carried out at 130C (266F) at 3000 psi (207 atm).
As a catalyst precursor, Co2(CO)g was added as a 6X toluene
solution under reaction conditions. The catalyst addition was mostly in
increments providing O.lX cobalt to the reaction mixture. The occurrence
of hydroformylation was tested by shutting off the synthesis gas supply and
observing the rate of pressure drop. In general, some pressure drop was
always observed on catalyst addition, but it was not sustained if the
amount of cobalt was insufficient. In such cases, an additional O.lX
cobalt was added every 60 minutes until a sustained reaction resulted.
With sufficlent amounts of cobalt, the pressure drop increased during
catalyst preforming and then gradually decreassd as thç olefin reactants
were depleted.
The reaction mixtures were periodically sampled and analyzed by
packed column and capillary gas chromatography (GC). The pressurs drop and
packet column GC data were used to estimate reaction raees, feed conversion
and overall selectivity to aldehydes, alcohols plus i`ormates and aldehyde
dimers plus trimers. The results obtainad by capillary GC are summarized
in TAble XXVI.
Table XXVI shows that the four feeds e~hibited increasing
reactivitle in this order: untreated broad, caustic washed broad,
-112- ~2~ 73
untreated narrow and caustic washed narrow. For these four feeds the
minimum effective concentration of cobalt catalyst was 0.4, 0.4, 0.3 and
0.2X, respectively. Although the effective catalyst concentration was 0.4Z
cobalt for both the untreated and the caustic washed feeds, the caustic
washed feed was much more reactive.
The packed GC data of Tabl Q X~I show that the GC percentage of
the total oxo-products by the end of the reaction ranged from about 39.3Z
to about 58.6Z. Since the GC response factor for aldehydes is about 1.3,
these GC percentage correspond to 45.7 wt. X and 64.8 wt. Z oxo-products,
respectively.
The percentages of oxo-products derived from the narrow olefinic
feeds are hi~her than those from the broad feeds. This is expected based
on the different olefin reactant content of the two types of feeds. It is
unexpected that the selectivity to total aldehydes is also higher in case
of the narrow feeds. It is believed that the decreased amount of
by-products in the reactlon mixtures derived from the narrow feeds are due
to the lower percentage of cobalt catalyst used. The selectivity was
clearly the highest in the case of the narrow, caustic treated feed where
the lesst catalyst was employed.
The composition of the hydroformylation reactlon mixtures was
further studied using a combination of capillary gas chromotography and
mass spectrometry. The main aldehyde products were identified primarily on
the basis of the characteristic MS fragmentation patterns involving the
McLafferty rearrangement. The formation of the isomeric Cg aldehyde
isomers found from tho C8 olefin isomers of the feed by hydroformylation is
outlined by the following reaction schemes:
i73
-113-
Table XXVI
The Con~crsion of th~ Olefinic Componen~s of C8 ~ractlons of
Fluid-Coker Naphtha by Hydro~or~ylation with 1/1 H2/CO at 130C and 3000 pgi
in ths Pre3Qnc~ of Cobalt Catalyst D2rlvot fro~ Co2(CO~a
Concentration in the Reaction
Run No. Effect- PMixeure by Packed GC. X a
and Total ive Co Drop,bUn-
Feed Time Time Conc. psireacted Alde- Alco- Di-
Used Min.Min~, ~ X ~ eedC hydes ~Q~ ers
120 150 0.2 1.4 93.2 1.9 3.6 1.3
Untreated 180 100 0.3 2.5 93.2 3.1 3.1 0.6
Broad 240 0 0.3 1.2 92.3 3.7 3.3 0.7
300 60 0.4 89.4 6.2 3.6 0.8
450 210 0.414.3 61.228.9 5.2 4.7
530 290 0.~ 57.333.7 5.4 3.6
0.2 2.5 93.2 2.5 3.1 1.2
Broad 120 0 0.3 3.6 92.4 3.6 3.3 0.7
Caustic180 60 0.4 9.1 88.9 6.5 3.9 0.7
Washed240 120 0.453.2 72.219.4 5.7 2.7
300 180 0.4 6.0 59.628.2 5.8 6.4
450 230 0.4 - 50.437.0 7.1 5.5
530 310 0.4 - 49.836.9 8.1 5.2
0 0.2 5.0 95.5 3.0 0.4 1.1
Narrow120 60 0.343.8 55.839.8 1.6 2.8
180 120 0.316.6 48.847.0 2.4 1.8
270 210 0.3 5.0 42.750.4 3.4 3.5
350 290 0.3 - 41.451.5 4.2 2.9
0 0.1 7.0 96.9 2.9 0.1 0.1
~larrow120 60 0.243.2 86.313.4 0.2 0.1
Causeic180 120 0.240.6 61.636.1 1.6 0.7
270 210 0.211.1 50.146.3 2.0 1.6
350 290 0.2 7.0 46.750.8 1.8 0.7
.
aGC concentrations are recorded as such; no conversion factors were used.
bThe rate of pressure drop was observed while H2/CO supply was shut off
fro~ the r~aceor. CBenzene solvent for the catalyst was excluded fro~ the
calculation~. dAlso includes formate esters.
f~3
-114-
Abreviation
C3H7CH2CH2CH~CH-CH2 ~ C3H7CH2C~2CH2CH2CH2CH0 n-
C3H7CH2CH2CH;~CHCH3 ~ C3H7CH2CH2CH2CHCH0 2-Me
~ C~3
C3H7cH2cH-cxcH2cH3 ~ C3H7cH2cH2cHcHo 2-Et
\~ C2H5
C3H7CH;CHCH2CH2CH3 ~ C3H7CH2CHC~0 2-Pr
C3H7
(CH3)2CHCH2CH2CH2CHCHO2,6-Di-Me
(CH3)2CHcH2cH2GH-CHCH3 CH3
(CH3)2CHCH2CH2CHCH02,5-Et,Me
~ I
(cH3)2cHcH2cH-cHcH2cH3 C2H5
(CH3)2CHCH2CHCH0 2,4-Pr,Me
C3H7
The linearities of the C8 aldehyde products derived from the two
pairs of C8 feeds are described by the capillary GC data of Table_ XXVII.
As expected, Cg aldehydes containing a higher percentage of normal nonanal
wera derived from the narrow feeds than ~rom the broad feeds. The final
n-nonanal percentages for the narrow feed derived products are 37.2 and
40X. From the broad feeds final products containing 28% and 23.7Z
n-nonanal ware derived. The difference between the products derived from
untreated and caustic washed feeds of the same hydrocarbon composition is
due to their different degrees of conversion.
With increasin~ conversion, ehe linearity of the products is de-
creasing. At first higher amounts of n-nonanal and 2-methylheptanal (2-Me)
are formed from the most reactivç I-n-octene feed component. As more and
more of the less reactive internal and branched octenes are
hydroformylaeed, the ratio of normal to iso-aldehydes is decreasin~. In
case of the broad feeds, the final n/i ratio is 0.39 and 0.31. Due to the
higher percentage of l-n-octene in the narrow feed, the final n/i ratio of
aldehyd~s there is 0.59 and 0.67.
~2~ 73
--I ,5
O ~ C ~ coo r~
~ ~ ~, ~ o ~ ~ ~ ~ ~ ~ ~ U~ ~o ~ ~ ~ ~ ~
o ¢ ¢ ~
.~ ~U c x
o ~ ~ ~~1~ ~ ~ ~ ~ ~ ~ ,., o ~o~ o c u o
v R r ~ ~ ~ ~ ~ ~ ~ ~ ~ P~ ,~
¢ IC:~ ~ ~ ~ w r~ ~ U7 o ~ 1~ .. o
O O O O O O O O O O O _~ O O O _
~rl ~ r ~ ~ 50 ~ O ~t O o~ o 3~ r~ ~ :~
u~ C u~ cr. o U ~ ~ C~
^u OOO OOOo OOO_~ OOOO
O C~ I ~ ¦ ~ ~0 It') ~ 1~ ~ ~ N C`~ ~ N ~ l ~ 5 C
g ~~ til C~ N ~ c~ ~ a ~ o
CO ~o U C~ o 1~ C~ o ~ ~ ~
c~l o ~ ~ o ~ ~ ~ ~o ~ ~ ~ I~ ~ o u
!~ ~DU ~ Q~ ~ ~ I~ ~ U~ ~ ~ Ir~ ~ r~ ~ ~ ~ ~D ~ ~q h 5
~ o cO u7 ~ ~5), C ~J)
O Cl O O CO CO O ~ r~ O O C~ O O _f O .,~
y O QO .~? c~l ~1 ~ ~ t~ 5 C n
--I U ~ N ~ J ~ ~ C~- ~ O X
U c~ ~ O O ~ l ~ C _ ~
o ~~ o ~ ~ qJ o c
_~ql V c~ r ~ co ~ C oJ L~ o
~ O ~ C ~ ~ O tO ~ 0 h ~ ~ ~
o ~ ~ C o
~ O O C~ ~ ~ O ~ ~ O ~ ~ 5
~ O ~ ¦ `O ~ CO 1` '1 11i t`~ ~1 CO 1~ ~ ~'- O ~ ,C 4~ C
O O O O O O O O O O O O O O O O O O O , 'U C o U
3 ¦ cJ C~ N N ~ 1 N h C~l h ,C
~ a U ~ ~ I ~ ~ U~ ~0 ~ I ~ O u~ ~ ~ N CO 1`~ Ul O O O S C O
0~ Z ~ U ~ o ~ N 1`'1 ~I C`l ~ U
~ O ~0 ~ I O O O O O O O O o o ~ C .~: C
l.J ~ ~ ~ 3 3 t'~ ~ _C~
h f~8 aJ h ~ ~ C _ O
a~ 3 æ z o 3 ~ ~ _ U
U t~ U
~ ~ h . --
73
-116-
Among the minor branched aldehyde components of the reaction
mixture, significant quantities of 2-ethylheptanal (2-Et: 3.75 to 5.09X)
and 2-propylhexanal (2-Pr) are formed. (The percentage of 2-propylhexanal
includes the GC response for an overlapping peak.) These two aldehydes and
2-methylheptanal plus-n-nonanal are all deri~ed from linear octenes.
The two ~ajor cyclic Cg aldehydes (cyclic 1 and 2) were also
formed in significant amounts ranging from 16.40 to 18.23Z of the C8
oxo-products. Compared to these, only lesser amounts of identified
dibranched aldehydes, 2,~-dimethylheptanal (2,6-Di-Me) and
2-methyl-5-ethylpentanal (2,5-Me,Et) were found. Their combined total
ranged from 2.89 to 4.25X.
Among the products derived from the broad C8 feeds, there were
also significant quantities of 2-propyl-4-methyl-pentanal (2,4-Me,Pr) and
cyclic C8 aldehydes. However, these lower boiling aldehydes not listed in
the table since most of their derivation clearly depends on cyclic C7
olefins which are not present in significant quantities in the narrow feed.
The total percentage of some by-products having longer retention
times than n-nonanal is also shown in Tabla II. These components are
cyclic Cg aldehydes, Cg alcohols and Cg alkyl formates. Their total in the
final reaction mixtures derived from the broad cut C8 feeds is 18.9 and
17.2X. The same by-products derived from the narrow C8 feeds amount to
only 6.42 and 4.41X, respectively. The greater amounts of broad feed
derived by-products are due to the formation of higher amounts of cyclic
aldehydas.
To assess the further processability of the hydroformylation
reaction mixtures, they were further analyzed by capillary GC using both a
flame ionization detector (FID) for organic compounds and a sulfur specific
detector (SSD) with quadratic response. As expected two different types of
chromatograms were obtained for the reaction mixtures derived from the
broad and narrow feeds. Uhether the feed was caustic treated or not did
not make a perceptible difference as far as the composition of the reaction
mixtura was concerned. The pentanethiol components of the untreated feeds
were essen~ially all converted during hydroformylation. The thiophenic
sulfur compounds remained essentially unchanged in all cases.
Only trace amounts of sulfur compounds (5-50 ppm range) boiling
in the Cg aldehyde range were formed during hydroformylation. Sulfur
specific GC showed that thelr formation was concurrent with tha early fact
period of hydroformylation. No high boiling sulfur compounds could be
~rd43 '~3
-117-
detected in the reaction mixture. It is recalled that the amount of dimers
and trimers is minimal under the mild hydroformylation conditions used.
In the following, the composition of the reaction mixtures is
illustrated by Fi~ure 14, showing comparable chromatograms based on FID and
SSD detection. Figure 14 shows chromatograms of a final, untreated mixture
derived from the methanolic potassium hydroxide washed narrow feed.
The lower FID trace of Figure 14 shows, that in the case of the
narrow cut feed there is a wide separation between the higher boiling C8
aromatic hydrocarbon feed components and the lower boillng dibranched Cg
aldehyde products. It i5 also noted t~at the total aldehyde product
selectivity is high. There are only small amounts of high boiling dimer
and trimer by-prod~lcts in the reaction mixture.
The upper SSD trace of Figure 14 shows that most of the sulfur is
in the region of the unconverted hydrocarbons. The thiophenic sulfur
components of the feed remained unchanged. However, some other sulfur
components were converted mostly to sulfur compounds of unknown structure.
Minor amounts o H2S are present in the reaction mixture. There are also
two very minor higher boiling sulfur compounds present. They have GC
retention times slightly greater than the aldehyde products. The sulfur
concentration of these two sulfur compounds is about 20 ppm while the
sulfur concentration in the hydrocarbon region is about 2,000 ppm.
All four reaction mixtures were aerated in the presence of
refluxing aqueous acetic acid to convert the cobalt compounds to water
soluble cobalt acetate. In case of the reaceion mixture derived from the
untreated broad cut feed some dark precipitate was formed on standing.
This was not dissolved completely during the cobalt removal procedure.
Thu~, the mixture was filtered to remove it. All the other reaction
mixtures were decobalted without complication. The products derived from
the narrow feed were easier to process. The methanolic KOH treated feed
gave a mixture which was particularly easy to phase separate after caustic
washing.
Capillary GC analysis of the cobalt free reaction mixtures
indicated no significant change during decobalting. However, the de-
cobalted mixtures do not appear to be storage stable. During two months
standing at room temperature, the formation of high boiling sulfur
compounds was observed by sulfur specific GC analysis of ~he decobalted
reaction mixture derived from the untreated broad cut feed. Also, more
dimer formation occurrsd during distillation if the decobalted aldehyde was
-118-
aged. (It is also noted that the distilled aldehyde also tends to
dimerize, i.e. aldolize, slowly during long term storage. In addition, the
aged aldehyde forms ~ore heavies during hydrogenation.)
The di~tillation of the decobalted aldehyde was carried out at a
very low pressure to avoid any thermally induced dimerization. At first
the uncon~erted C8 hydrocarbons were distllled at about 20-25C under 1.2
mm pressure. Most oi the hydrocarbon fractions from the broad cut feeds
and all the hydrocarbon distillates from the narrow cut feed were color-
less. Thereafter, the vacuum was decreased to 0.1 ~m and the aldehydes
were distilled. The aldehydes derived from the broad cut were fractionated
between about 20 and 35C, while those of the narrow cut feed were obtained
between 23 and 31C. Several aldehyde fraceions were taken. ~ost of them
were colorless but so~e of them were slightly yellow. The alcohols and
formate esters were distilled between about 31 and 42C at 0.1 mm. They
were also clear, colorless liquids. However, distillation of the formates
at higher temperature (i.e. under increased pressure) resulted in de-
composition and a slightly yellow distillate. There was no attempt made to
obtain pure alcohol and formate fractions.
The results of the distillations of the various hydroformylation
mixtures were summarized and compared. The aldehyde plus alcohol and
formate distillates were combined in each case and designated as oxo-
products. Based on che results the yields of oxo-products and resLdual
heavy (dimeric and trimeric) by-products per 1000 g reaction mixture were
calculated. The comparative data obtained are tabulated below:
Yields of Oxo-Distillate Products
and Residual By-Products From
Various Hydroformylation Mixtures,
g/1000 g DerivedFrom Different C8
Flexicoker Naphtha Fractions
Broad Broad Narrow Narrow
Un- Caustic- Un- Caustic-
treated treated treated treated
, . __~ , ._ _
Aldehydes 397 494 525 534
Di~ers 85 79 72 53
The tabulation shows that the yield of distilled aldehydes
per 1000 g reaction mixture varied widsly, from 394 to 534 g. As expected,
great~r yields of distilled oxo-products were obtained from the narrow C8
cut feeds of higher olefin content than fro~ the broad C8 fractions. Fro~
- 119-
the two broad cuts, the caustic treated led to a much higher yield than the
untreated because of the higher feed conversion (See Table I).
The Cg aldehyde distillates (9OZ or more) obtained from the
different C8 Flexicoker naphtha ~ractions were mostly combined to provide
feeds for hydrogenation to produce the corresponding Cg alcohol products.
It is noted that in the case of the products derived from
the narrow cut untreated distillates, the normal n-nonanal content was
generally lower and the higher boiling components were more prevalent than
in the narrow cut feed derived products. All the hydrogenations were
carried to in the previously described manner in the presence of 5X water
and lOX Co5/MoS based catalyst at 160C under 3000 psi pressure for 20
hours. The same catalyst was used repeatedly in the present tests.
Analysis of the hydrogenated raction mixtures by packed and
capillary GC indicated that the Cg aldehydes were reduced to the
corresponding Cg alcohols in a selective manner. Alcohol selectivities
ranged from 85 to 97~.
According to packed GC, the hydrogenation of the aldehyde
derived from the broad C8 fraction occurred with less than 2% dimer
formation. In the case of the narrow cut derived aldehydes, dimer
formation was about 15X.
Capillary GC indicated that paraffln for~ation was minimal,
less than 5%, in all cases. n-Nonane was by far the largest paraffin by-
product. Its concentration was leqs than 4X of the alcohol products. In
general, the selectivity toward the isomeric nonyl alcohol products, was
very high.
Sulfur specific GC shows that most of the low boiling
sulfur impurities are dimethylthiophenes, i.e. components of the broad cut
C8 feed. There was no sulfur in the alcohol retention time range.
However, all of the ~ixtures showed the presence of some sulfur in the
dimer range. Apparently, the minute smounes of aldehyde range sulfur
compounds, which were present in the feed, were convert~d during
hydrogenation into sul~ur derivatives of low volatility.
The composition of the low boiling components o~ the
aldeh~de ~eeds and alcohol product mixtures was studied by capillary GC and
compared in Table XXyIlI~ The data of Table XXVIII show that both of tha
feeds and the products derived ~rom the broad C8 cut contain less normal,
i.e. less C3 straight chain, oxygenates and more higher boiling components
than those of the narrow feeds. The concentration of n-nonyl alcohol
-120- ~$~73
Table XXVIII
Hydrog~natlon of tha Gg Ald~h~des Deriv~d Via the Hydroformylation of
Various C8 ~losicoker Naphtha Fractions
Components Composition by Capillary GC X
in Relation (of Reactants and Products Derived
to Their ~from Various C8 Fractions
TypeRetention
oftimes to Broad Broad Narrow Narrow
MixtureNormal Un- Caustic Un- Caustic
~31Y3~ g~ reated Treated tre~ted Treated
Aldehyde ShorterC 57 52 64 56
Reactant Normala 27 21 33 37
Longerd 16 27 3 7
AlcoholParaffinse 1 4 2 0
ProductShorterf 61 52 60 59
Normala 22 17 29 35
Longerg i6 27 9 6
a)Normal n-nonanal reactant or n-nonyl alcohol product. b)Based on
analyses of hydrogenation feeds and reaction mixtures. C)Branched
aldehydes of shorter retention time. d)Aldehdyes of longer retention
time. e)c~ Paraffin by-products. f)Alcohols of shorter retention
times. g)Alcohols of longer retention time, excluding dimers.
.
73
-121-
products is generally lower than that of their n-nonanal presursors. This
is due to the preferred aldolization of n-nonanal to provide the
corresponding dimer. The exact concentrations of dimers could not be
determined by capillary due to their limited volatility. The concentration
of volatile C8 paraffin by-products was generally very low, 0 tO 4X, as
indlcated by the Table XXIII.
The hydrogenation reaction mixtures wer~ washed with lOZ
aqueous sodium hydroxide solution and then water to remove hydrogen -~ulfide
and carboxylic acid by-products. The separation of the aqueous and organic
phases occurred readily. After a final water wash, the mlxtures were
fractionally distilled to recover the alcohol products.
A 24 plate Oldershaw, column was employed to separate the
hydrocarbon solvent and by products from alcohol product fractions. The
dlmer and trimer by-products wers usually obtained as a distillation
residue. The fractional distillations were carried out under reduced
pressure using a heating bath of less than 200C to avoid the decomposition
of sul~ur containing dimeric by-products.
All the Cg alcohol distillates were colorless clear
liquids. The alcohol fractions of the reaction mixture derived from the
broad C8 feed fractions, were distilled between 91 and 111C at 18 mm. As
expected, the alcohol distillates derived from the narrow C8 feed had a
narrower boiling range. They were obtained be~.ween 95 and 107C at 18 mm.
The dimer by-product derived from the narrow C8 feed was also distilled.
It was obtained as a clear colorless liquid between 88 and 98C at 0.05 mm.
The alcohol distillate products derived from each of the
four C8 Flexicoker feed~ were analyzed by capillary GC and combined to
provide four alcohol products. The distillation residues consisting of
undiqtilled alcohols, dimers and trimers were anlayzed using a packed
colu~n GC. The yields of products and by-products, obtained from the crude
products and by-products, obtained from the crude product mixture after
distiling of the hydrocarbons, are shown togather with the yields of
combined alcohol distillates in the following tabulation:
122~ 73
Yields of Alcohol Distillate Products
and Residual Products, wt Z
(Derived from Different C8 Flexicoker Fractions)
.
Broad Broad Narrow Narrow
Un- Caustic Un- Caustic
TreatedTreated Treated Treated
.. .. _ . . _
Alcohol Distillate 90 58 77 6~
Residue 10 42 23 40
Alcohol 9 10 3 10
Dimer 1 31 18 30
Trimer - 1 2
As it is shown by the above data, the yields of alcohol
distillates range fro~ 58 to 90Z. The large differences in Cg alcohol
yields are apparently due to the different degrees dimer by-product
formation. The dimers are dexived from the aldehyde reactants via
aldolization hydrogenation. It is noted that there is less dimer formation
from the aldehydes derived from ehe untreated C8 feeds, possibly due to the
presence of aldolization inhibitors.
For a comparatlve characterization of the composition of
the free alcohols based on eheir capillary GC, the conceneraeions of the
components, having shorter retention eimes than n-nonyl alcohol, were added
up. Similarly, the total percentage of the components having longer
retention times was determined. These percentages were ehen compared wieh
that of the n-nonyl alcohol componen~. They~are shown for all four alcohol
products by the following tahulation:
: :
73
-123-
Composition of Cg Alcohol Distillate Products
(Derived from Different C8 Flexicoker Fractions)~
Grouping of
C~mponents Broad Narrow
According to GCBroad Caustic Narrow Caustic
Retention TimesUnTreatedTreated UnTreated Treated
Shorter ~4.2 73.7 63.5 67.0
n-Nonanol 26.3 19.1 34.5 31.6
Longer 9.5 7.2 2.0 1.4
The data of the tabulation show that the broad C8 feed
derived alcohols have a lower percentage of n-nonyl alcohol component than
those based on narrow C8 feeds. The differences betwen the n-nonanol
content of distilled alcohol products derived- form untreated and caustic
treated C8 feeds appear to be due to difEerences in alcohol recovery. The
distillation of higher boiling alcohol components was less complete from
the product mixtures derived from the caustic treated feeds.
The above discussed four Cg alcohol distillates did not
contain any sulfur detectable by the capillary GC method employed (This
method would have detected any single sulfur compound present in 5 ppm
concentration or more). Samples of these distillates were submitted for
total sulfur analyses. The broad untreated and treated distillat~s were
found to contain 22 and 43 ppm sulfur while the corresponding distillates
derived from the narrow cut feed contained 13 and 31 ppm, respectively.
Overall, the above analytical results and other observations suggest that
most of the sulfur compounds, distillin~ in the dimer by-product range,
were formed during the aldehyde to alcohol hydrogenation.
A series of comparati~e odor tests were carried out with
the alcohol products. The results showed that these alcohols have odors
typical of Cg oxo alcohols in general.
The aicohols were converted to semilinear diheptyl
phthalate which was evaluated as a plasticizer.
g~3
-124-
Examples 35 and 36
Hydroformylation of A C9 Olefinic Fraction of Naphtha by
H2/C0 with Cobalt fit 3000 pSi in the 130-150C Tempera~ure Range
The Cg olefinic feed for the present hydroformylation
experiments was derived from a C4 to C12 Fluid-coker naphtha by a double
15/10 type distillation. The second distillation started with a broad Clo
cut of bp. 145 ~o 155C and produced a narrow cut of bp. 143 to 148 in
about 40X yield. The concentrations of the major components of the broad
and narrow boiling fractions is shown by the following tabulation:
Cg Olefinic Feeds
Boiling Point ~
F Narrow Cut Broad Cut
Ide~iflcation C _ A~prox.Bp! (143-148C)Bp. (145-155C)
Ethylbenzene 136.2 277 0.35 2.10
2,5-DiMe-
Thiophene 136.7 278
p-Xylene 138.3 281 1.82 7.04
m-Xylene 139.1 282 0.64 2.05
o-Xylene 144.4 292 4.93 7.90
l-Nonene 146 295 24.09 21.06
n Nonane 150.8 303 17.43 15.45
2,3,5-TriMe-
Thiophene 160.1 320
l-Me, 3-Et-
Benzene 161.3 322 0.75 2.17
It is apparent that the second 15/10 distillation was not
sufficiently effective to produce the desired narrow l-n-nonene rich
fraction in a high yield. However, it was possible to exclude most of the
aromatic components from the narrow nonenes fraction by accepting a low
distillate yield. Sulfur GC indicated that most of dimethylthiophenes and
trimethylthiophenes were removed during the second fractionation with the
xylene~ and l-methyl-3-ethylbenzene respectively. The sulfur content was
reduced from about 1.5 to 0.2%.
The narrow, olefinic fraction of the Cg Fluid-Coker naphtha
(E-7285~ was hydroformylated using a 1/1 mixture f H2 and C0 in the
presenca of 0.2Z Co. The cobalt catalyst was introduced as a 13X solution
of its precur~or, Co2~CO)g, in toluene. The reaction was carried out at
3000 psi at variable temperatures. The tem~erature was increased during
-125-
the course of the reaction to convert the various types of olefins at their
minimum reaction temperature.
The solution of the Co2(CO)g catalyst precursor was added
at 120C. This reaction temperature was maintained for 1 hour.
Thereafter, the reaction temperature was raised to 130C. Similarly, the
temperature was increased to 140 and then 150C after 1 and 2 hours,
respectively. After a total reaction time of 4 hours, the reaction was
discontinued.
The results of the hydroformylation are shown by Table
XXI~. For comparison, Table XXIX also lists some of the data obtained in
an experiment carried out with 0.1~ catalyst in an identical manner.
The composition of the reaction mlxtures by packed GC
showed that the reactlon was highly selective to aldehydes. After 4 hours
in the presence of 0.2X Co, the hydroformylation reaction~was essentially
complete. According to GC, the concentration of aldehydes in the reaction
mixture reached 45X. Experiments to determine GC response factors with
n-decane, n-decanal, n decanol mixtures indicated that the 45X GC response
corresponds to about 50% by weight of aldehyde. To reach this aldehyde
concentration, a minimum of 44.7X olefins in the feed had to be hydro-
formylated. At this point, the reaction mixture still contained only about
5X alcohols plus formate esters and about 3X dimers and trimers.
The isomeric Clo aldehyde distribution by capillary GC
showed that the n-decanal was far the most prevalent oxo product.
n-Decanal, of course, was mostly derived from the most reactive l-n-nonene
olefin component of the feed. Thus, its percentage of the total oxo-
products wa particularly high (58.2X) during the early phase of the
reaction. At the completion of the reaction, the percentage of the
n-decanal was 44.8X. The percentage of the second largest Clo aldehyde
isomer, 2-methylnonanal was 16.2X. Thus, these two aldehyde isomers which
can-be derived from l-n-nonene made up 61X of the oxo products. As
expected the other 2-alkyl substituted Clo aldehyd~s derived from linear
internal octenes (2-ethyloctanal, 3-propylheptanal and 4-butyloctanal~ were
other significant product isomers, in a total concentration of 71.3X.
Thus, the total concentration of oxo products derived from linear olefins
is about 84.8X.
Capillary GC also indicated the formation of comparable
amounts of isomeric alcohols and their fcrmate esters having alkyl
structures corresponding to the isomeric decanal products. These secondary
--126--
3 ~ o 3 ¦ ~ ~ ~
~ ~y ~o ¢ U ~ o o o
X U
o ~ '~
~o ~ ,~ ~
.~¢ ~oo ,~ "
~- ~ t~ ~ 0~ A 'g
8 ~ ~ " o ,. o u~
~ ~j o 3 3 C ~æ: rC a~ D O
~ ~ ~ ~ z ~ = 3
O N '~ C ¦ ~ ~ ~1 ~
-¢~ o I O~
O ~ O o 0 ¦ ~o ~0 o~ ~ ~ ~ ,~ r ~
~ ~ cC ~ ~ ~
o 3 ~~ ~c ~ ~ o o ~ E~ '~
~- ~ ~ l u ~ 7
@ U~ C~ OOOO OO
~,o ~~ ox C~
C E~ ~ N
-127-
by-products were rich in the normal isomers, particularly the alkyl
formates.
The decobalted combined hydroformylation reaction mixtures
w~re fractionally distilled in vacuo uslng a two foot packed column. At
first 1160.5 g ~34.7X) of unreacted hydrocarbon components were removed at
close to room temperature under 1 mm pressure. Thereafter, the remaining
2184.5 g (65.3X) mixture of oxygenated products was fractionated. Most of
the isomeric Clo aldehyde products were received between 43 and 49C at 0.5
mm. me total amount of the aldehyde distlllates was 1197.5 g (35.8X of
~he reaction mixture). No attempt was made to separate the Clo alcohol and
Clo alkyl formate products. They were d1stilled between 40 and 55C at
0.05 ~m and received as 466.5 g (14X) of a colorless to light yellow
liquid. Thus, the combined weight percentage of alcohols and alcohol
precursors in the reaction mixture was 49.8. The C20 dimer products of
aldehyde condensation were largely distilled be~ween 118 and 122C at 0.05
mm. About 296 g (11.8X) of these dimers were obtained as a pale yellow
liquid, Finally, 102.5 g (3.2X) C30 trimers were also obtained largely at
abut 215C at 0.5 mm. as a clear yellow distillate. The last of the
trimers wers distilled with some decomposition. The distillation residue
was 22 g (0.5%) of the reaction mixture.
To prepare the desired semilinear Clo alcohol, a combined
Clo aldehyde feed of the following composition was used.
2-Butylhexanal 1.0 n-Decanal 23.4
2-Propylhexanal 3.3 n-Decanol 2.1
2-Ethyloctanal 3.9 n-Decyl Formate 4.2
2-Methylnonanal 10.1 29.7
18.3
The percentage of the n-decanal in this feed (23.4X) is low due to its
preferential condensation and further side reactions of n-decanal during
distillation. Sulfur GC of this aldehyde showed no sulfur compounds in the
aldehyde range. Trimethylthiophenes were present in about 40 ppm
concentration indicatLng an imperfect separation of feed hydrocarbons from
product aldehydes by distillation.
The above Clo aldehyds feed was hydrogenated in ~he
presence of 5Z water 10.7 wt.X CoS/MoS catalyst at 150C (302F) under 3000
-128-
psi (307 atm) for 40 hours. The desired al~ehyde to alcohol conversion was
complete. Combined GC/MS analyses indicated the absence of aldehydes.
The percentage of n-decyl alcohol in the crude product
29.6Z. This percentage corresponds to the combined concentration of
n decanal, n-decyl formate plus n-decyl alcohol in the aldehyde feed.
Sulfur GC of the crude alcohol indicated that the
trimethylthiophenes were the main components (61X). However, minor amounts
of sulfur (39%, about 14 pp~) was also present in the alcohol range. These
latter sulfur compounds were apparently formed from the low molecular
weight sulfur compounds during hydrogenation.
Most of the crude Clo alcohol hydrogenation product (1356
g) was fractionally distilled using a 24 plate Oldershaw column. An early
product fraction (47 g) containing aromatic hydrocarbons and
trimethylthiophenes was obtained between 21 and 110C at l9 mm.
After the above fraction, six colorless, clear isomeric
decyl alcohol distillate fractions were obtained. Their amounts, boiling
ranges, linearity and total sulfur content are listed in the following:
Bp. _ _cohols,_Z _
Fraction AmountC/mm Decyl- Highera Approx.
No. g n- i- S, ppm
IV 82 111/19
V 222 111-116/19 6.7 93.3 50
VI 222 116-117/19 14.1 84.7 2.2 20
VII 423 117-121/19 41.9 49.0 9.1 40
VIII 196 121/19 58.3 41.717.3 30
XI 3~ 58/0.1 2.0 83.083.0
The higher alcohols having retention times lon~er than
n-decyl alcohol are probably dibranched undecanols.
The above tabulation shows that ~ractions enriched in the
linear alcohol can be obtained. Fractions VI, VII and VIII were selected
as heart cuts ~or conversion to semilinear didecyl phthalate esters, which
are evaluated ~s plastlcizers.
Altogether 1230 g (86Z) of clear, colorless alcohol
products were recovered by distillation between 111 and 121C at l9m~.
About 45 g (3.4 wt. X of the feed) of a clear yallow distillate was
recovered ~n the broad dimer range. Apparently, some aldehyde condensation
73
-129-
occurred during hydrogenation. Most of the dimer distilled between 165 to
172C at 0.1 mm. Packed GC of the distillation residue (18 g) indicated
that its volatile components were in the trimer range. The aldehyde
fraction had no sulfur detectable by GC. However, the dimeric aldol
alcohol contained about 1.2X sulfur.
Examples 37 and 38
Hydro~ormylation o~ Clo Naphtha B7 3/2 H2/CO
wi~h 0.2 and lX C~balt at 130C ~nd 3~00 psi
The preYiously described Clo fraction of the Fluid coker naphtha
was hydroformylated as a 1/1 mixture with hexane at 130C by an about 60/40
mixture of H2/CO at 3000 psi, using the high pressure procedure. The
catalyst precursor was dicobalt octacarbonyl.
In the first experiment, the cobalt complex catalyst used was
equivalent to 0.2X cobalt, i.e., 34mM. The reaction mixture was period-
ically sampled and analyzed by capillary GG. The progress of the reaction
was followed by determining both the l-decene reactant consumed and the
aldehyde product. The main aldehyde produts were the n-aldehyde and
2-methyl substituted aldehyde derived from l-decene. The data obtained are
tabulated in the following:
_ Reaction Time. Min
_10 30 60 120
l-Octene Converted, X 12 54 100 100
Ma~or Aldehydes Formed, Z 7 51 93 105
Total Aldehydes Formed, X 143 203
n/i Ratio of Ma~or Aldehydes 3.35 3.39 3.15
It is apparent from the data that the l-n-decene was converted at
first. However, by the end of the 2 hour reaction period a significant
reactlon o~ the isomeric decenes also occurred. The final ratio of the two
ma~or aldehydes formed was 3.15. No significant secondary reaction took
place. Alcohol formation was negligible. High boiling by-products were
virtually absent.
In ~he second experiment, the same reaction was carried out in
the presence of 1~ cobalt. This resulted in a very fast reaction. In 10
minutes, the l-decene component was completely converted. The amount of
the two ma~or aldehydes formed was 105~ of the theoretical quantity
-130~ L~ ,3
derivable from l-decene. The total aldehydes formed were 212X of this
calculated value. The n/i ratio of the two major aldehyde products was
2.71.
The second experiment was also run for 2 hours. During the
second hour much hydrogenation occurred. By the end of the second hour,
essentially all the primary aldehyde products were converted to the
corresponding alcohols.
Examples 39 and 40
~ydro~or~yla~ion of C8 Naphtha by 3/2 and 1/1
H2/CO with Cobalt at 130C and 3000 psi
The C8 fraction of the previously described naphtha was hydro-
formylated in hexane in the presence of 0.2Z cobalt at 130C and 3000 psi
in two experiments. The H2/CO reactant ratio was about 60/40 in the first
experiment while an equimolar mixture of synthesis gas was used in the
second.
Qualitatively, the reaction of octenes in this example was
similar to that of decenes as described in the previous examples. However,
the reaction rates were generally lower. A summary of data obtained in the
first experiment with 60/40 H2/C0 is provided by the following tabulation:
_ Reation~Time. Minutes
30 _ 60 120
l-Octsne Converted, X 6 14 29 100
~ajor Aldehyde Formed, X 3 10 21 92
The reaction had an induction period during the first hour. However, the
conversion of l-n-octene and some of the isomeric octenes was rapid during
the second hour. The total amount of aldehydes formed was 144X of the
theoretical amount produced from l-n-octene. Nevertheless, due to the low
reaction temperature, no aldehyde hydrogenation to alcohol occurred. The
n/i ratio of ehe two major products was 2.78, definitely lower than in the
analogous experiment of the previous example.
The second experiment of this example was carried out under the
same process conditions, but using a l/l rather than 3/2 mixture of H2 and
CO reactant. The results of the two experiments were very similar; the
H2/CO reactant ratio had no apparent major effect at this temperature. The
second experiment using 1/1 H2/CO appeared to have a slighely longer
$73
-131-
induction period. Howsver, during the second hour of the reaction, a rapid
conversion took place. By the end of the second hour, all the l-n-octene
was converted. The reaction was continued for a third hour. Additional
conversion of the other isomers occurred. After three hours reaction time,
the total amount of aldehydes formed was 187X of the theoretical yield
calculated for the l-n-octene component of the feed. On the same basis,
the yield of the total aldehydes formed in 2 hours was 125X.
Examples 41-42
Hydroformylation of Cg Naphtha by H2/CO ~i~tureg
of Va~ying Ratio~ with Dlcobalt Oceacarbonyl
at 150C and 3000 p~i
C8 naphtha fraction was hydroformylated in hexane solution as
usual in the presence of 0.2X ~obalt provided as dicobalt octacarbonyl.
Compared to the previous example, the only significant difference was the
use of a higher temperaturs, 150C. Three experiments were run with
different initial and/or final H2/CO ratios.
In the first experiment, where a 3/2 ratio of H2/CO was used all
through the reaction, a severe inhibition of hydroformylation was observed.
After 1 and 2 hours reaction time, the amounts of reacted l-n-octene were
only 20 and 27X, respectively. As expected, the significant products were
n-nonanal and 2-methyl octanal. Their ratio was 3.48.
In the second experiment with an initially equimolar H2/CO
reactant, a much faster reaction was observed. About 20X of the l-n-octene
component reacted in 10 minutes according to GC; all ~he l-octene reacted
in 30 minutes. In 60 minutes, much of the linear octenes and 2-methyl
heptene-l wera also converted. The product data obtained on GC analyses of
product ~amples were the following.
-~@i9s12D_~L~e__~in _
30 _ 60 120
Two Ma~or Aldehydes Formed, X 59 92 84
Total Aldehydes Formed, X 82 182 201
n/i Raeio of Major Aldehydes 2.59 2.41 1.92
The data indicate that significant amounts of olefin
isomerization occurred during hydroPormylation. Dur~ng the first part of
the reaction, the ma~or l-n-octene component was partly isomerized to the
thermodynamically favored linear octene Thus, no l-octene was shown in
~ ~ 6 3
-132-
the reaction mixture after 30 minutes, even though only 59~ of the products
derivable from l-n-oc~ene were formed. Most of the hydrofor~ylation took
place during the subseq~-ent 30 minutes. An apparent side reaction during
the second hour was the hydrogenation of aldehyde products to the
corresponding alcohols. By the end of the reaction, llZ of the total
n-octanal formed was converted to n-octanol. However, the hydroformylation
of internal octenes during the same period more than made up for the loss
of total aldehydes via hydro~enation. During the second half of the
hydrogenation period, the yield of the total aldehydes for~ed increased
from 182X to 201X of the calculated yield for l-n-octene. At the end of
the reaction, less than half of ehe aldehydes were derived from l-n-octene.
As the amount of aldehydes formed from isomeric octenes rather than
l-n-octene increased with time, the n/i raeio of the two main aldehyde
products dropped from 2.59 to 1.92. The apparent increase of
2-methyloctanal formed in part was due to the overlap of GC peaks.
However, additional amounts were formed from 2-octene.
It is noted that although the initial H2/CO mixture used to
pressure the reaction vessel was equimolar, the feed gas durin~, the
reaction had a H2/CO ratio of about 60/40. Since the liquid reaction
mixture was sampled four times with considerable gas loss, by the end of
the reaction the H2/CO ratio Increased to 60/40. It is felt that the
initially low value of H2/CO was critical in overcoming reaction
inhlbition.
In the third experiment, the H2/CO reactant ratio of both the
initial and run synth~sis gas was equimolar. However, the maintenance of
the low H2/CO ratio r~sulted in decreased reaction rates when compared to
the prevlou~ experiment.
The a~ounts of l-octene converted after lO, 30, 60 and 120
~inutes, were 30, 38, 79 and 100%, respectively. The yields of the t~o
major products, n-octanal plus 2-methyl heptanal, after 60 and 120 minutes
were 44 and 86X, respectively, based on l-n-octenf~. During the same last
two periods, the yield of the total aldehydes for~ed was ~l and 170%. The
n/i ratio of the two ma~or products was 2.70 and 2.48, respectively. By
the end of the reaction, 3.5X of the n-oceanal was hydrogenated to
n-octanol. Overall, ths GC data obtained showed that although l-octene
conversion started immediately, the final extent of hydroformylaeion was
lower than in ehe previous example. High CO partial pressure was important
$ L~: ~ 7 3
-133-
in overcomin~ the initial inhibition, but the H2 partial pressure was
insufficient to assure a high hydroformylation rate.
Example 43
Hydroformylation of C8 Naphtha by 3/2 H2/CO wlth
Dicobalt Octaearbonyl at 150C and 4500 p8i
A hexan0 solution of C8 naphtha was hydroformylated as usual in
the presence of 0.2X cobalt by 3/2 H2/CO at 150C and 4500 psi. The
conditions were identical to those of the first experiment of the previous
example, except the pressure was increased In the present experiment from
3000 to 4500 psi. This resulted in a drastically reduced initiation period
and a much more complete conversion of the olefin components during the two
hour reaction period.
In ten minutes, 19% of the l-n-octene was converted and n-octanal
was formed in amounts corresponding to llX of the starting l-n-octene
reactant. Thereafter, a rapid reaction took place. In 30 minutes,
essentially all the l-n-octene and the 2-methyl heptene-l were converted.
GC analyses provided the following data on the products formed.
Reaction ti~ Min.
120
Two Major Aldehydes Formed, X 95 120 105
Total Aldehydes Formed, X 149 247 291
n/i Ratio of Ma~or Aldehydes 2.9 2.7 2.5
n-Octanal Converted to n-Octanol, Z 10 16
It is particularly noted, that after the initial conversion of
the l-n-octene in 30 minutes, the total yield of aldehydes increased from
149 to 291% of the calculated yield for l-n-octene. This increase is due
to the conversion of internal olefins. It should also be noted that the
final n~i ratio of the two majo~ aldehyde products was fairly high (2.5),
considering the high conversion of intPrnal olefins.
During the second hour of the reaction period, there was a ~light
decrease of ~he two ma~or aldehydes in the mixture. This is apparently due
to hydrogenation of aldehydes to alcohols. A comparison of the GC signal
intensities indicated that about 16X of the n-octanal formed was converted
to n-octanol.
-134- 1~7~
Thus the results show that at the increased pressure of the 3/2
H2/CO mixture, the concentration of C0 is sufficient to overcome the sulfur
inhibition. The high partial pressure of hydrogen results in a high
reaction rate of both l-n-olefins and internal olefins.
Example 44
Hydroformylation f Clo Naphtha By H2/CO Mixtures of Vsrying
Ratios ant With Varying Concentrations of Cobalt
and Sep~ration of Cll Aldehyde Products
The Clo fraction used was a high boiling naphtha fraction. The
l-decene content of this fraction by GC was about 16X. Based on an NMR
analysis, the type distribution of the decene components was the following:
RCH-CH~ RCH~C~ R2C CH2 R2C-CHR Decadiene
I II III IV Conjugaeed
43% 22X 14X 9X 12%
Ass~ing that l-decene is the only type I olefin present, the total
percentage of olefinic unsaturates was 37X.
About 1900g portions of a Clo Fluid-coker naphtha fraction
similar to the one previously described were hydroformylated without any
significant amount of added solvent in a 1 gallon reactor. The cobalt
catalyst was added as an approxi~ately lOX solution of dicobalt
octacarbonyl in toluene. The resulting essentially non-diluted feeds
contained increased concentra~ions of both olefin reactants and sulfur
inhibitors. As such, they required greater amounts of cobalt for effective
ca~talysis.
There were two experimenes carried out using dicobalt
octacarbonyl as a catalyst precursor at 130C under 3000 psi pressure, with
1/1 H2/C0 and 3/2 H2/C0 reactant gas, respectlvely. The initial amount of
the catalyst employed was equivalent to 0.2% cobalt in both cases. This
amount of catalyst did not lead to any significant hydroformylation in S
hours in either case. Thereafter~ an additional O.lX and 0.2X,
respectively, of cobalt were added after cooling the mixtur~ and starting
the reactions again.
-135- ~2~73
When the first experiment was resumed in the presence of a total
of 0.3X cobalt, hydroformylation occurred at a moderate ra~e. All the
l-n-decene was consumed in 120 minutes. The total reaction time was 5
hours. GC analysis of the final reaction mixture indicated a total
aldehyde product yield of about 253~, based on the amount of l-n-decene in
the feed. The n/i ratio of the two ma~or aldehydes was about 2.7. Ths
percentage of these aldehydes in the total aldehyde mixture was 41Z. In
the case of the second experiment (Example 30~, with a total of 0.4%
cobalt, the hydrofor~ylation was fast. All the l-decene was converted
within 10 minutes. This reaction was continued with the increased amounts
of cobalt for 3 hours.
Overall, the two experiments gave similar results, and indicated
that the initial small amoun~s of cobalt catalyst were deactivated, but the
inhibitors were thus consumed. Thus, the added amounts of cobalt showed
high activity which was little dependent on the H2/CO ratios employed.
The composition of the combined final reaction mixtures is shown
by capillary GC and packed column GC's in Figures 8 and 9, respec~ively.
Fi~ure 15 shows a typical reaction mixture containing major
amounts of n-paraffin and n-aldehyde. Clearly, recognizable isomeric
aldehyde products are also shown. These 2-alkyl substituted aldehydes are
apparently derived from thc various linear olefin isomers of the feed.
Their structure was established in GC/MS studies on the basis of the
characteristic ions ~ormed on electron impact ionization. As it is
indicated by the spectrum, decreasing amounts methyl, ethyl, propyl and
butyl branched aldehydes are present.
Fi~ur~ 16 shows the packed column GC of the same reaction
mixture. This GC shows less separation of the individual components, but
extends the analysis to the high boiling aldehyde di~er and trimer
by-products. It indicated that they amount only to about 2.9X of the total
reaction mixture.
For a more detailed study of the products, it was decided to
distill the reaction mixtures. The t~o products were combined. The cobalt
was removed as cobalt acetate by hot aqueous acetic acid plus air treat
ment. The organic phase (976g) was then fractionally distillsd in high
vacuo using a one foot packed column. The unreacted Clo hydrocarbons were
distilled at room temperature at 0.1mm and were collected in a cold erap,
(491g, 50 wtX~. Therea~ter, the Clo aldehydes were dlstilled. Durin~ the
distillation, some thermal decomposition of the residual liquid (probably
-136~ $ ~3
of the formate by-products) took place. As a consequence, the vac~-um
dropped to 0.5mm. How~ver, while the bath temperature was slowly increased
to 100C, the decompositlon has subsided, the vacuu~ improved and the Cll
aldehyde products were distilled between about 50 and 60C at 0.lmm and
received as colorless liquids (371g, 38 wtX). The residual liquid dimers
and trimers were 112g, 12 wtX. Packed CC indicated that about 2/3 of this
residue was consisted of very high boiling compounds, probably trimers. A
large percentage of ~hese heavy by-products was formed upon heating the
mixture during fractional distillation.
The distlllation results indicate that the total oxygenated
product corresponds to ths yield calculated for a feed at 45% olefin
content assuming complete conversion. The isolated aldehyde content is
less, it corresponds to an effective utilization of about 36% of the total
feed.
Capillary GC of the distillate product showed that the two major
aldehyde products are derived via the hydroformylation of l-n-decene:
C8H17CH-CH2 C/H2~ C8H17CH2CH2CHO + CgH17CHCHO
CH3
These two ma~or products, n-undecanal and 2-~ethyldecanal, constltute 49X
of the aldehydes. Their ratio is 2.23. Other minor aldehydes were also
identified by GC/MS.
Based on the above detailed analyses, it was calculated that the
total oxygenated products contain 0.65 branch per molecule.
The Cll aldehyde products were reduced to the corresponding C
alcohols which were converted to semilinear diundecyl phthalates. The
latter were evaluated as plasticizers.
Examples 45-47
Hydro~or~ylation of Atmo~ph8rically and Vacuum
Distilled Clo Naphtha Fractlons ~ith Cobalt
A series of three hydroformylation experiments was carried oue
w~th three different Clo naphtha fractions in a manner described in the
prevlous two examples to determine the effect of the conditions of the
fractional distillation of the naphtha feed on the reaceivity. Infor~ation
about the feeds and hydroformyla~ion results i5 sum~arized in Tabla_XXX.
The first fraction employed as a ieed was an atmospherically
-137- ~ $~3
C I ~ ~ ~
~, ~ ~ _
_ ~Ql G' O et ~ --O
C ~ C I ~ o ~ ~
- ~ .l ._
33 ; ~1 ~' ~-- ~ . ~a
O ~, L
~æ ~ ~ c
a ~i3c E ¦ O O O O O O ~77 0 ~ v~
o c~
C ~ ~ l OO~ 3
.~ I -~a ~ O a
: ~ a~ ~1~ co _ ~ ~ o cr o~ _ o o~ ~ O ~
~_ ~ e t,~ 1~ _ O O ~ D O ~ N r~ 0 r~ ~ ~ _ X
_~ ~ ~ ~ D W C~ O ~ ~ e
~O ,0 ~ .
O E co O O o o o O o O o O o o o
LL ~ ~ ~_
~ a~ V~ 1-+ + -+~ ~
~a ~ a
~ o ~ ~ ~
O ~ ~,
¦ o c e o
~ ~ ~ ~ E ~
o o ~ ~ ~ c .'~ ~ E a;l G
a ~ -- ~ ~ E s ~) aa g c
z E v~ o~n ~t 0~ E ~ ~ _ o
~ .C ~ ~ ~ c ~ --
E 2~ ~
L.J ~ 1' "
7~3
-138-
distilled Clo cut between 342 and 350F (172-177C). According to
capillary ~C, it contained 10.9X l-n-decene and 13.9X n-decane. About
55.5X of the components of this cut had longer retention times than
n-decane. These components included indene.
The second fraction was obtained at reduced pressure under 240mm.
It contained 17.0Z l-n-d~cene and 15.0Z n-decane plus 42.7~ of higher
boiling components.
The third fraction was derived from an atmospherically distilled
Clo fraction by redlstilling it in vacuo at 50~m. This vacuum distilled
fraction mainly consisted of compounds boiling in the range of l-n-decene,
n-decane or lower. The n-decene and n-decane contents were 19.5 and 16.5X
respectively. Only 23.lX of this fraction had GC retention times greater
than that of n-decane.
The above described, somewhat different, three Clo fractions were
used as hydroformyla~ion feeds in the presence of 0.lX and then an
additional 0.1X Co catalyst, both added as Co2(C0)g. Each run was carried
out using 1/1 H2/CO as reactant gas under 3000 psi at 130C (266'F). The
reaction mixtures were sampled at intervals and analyzed by packed and
capillary GC columns. The results are summarized in Table XXX.
The GC composition data of the threa Clo reaction mixtures
hydroformylated in the presence of 0.1~ cobalt in athe a series of
experiments in Table XXX) show that no significant hydroformylation
occurred in 360 minutes. There was some initial reaction as indicated by a
small pressure drop and minor aldehyde formation during the first cen
minutes. However, the reaction soon virtually stopped. It is apparent
that the cobalt carbonyl was deactivated by the inhibitors present in the
Clo coker dlstillate feed.
After the unsuccessful attempts of reacting the three Clo
fraetions in the presence of 0.lX cobalt, an additional 0.1~ cobalt was
added to the reaction mixtures. This resulted in effective
hydroformylation in all three cases (in the b series of experiments).
However, the hydroformylation rates were somewhat dependent on the
particular Clo feed as described in the following.
The atmospherically distilled Clo naphtha was the least reactive.
Even after the addltion of the incremental cobalt the reaction was slow to
start and sluggish as it indicated by the minor amounts of products formed
in an hour. The vacuum distilled naphtha fraction was significantly more
reactive. When the additional amount of cobalt was added, major amounts of
-139- ~ 73
aldehyde products (29Z) were formed within an hour. The reaction was
essentially complete in 3 hours. The atmospheric Clo naphtha cut which was
redistilled in vacuo was somewhat more reactive. However, the vacuum
distilled naphtha was more active than the atmospheric naphtha redistilled
in vacuo. This seems to indicate that the inhibitors formed during
atmospheric distillation are not removed on redistillation in vacuo.
The data oi the table also show that there was very little dimer
by-product formation in all cases. The amount of dimers formed during
these reactions was less than 3X of the main aldehyde products. Although
the amounts of trimers fo~med were not determined in this series of
experiments, it is noted that as a rule considerably less trimer is formed
than dlmer.
Analyses by capillary GC show that, as expected, the two main
products of these hydroformylations were n-undecanal and 2-meehyldecanal,
derived from l-n-decene. As it is shown by Table XXX, the n/i ratio of
these two main products in the final reaction mixture was in the 2.9 to 3.7
range. There were, of course, other minor branched aldehydes present.
These were derived fron internal and branched olefins. The amount of the
completely linear aldehyde, n-decanal, in the final reaction mixtures
ranges from 31.1 to 38.3X. This variation clearly reflects the different
percentages of l-n-decene present in these feeds. Similarly, as a
consequence of the varying feed composition, the combined amounts of
n-undecanal and 2-methyldecanal (n+i) changed from 41.7X to 51.lX. The
rest of the product largely consisted of other monobranched 2-alkyl
substituted Cll aldehydes such as 2-ethylnonanal, 2-propyloctanal and
2-butylheptanal. These monobranched aldehydes were apparently derived from
isomeric linear internal decenes.
In general, comparisons of samples, taken from the reaction
mixtures at different intervals, indicate that the l-n-decene component
reacted at first, as axpected. Consequently, the products of partially
reacted feeds were m~inly consisting of n-undecanal and 2-methyldecanal. As
the reaction proceeded, and the internal and branched olefinic components
were also converted, various branched aldehydes were formed and the
relative amounts of the two major products derived from l n-decene
decreased.
Only minimal amounts of the aldehyde hydroformylation products
were reduced by hydrogen to the corresponding ~lcohols. The only
9~ 3
-140-
identifiable alcohol by-product was n-undecanol. Its amount was below 1
of the Cll aldehyde products.
The three final reaction mixtures obtained were brown, as usual.
Some of the brown color of the mixture derived from the atmospherically
distilled feed persis~ed after the removal of the cobalt by the usual
aqueous acetic acid, air treatment. However, the brown color of the
mixture derived from the vacuum distilled feeds changed to dark yellow
upon cobalt removal.
The cobalt free reaction mixtures were fractionally distilled,
using a 2 ft. packed colu~n in vacuo, at pressures in the range of 0.1 - 50
O.2mm. The unconverted feed components were distilled as colorless liquids
with a yellow tint at ambient temperatures (20 to 30C) using a dry ice
cooled recelver. The aldehyde products were obtained as lighe yellow
liquids between 47 and 57C at O.lmm pressure.
Due to the relatively low distillation and heating bath
temperatures (100-135C bath), relatively little aldehyde dimerization and
trimerization occurred during distillation. For example, in the experiment
using vacuum redistilled feed, 1700g of the crude reaction mixture was
distilled to obtsin 570g product and 51g distillation residue. GC analysis
indicated that this residue contained 31Z product, 43X dimer and 26X
trimer. Thus, the combined dimer and trimer product was 35.2 g i.e., about
6X of the main product.
The aldehyde distillate products of the three runs were combined.
The combined product contained 37.lX n-undecanal, 10.4X 2-methyldecanal,
about 8.6X of other 2-alkyl substituted monobranched aldehydes, about 28.7X
of aldehy~es having retention times longer than that of n-decanal. These
latter compounds include doubly branched and possibly C12 aldehydes. The
amount of n-undecanol is minimal, about O.2Z.
Hydrofor~ylation cf C~-C 5 Fluid Coker
Light Gas Oil Fractlons ~th Co~alt (E~amples 4~-64
,~
The previously described Cg to Cls light coker gas oil and its
distillate fractions were hydroformylated without prior treating in the
presence of cobalt at high pressure.
The hydroformylation of the non-fractionated Cg to C16 light gas
oil was studied with cobalt in the presence and in the absence of added
phosphine ligand. Thereafter, the hydroformylation of narrow single carbon
distillate fractions from Cll to Cls was investiga~ed in the presenca of
73
-141-
cobalt st 3000 psi. In general, it was found that the gas oil fractions
were more reactive than the naphtha fractions, particularly when distilled
in vacuo. The reaction rates were directly related to the temperature, in
the 110 to 170C range. The n/i ratio of the aldehyde products was
inversely related to the reaction temperature. The isomeric aldehyde
products were isolated from the reaction mixtures by fractional
distillAtion in vacuo. The two major types of products were n-aldehydes
and the corresponding 2-methyl aldehydes. The aldehydes products were
reduced to the corresponding alcohols, in the presence of a sulfur
resistant Co/Mo catalyst.
Example 48
Hydroformylation of Cg-Cls ~hole Coker Light
Gas Oil ~ith Cobalt st 150C and 4500 psi
The previously described Cg-Cls light gas oil was hydroformylated
withou~ solvent by a 1:1 mixture of H2/CO. A toIuene solution of Co2(CO)g
was introduced at 120C temperature and 3000 psi pressure into the reaction
mixture to provide a cobalt concentration of 0.4X. When no reaction
occurred, the conditions were changed to 150C and 4500 psi. After a 30
minute induction period, a rapid hydroformylation reaction occurred. This
agrees with the hypothe~is that there are equilibrl~ among the various
sulfur substituted cobalt carbonyl complexes. Dapendent upon the types and
amounts of sulfur compounds present in the feed, sufficiently high
concentrations of CO are required to avoid the formation of inactive
carbonyl-frea complexes.
After a total reaction period of 3 hours, the reaction was
discontinued. Th~ capillary GC of the resulting mixture is shown by Fi~ure
17, It is apparent from the figure that the prominent l-n-olefin peaks of
the gas oil feed are absent after hydroformylation. The l-n-olefins were
converted mainly ~o n-aldehydes which show up as prominent peaks in the
high retention region of the GC. ~he relative intensities of the Cll eO
C16 aldehyde peaks are about the same as those of the parent Clo to Cls
olefins. The l-n-olefins of the feed appear to be of similar reactivity
without regard eo their carbon number. This is in contrast to the behavior
of branched higher olefins whose reactivity i5 rapidly decreasing with
increasing carbon number.
-142~ 73
Examples 49-51
Hydroformylation of At~osph~rically a~d V~c~um Distilled
Cll Naphtha ~nd Gas Oil Fractions with Cobalt
A series of three hydroformylation experiments was carried out
with a Cll fraction of naphtha and the combined Cll light gas oil fractions
of a Fluid-coker distLllate in the manner described in Examples 41 to 45.
The experim2nts were designed to determine the effect of the conditions of
the distillation of the gas oil feed on reactivity. Information about the
feeds used and the hydroformylation results obtained is summarized in Table
~1. Some of the details are described in the following.
A narrow cut Cll naphtha fraction boiling between 63 to 71C (146
to 150F) under 238mm pressure was used in Example 49. In Example 50, the
previously described combined Cll fractions of light Fluid-coker gas oil,
were employed. These fractions were obtained between 185 to 196C (365 to
385F) at atmospheric pressure. Part of tha same Cll fraction of light
coker gas oil was redistilled without fractionation at 50mm pressure. This
redistillation of the orange Cll fractions gave a yellow distillate, used
as a hydroformylation feed in Example 51.
Each of the above Cll feeds was hydroformylated Ln the presence
of O.lZ Co, added as Co2(CO)g. Each run was carried out using 1/1 H2/CO
under 3000 psi at 130C (266F). The reaction mixtures were sampled at
intervals and analyzed by packed column and capillary GC.
The GC composition data of the reaction mixtures of Table XIX
show that all the Cll fractions could be hydroformylated under tha above
conditions but at different rates. The vacuum distilled naphtha fraction
was more reactive than the atmospherically distilled gas oil fraction
(Examples 49 and 50, Seq. Nos. 1 and 2). The gas oil redistilled in vacuo
was the most reactive Cll fraction of all (Example 51).
It is clear from the comparative reactivities observed that
distillation in vacuo rather than at aemospheric pressure resulted in
increased rsactivity. While the present invention is independent of the
explanation of thes~ findings. We hypothesize that atmospheric distilla-
tion at high temperatur~ results in the thermal decomposition of some of
the ~hiol components to H2S plus olefin. Some of tba H2S formed may
dissolve in the atmospheric distlllate and inhibit the hydroformylation
proc0ss.
- 143-
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o L~ ,~ Ln ~ ~
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L~ 8 ~ u u~
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~_ L ~
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`~5 o o o o o o o o o o ~ CL o ~ .C
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O ~1~ ~ ~ ~ O._ ~ U~ ~ _ U7 '_ ~ O O.
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O ~
e a1 o.c x ~--
._ _ V ~ O
L 13 O a~ O ~ 41 e C~l o o
a~ ~ z ~ ~C ~ ~: a:
~ el
-144- ~ 73
The analyses of the total reaction mixture by packed column GC
show that, concurrent with the decrease of the percentage of the Cll feeds,
mostly C12 aldehydes formed. There is very little aldehyde dimer and
trimer formation; only about 3X of the main aldehyde products
Analyses by capillary GC show that the two main products are
n-dodecanal and 2-methylundecanal derived from the l-n-undecene component
of the feeds. As it is shown by the table, the ratio of these two products
in the final reaction mixtures is in the 2.7 to 3.1 range. There are of
course, other branched aldehydes present. These are derived fro~ internal
and branched olefins. Thus, the amount of the completely linear aldehyde,
l-n-dodecanal, is ranging from 37.7 to 39.4Z of the total C12 oxygenated
products. l-n-Dodecanal and 2-methylundecanal together represent 48.2 to
51.9%. The rest of the product contains major amounts of other,
monobranched 2-alkyl substituted C12 aldehydes such as 2-ethyldecanal,
2-propylnonanal, 2-bueyloctanal and 2-pentylheptanal. These monobranched
aldehydes were apparently derived from isomeric linear internal undecenes.
Only minimal amounts of the aldehyde hydroformylation products were reduced
by hydrogen to give the corresponding alcohols. The only identifiable
alcohol by-products were n-dodecanol and 2-methyl-undecanol. Their combined
concentration was only l to 3X of that of the total aldehydes.
The three reaction mixtures obtained in the above described three
examples of Cll coker distillate hydroformylation were worked up in a
manner similar to that described in Examples 41 to 45.
It was noted that the reaction mixtures derived from the vacuum
distilled Cll feeds were of definitely lighter brown color than that from
ths atmospheric distillate feed. The removal of cobalt by the usual
aqueous aceeic acid, air treatm2nt reduced the color of all the mixtures.
However, the difference between the now generally lighter colored mixtures
persisted. All the mixtures were clear, free of any precipitate.
The cobalt free reaction mixtures were fractionally distilled
using a 2 ft. packed column, at about 0.1mm pressure. The unconverted feed
components were distilled at close to amblent temperatures (20 to 30C).
The aldebyde product was obtained between 57 to 67C. Both distillates
were light yellow, clear liquids. Due to the relatively low distillation
temperature of the aldehyde products, relatively little aldehyde
dimerization and trimerization occurred during distillation. The residual
dimers were only about 2.5X of the total oxygenated products formed. The
-145- ~2~ 3
trimers were less than lZ although it is noted that their accurate
determination by GC was not possible.
Examples 52-55
Hydro~ormylation of C12 Gas Oil with Cobalt
in the 110 to 150C Temperature Range
A series of four hydroformylation experiments was carried out
with a previously described, vacuu~ distilled combinsd C12 fraction of gas
oil in a manner described in Examples 44 and 45 to determine the effect of
temperature on reaction rate and selectivity. Each run wac carried out
using 1/1 H2/CO at 3000 psi. The reaction temperatures employed were 110,
120, 130 and 150C. The reaction mixtures were sampled at intervals and
analyzed by packed and capillary GC as usual. The results are summarized
in Table XXX U-
The results of the table show that the C12 fraction was morereactive than the lower boiling fractions produced by the same Fluid-coker
unit. About O.lX cobalt was found effective in the first three examples of
the present series, while 0.2 to 0.4X cobalt was required in the previous
axperiments.
As the temperature was increased from 100 to 130C in Examples
52, 53 and 54, the reaction rate significantly increased, At 150C in
Example 4, only 0.05Z cobalt was used. Hydroformylation occurred,
nevertheless, indlcatlng increased activiey. The composition of the final
reaction mixtures indicated that in the hydroformylations 130 and 150DC, at
about 1/3 of the feed was converted to aldehydes.
It was found that selectivity of hydroformylation to produce a
high n/i ratio of the two major aldehyde products decreased with increasin~
temperature. Also, more aldehyde d$mer by-product and alcohol
hydrogenation products were formed at 150C than at lower teMperatures.
For the selective production of aldehydes with good 012fin
conversions, temperatures in the order of 130C are preferable. The daea
indicate that, in general, the l-n-dodecene is selectively hydrofor~ylated
at first, producing a high ratio of n-tridecanal and 2-methyldodecanal.
Thereafter, the linear internal olefin components are con~erted to various
2-alkyl substituted aldehydes. Concurrently, hydroformylation of the minor
branched olefins also occurs to give some further branched aldehydes. Thus,
with increa~lng conversion, product llnearity decreases. For e~ample, at
-146- ~99~73
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-147- ~2~73
130C in Example 54, the percentage of n-tridecanal decreases from 55.6 to
44.lX a~ the percentage of unconverted feed drops from 73 to 66~.
Example 53 additionally shows a low temperature ~eneration of the
active catalyst species from a cobalt carboxylate rather than dicobalt
octacarbonyl. In this Example, the use of cobalt naphthenate at 120C
resulted in approximately the same conversion as that of Co2(CO)g at 110C
in Example S2.
The four reaction mixtures of these four examples were worked up
to isolate the products in a manner similar to that of Examples 44 and 45.
All the hydroformylation product mixtures were clear dark brown liquids,
free from precipitates. They were readily decobalted with aqueous acetic
acid plus air treatment in the usual manner. The cobalt free mixtures were
lighter brown. They were worked up separately.
Fractional distillation of the cobalt free mixtures yielded
almost colorless distillate fractions of unconverted components and
colorless to light yellow C13 aldehyde products. The aldehyde products
were distllled using a 1-l/2 ft column between about 70 and 80C under
about O.lmm pressure with an oil bath of 130-160C. Durln~ the slow
distillation of about 8 hours, significant additional unsaturated aldehyde
dimer formation occurred. l'his was the ma~or factor in determining the
isolated product yields. If alcohols are the desired products,
hydrogenation of the decobalted reaction mixture prior to fractional
distillation is preferred.
The dl~tillate aldehyde products of the four examples were
combined to provide sufficient amounts for subsequent hydrogenation.
According to capillary GC, the combined product contained 40X
n-tri-decanal, 14.4% 2-methyldodecanal and 17.6X of 2-alkyl substituted
aldehyde~ plu~ minor amounts of alcohols in the order of 2X.
The detailed structure of the isomeric aldehydes is illustrated
by Fi~ure_l~ which shows the aldehyda region of the capillary gas
chromatogram of a reaction mixture. Based on GC/MS studies, the figure
indicates that besides the ma~or n-tridecanal, the 2-methyl and higher
2-alkyl branchcd isomeric aldehydes are present in decreasin~ a~ounts.
Mass spectrometric studies also showed that 2-methyldodecanal 3-methyl-
dotscanal are present in comparable amounts.
Example 56
Hydroformylation-Acstslization of C12 Light &a~ Oil with
Methanol ~ rho Pre~qnc~ O.lX Cobalt in tha 120-150-C Ran8o
73
-148-
A C12 Fluid-coker naphtha fraction of bp. 207 ta 217C was
hydrofor~ylated in a one to three molar mixture with methanol at 3000 psi
(207 atm), in the presence of O.lZ cobalt added as a toluene solution of
Co2COg at 130C. The reaction took off immediately, and proceeded at a
faster rate than without the added methanol. Nevertheless, to complete the
reaction of branched olefin components, the temperature was raised to 140C
after 2 hours and to 150C after a total of 4 hours. The reaction was
discontinued after a total of 6 hours. GC analysis of the reaction mixture
after standing at room temperature showed a highly selective formation of
the dimethyl acetal derivatives of the C13 aldehyde products and negligible
dimer formation.
The reaceion mixture was diluted with aqueous methanol to
separate the cobalt and then was distilled in vacuo. The dimethyl acetal
of the tridecanal hydroformylation product was distillPd using a 2 ft.
packed column and obtained as a clear colorless liquid between 80 and 85C
at 0.05 mm. Capillary CC/MS indicated that the isomer distribution was
similar to that observed in the absence of methanol.
Examples 57-60
Hydroformylation of C13 Gas Oil with Cobalt
in the 130 to 170C Tcmpersture Range
A series of four hydroformylation experiments were carried out
with a previously described, vacuum dis~illed combined C13 fraction of gas
oil in a manner described in Examples 41 to 45. The reaction conditions
were the same as those in the previous example. The experiments were to
determine the effect of increased reaction temperature up to 170C. The
results are summarized in Table XXXIII.
The data of the table show that the rate of the reaction
increased right up to 170C. This is in contrast to the hydroformylation
behavior found in studies of the C~ naphtha fraceion.
As it is indicated by these data, reaction temperatures below
150C were ad~antageous for the selective production of aldehydes (Examples
57 and 58). The percentage of dimer and trimer by-products increased with
the temperature. At 170C, major amounts of alcohols were formed ~Example
60).
1294~3
-149-
I O
~ , o _ ~ o
~ ~ ~1: _~
.", ~ o
~1 O .+ D O ~U~ ~ O
~a ~ o c u~
~;~ ~ _ ~o ~o ~o U~ U
o
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':~ ~ O U
L~ ~~Y _~
~_ V)
~ ~ _ .
o U ~ ~o o
E ~ o
,, Oa~~ .t,~ 00 00 0_ ~" O
L
.~X ~ O O ~ 30
E~ ~ _ ~ ~ ~ r _ U~ ~ CO ~ ~ ~ ~
, ~ ~ ~ ~ ~ ~ ~ ~ ~ ~0 -C
CC ~ ~
c
0~I ~ cooa ~ oln D~ C ~
~~ O~ I~ C
'I ~ ~-
~0 C O
~ S -- ~ LL. ~O $ O f'- ~ ~
C o C~ ~0
O ~ ~_ ~
o a~0~ ~0 0 ~O ~G ro
_ _ _ ~ lCy
oJ ~
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-150~
It was also observed that the percentage of the n-aldehyde
component of the total aldehyde product decreased with the temperature.
Thus, the data show that reduced reaction temperatures result in ircreased
product linearity and decreased by-product formation. It should be noted,
though, that the sharply decreased n-aldehyde content of the 170C reaction
mixture is largely due to hydrogenation to n-alcohol. At 170C, aldehyde
formation is essentially complete in 60 minutes. Thereafter, the prevalent
reaction is aldehyde hydrogenation to alcohols.
All the hydroformylation product mixtures were clear brown
liquids, free from precipitates. They were readily decobalted with aqueous
acetic acid plus air treatment in the usual manner. Some additional
dimerization of the aldehyde product occurred during distillation at O.lmm
using a 2 ft packed column and a heating bath of about 135C. The
aldehydes distilled between 75 and 85C at O.lmm.
It was interesting to observe during the distillation of the
reaction mixtures, that the color of both the unconverted componen~s and
the aldehyde products were dependent on the reaction temperature. The
mixture from the 130C reaction yielded yellow distillates of both
unconverted gas oil components and aldehyde products. The mixtures of the
140 and lS0C reactions gave colorless hydrocarbon distillates but yellow
aldehyde products. The 170C reaction mixture yielded colorless
distillates of both hydrocarbon and aldehyde fractions.
The above observations indicate that during hydroformylation,
double bond hydrogenation and, probably, desulfurization via hydrogenation
become increasingly significant side reactions with increasing reaction
temperatures. It is felt, though, that these hydrogenations are better
carried out during the subsequent hydro~enation of the reaction mixture
which provides the usually desired higher alcohol product.
The distilled aldehyde products all contained tetradecanal and
2-methyltridecanal as the major components. As it was also found in the
previous examples, other 2-alkyl substituted C14 aldehydes, when combined,
constituted the third group of product components. It was shown by GC~S
studies that the 2-alkyl substituents of these aIdehydes ranged from C2 to
C6 n-alkyl.
-151~ 73
Examples 61-63
Hydroformylation of C14 Ga~ Oil w~th Cobalt
in the 110 to 130C Temperature Range
A series of three hydroformylation experiments were carried out
with a previously described, vacuum distilled combined C14 fraction of gas
oil in a ~anner described in Examples 44 and 45. The rPaction conditions
were the same as in Examples 52 to 54, however, the amount of cobalt
catalyst used was increased from 0.1 to 0.3X. The results are shown in
~!
The data indicate that the reaction rate was the smallest, but
product linearity was the greatest, at 110C, the low temperature of
Example 61. Conversely, at 130C, i.e., the high temperature of Example
49, the reaction rate was the greatest but product linearity was the
smallest. Since the reaction temperatures were relatively low in all three
examples, there was no significant aldehyde dimer and trimer formation. The
amount of alcohol hydrogenation by-products also remained low, around 3~ of
the aldehydes.
The product linearity is best indicated by the percentage of the
n-aldehyde (and n-alcohol) in the total oxygenated products. At the end of
the hydroformylation, this value was 45.2X at 110C, 42.2X at 120C and
40.8X at 130~C. The percentage of the l-n-olefin derived n-aldehyde was
inversely dependent on the hydroformylation o the less reactive internal
and branched olefins which provide branched aldehydes. Thus, the
n-aldehyde percentage was inversely proportional to the total olefin
conversion.
Tha n/i ratio of the two main aldehyde products, n-pentadecanal
to 2-methyl-tetradecanal, was more independent of olefin conversion since
both of these products can be derived from the reactive l-n-olefin
component, l-n-tetradecene. (2-Methyl-tetradecanal can be also derived
from 2-tetradecene). This n/i ratio was largely dependent on the
temperature. It was inversely proportional to it as it is indicated by the
data of ~he table.
The data of these and the previous examples suggest thac a
preferred method of hydroformylation is c~rried out at variable
temperatures wherein the l-n-olefin component is substantially converted at
130C or b~low, and the other olefins are malnly reacted at temperatures
exceeding 130C up to 170C. Such a variable temperature operation can bs
973
--152--
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_ O ~ 0 ~ O 1~ 0 U~ ~ ~ U ~
O ~! -~IJQ
_ ,~ I r ~ C~ L
~- ~ c ~ o
01~ Cl. I ~r~ ,~,~, ~ ~'_~
~ _ C~ O
r~ ~ ~ c r~
~~ L ~ E ~N u~ O r~ a~ O _ _ ~> L
X~1 ~ C~1 E ~ c~ J O O ~ O O .-
U8 ~ O _ -c lLv)
X C-~ ~ cO ~ -- ~ '- ~ C
_ ~ ~ Oa~ ~ 2_ a) ~ ~ ~ ~ c ~ ~ ~
~ O ~ ~ C O L
~ 3 ~ ~ _ ~
O ~ .CI ~ ~ L E
d' , ~ a.1 o 30
æ ~ aLI ar~ O
0 0 c C ~ ~-- ~ ~ æ
0 ~ o ¦ ~ O ~ _ C ~IJ
,C ,, U ~ ~ _
'~ X ~ a~ ~
LL ~ ~ ~ ~
'73
-153-
carried out in reactor system comprising reactors operating at different
temperatures.
All the hydroformylation product mixtures were decobalted with
aqueous acetic acid plus air treatment in the usual mannçr, and then
fractionally distilled in vacuo. The Cls aldehyde product was obtained as
a clear yellow liquid distillate boiling between 95 and 111C at O.lmm.
Using a relatively low temperature bath of 120-140~C, relatively little,
about 5X, of the aldehyde was converted into dimers and trimers during
distillat~on.
Analyses of the distilled Cls aldehyde product showed that it was
essentially free from hydrocarbon impurLties. Combined GC/~S studies
lndicated the presence of about 47X n-pentadecanal, 15.5X 2-methyl-
tetradecanal and 16X 2-(C2 to C6 alkyl) substituted aldehydes. A distinct
dibranched C16 aldehyde was also found in the ~ixeure in about 7.9X
concentration. Minor amounts (0.5X) of n-pentadecanol were alsa presene.
Example 64
Hydroformylation of a C14 Fraction o L~ght Gas Oil by H2/CO
~ith Cobalt under 3000 ps1 Pra~sure at Variable Temp~ratures
and the Hydrogenation of the Cls Aldehyde Product
The C14 olefinic feed for the present hydroformylation was
separated from a light Fluid-coker gas oil by a double 15/10 type
distillation. It was hydroformylated either in the presence of 0.2 or
O.lZ. As a catalyst precursor, Co2~CO)g was used. It was introduced at
120C as an approximately 6Z solution in isomeric xylenes. The temperature
was increased from 120 to 150C during the course of the reaction to
convert the various types of olefins at their minimu~ reaction temperature.
The results of both hydroformylation experiments,using 0.2 and
O.lX cobalt, respectively, are shown by Ta~e X~- Good olefin conversion
was achieved at both catalyst concentrations. The maxim~ aldehyde content
of the reaction mixtures was about 30X. However, the n-aldehyde
selectivities appeared to be slightly higher at 0.1~ Co.
The decrease in pressure drop with the reaction ~ime indicated
and the composition of the reactlon mixture by packed GC showed that the
reaction was essentially complete in 4 hours. As expected, the reaction
was fastcr at the higher catalyst concen~ration. The final reaction
mixtures still contained only minimum amounts of by-products; in the range
of 2 to 3% of dimers.
-156.- ~ 73
-- -- c a ¦ o ID ~
O ~ ~. G O " ¦ ~ , N ~-- ~
~ ~ " u ~ ~ o ~ ~ I .~
,0 ~ ~ æ ~1 l ~ ' g
_ . .13 C ~ C ~ ~ S J t~~ N N ~ ~
~ O w ~ O I IO O S, O ~r~ N ,~ ~ r. -- C
C _ O L
L ~. O C~ O ~ o~ ~ o ~
O S~ 'O I ~ . ~ o O
1~ o ~ c r I N N _1 N N N ~ L
~~ g ~ L N~ ~ ~ _ N ~D Qa ~ ~t C
5a J o 1~ a N Od ~ ~> N ~ ~ r
~c ~ ~ ~ ~ 3
E--~ c ~_ L 8 O O ~ ~ Ul O~ ~ ~ i~ V~ O _ C
O ~- L ~ ~ 11~1 ~ N N ~ ~ q C ~1~ C
L _ Cl Q O O ~ O ~ 1 ~ O
O ~ _ o ;~ ¦ 5 ~ ~ ~ ~ ie ~
~ ~ ~ ~ o ~
_ ~ S ~ O _ _ N N _ _ N ~-- a
e Q 1_ ,0o n ¦o ~ O o o N ~- D
o " O ~ ~cn ~ ~ o ~ oo o o o o .,n
IC e_ 11~ N N NN ~ o ~ O IZ~ _ ~
~ ~ e~ 3 ~ ~o ~ ~
o ~ o ~_ ~ _ ~ o ~ro o ~ ~ o 10 ~ i
o ~ ~ e n c~ o ~ ~ L
~ e c~~ eI o o o o o oo o o e o o ~ o
4~ V~ ~ o
o ~9 ~ O o O 06:~ o
. ~ ~ o . _ ~ ~ ~ ~ ~ ~ L
o c o ~ 1~ e
~ s~ v I o i -- ~
-155- ~.4~ 73
Capillary GC showed tht the n-pentadecanal was the most prevalent
Cls aldehyde isomer forred. It was, of course, mostly derived from the
main and most reactive olefin component of the feed l-n-tetradecene. Thus,
its percentages, 56.0 to 48.9X, were particularly high durin~ the early
stages of the reaction. At the completion of the reaction, the
n-pentadecanal concentration was 33.1 to 36.1~ of the isomeric
pentadecanals.
The monobranched pentadecanals derived from and were the largest
group of branched isomers. The percentage of the largest branched Cls
aldehyde isomer 2-methyl-tetradecanal ranged from 12.0 to 13.5. The second
largest isomer, 2-ethyl-tridecanal was present in concentrations ranging
from 5.7 to S.8X. The other monobranched Cls aldehydes derived from
n-pentadecenes were also present in concentrations ranging from 1.8 to
3.8~. As expected, these minor aldehyde isomers had n-propyl, n-butyl,
n-pentyl and n~hexyl branches in the 2-position. The largest of these
minors, 2-propyl-tridecanal was present in the 2.1 to 3.9Z concentration
range. It is noted that at low feed conversion ehe recorded relative
concentrations of these minor isomers in the table are low because of the
limitation of the GC method of determination.
The selectivity of the hydroformylatlon of the l-pentadecene
component is characterized by the ratio of n-pentadecanal to
2-methyltetradecanal (n/Me). This ratio is decreasing from a top value of
about 3.4 down to 2.7 with increasing reaction temperature and olefin
conversion. The overall Cls aldehyde linearity is described by the ratio
of the normal isomer to the sum of all the iso-, i.e. branched, aldehydes.
This ratio also drops from 1.27 to 0.49.
Capillary GC also showed the presence of significant amounts
isomeric Cls alcohols and Cls formates in the reaction mixture. Their GC
peaks partially overlapped, ~ut n-pentadecanol and n-pentadecyl formate
could be distinguished. The combined amounts of alcohols and formates in
the final reaction mixture ranged from 14.5 to 17.0X of the eotal
oxygenated products. The ratios of the n-alcohol to the n-alkyl formate
were from 2.4 to 3.5
Sulfur GC of the reaction mixture indicated that most of the
sulfur compound components are in the retention time region of the C14
hydrocarbon feed. Relatively very small ~mounts of sulfur were found in
thc aldehyde region.
-156-
The hydroformylation reaction mixtures were decobalted with
aerated aqueous acetic acid as usual. Then they were hydrogenated in the
presence of 10% of a CoS/MoS based catalyst and 5~ water at 3000 psi (306
atm) in the 150 to 170C temperature range. The reduction of the aldehydes
was co~plete in 20 hours. Sulfur GC indicated that most of the sulfur
compounds in the feed region remained unrhanged during hydrogenation.
The hydrogenation of the aldehyde components of the reaction
mixture was studied in some detail. Hydrogenations were carried out under
comparative conditions at 150, 155 and 160C under 3000 psi pressure in a 1
lieer stirred autoclave with reaction mixtures described above Samples
taken after 2, 5 and 20 hours were analyzed for aldehyde and alcohol
content by capillary GC. The results are shown by Table XXXVT.
The data of the table show that hydrogenation occurs at a
moderate rate at all three temperatures. The conversion of the
n-pentadecanal to n-pentadecanol is 96X or more. The conversion of all the
isomeric aldehydes is about 85 to 90Z as a minimum. (The total conversion
could not be exactly deter~ined because of GC peak overlap between
aldehydes and alcohols. This overlap of minor alcohol components was
dlsregarded and all the components having shorter retention times than
n-pentadecanal were counted as aldehydes.)
It is noted that the data of Table XXXVI show a slightly
decreased aldehyde to alcohol conversion with increased temperature. This
is apparently due to a slight decrease in catalyst activity in the three
experiments of increasing temperature. It is interesting eo note that the
amount of n-pentadecane secondary product derived from n-pentadecanol
increased with the temperature from a level below detection to an amount
equal to 1.3X o~ that of n-pentadecanol. It appears that the n-alcohol to
n-paraffin conversion is more temperature dependent than the n-aldehyde tQ
n-alcohol conversion.
The hydrogenated reaction mixtures from the hydroformylation of
C14 Fluid-coker light gas oil frac~ion were combined and worked up to
isolate the isomeric Cls alcohol products. The combined mixture was then
washed with fifty volume percen tof a lOX aqueous sodium hydroxide solution
to remove the H2S and any carboxylic acid by-products. This wash resulted
in e~ulsion formation. The emulsion phase was largely broken by the
addition of xylene. The organic phase was then washed with water and dried
over anhydrous MgSO4. The xylene solvent was then mostly removed by film
-157-
Table XXXVI
~drogenation of th~ Cls Ald0hyt~ Co~ponont3 of the
Hydrofor~yl~ion Reactlon ~ture Derivod fro~
C14 Fluit-Coksr Nsphtha fro~ Bllling~A)
Convsrsion to C15 Alcohol Products Based on
Alcohol Product to Aldehyde Precur~or Ratio
. _ ~ .. . . ._ .
At 150-C At 155~C Ae 160C
(E-7630) (E-7633) (E-7636)
Action Alcohol X Alcohol X Alcohol X
Ti~eb Wor- To- Nor- To- Nor- To-
Hrs.malC tald malC tald malC tald
245 31 38 33 32 24
568 54 62 50 58 44
~9~ 90 9~ 88 96 85
a) Hydrogenation with 6 wtZ CoS/MoS catalyst on
alumina support in the presence of 5X water under
3000 ps L pressure
b) From the time the mlxture reached reaction
temperature
c) The percentage of n-peneadecana]. converted to
n-pentadecsnol
d) The percentage of Cls aldehydes converted to Cls
alcohols based on oxygenated co~pounds up to and
including n-pentadecanal.
973
-158-
evaporation in vacuo and the residual liquid was fractionally distilled in
vacuo.
Fractional distillation reco~ered the unreacted C14 hydrocarbons
as a clear colorless liquid between 61 and 72C at about 0.1 mm. The
oxo-product residua was about 1 kg. On further distillation the Cls
alcohol product was distilled betwen 112 and 129C at 0.1 ~m. About 70X of
the oxo-products were obtained as the C1s alcohol distillate, a colorless
clear liquid. Another 17X was recei~ed as a yellow liquid distillate
mixture between 129 and 245C. This mixture contained C1s alcohols and
dim0rs in a 1 to 2 r~tio. The residue was about 12X.
During the distillation of ehe Cls alcohol, it was noted that the
n-pentadecanol crystallized on cooling from the higher boiling more linear
fraction~. Linear detergent alcohols can be apparently isolated from the
present alcohol mixtures by crystallization.
Example 65
Hydroformylation of Cls Gas Oil wlth
O.lX Cobalt at 140C
~ The previou~ly described, vacuum distilled combined C1s fraction
of gas oil was hydroformylated in a manner described in Exa~ples 41 to 45
at 140C under the conditions of Examples 49 to 52. The results are
s = arized in Table,~
Table XXXVII
Hyt~oformylation of C1s Ole~inic Fraction o~
G~s 011 from a Fluld Cokor in tho P~osonco of O.lX Cobalt
C~taly~t Dorivod from Co2(CO)g uith 1/1 ~2/CO at 3000 p5i
Reaction Mixture
Time CQmponents~ X Two Ma~or
Min Un-Aldehydesb Products
fA~o~ n/i,RatioC
973 3.14
180 8911 2.87
360 7129 2.76
aDetQrmined on packed column GC.
bMostly aldehydes.
Cn-Hexadecanal to 2-methylpenLadecanal
-159~ 7~
The data of the table show that at the low concentration of
catalyst used, thare was a long induction period. After 1 hour reaction
eime, less than 3~ of aldehydes were formed. In three hours, product
formation was still minimal. The maximum rate of hydroformylation was
reached after 4 hours as indicated by the rate of synthesis gas
consumption. A complete conversion of the l-n-pentadecene feed component
was obtained in 5 hours. After 6 hours, the amount of products in the
reaction mixture was 29X and gas consumption was low. Thus, the reaction
was discontinued.
Analyses of the reaction products showed high selectivity to
aldehydes. The amount of alcohols and dimers each was about lX in the
final reaction mixture. The main reaction produc~s were n-hexadecanal and
2-methylpentadecanal in an n/i ratio of 2.76. These two products amounted
to 73.5X of all the C16 aldehyde products. Most of the rest were 2-alkyl
substituted C16 aldehydes.
The final reaction mixture was decobalted as usual and
fractionally distilled at 0.lmm to separate the C16 aldehyde product. The
aldehyde was obtained as a clear yellow liquid distillate, boiling between
115 and 125C at 0.1mm using a heating bath of 150 to 160C. During
fractional distillation, significant aldehyde dimer and trimer formation
occurred. Only 70X of the C16 aldehyde present in the reaction mixture was
recovsred by distillation.
Examples 66-70
Hydro~enation of the Cll-Cls Aldehydes Derived from
Coker Distillates to Produce the Corresponding Alcohols
The combined distilled Cll to Cls aldehyde products were
hydrogenated in the presence of a sulfur insensitive cobalt/molybdenum
based hydrogenation catalyst in the manner previously described in the
Experimental procedures. After about 24 hours hydrogenation at 232~C under
300 p9i pressure, the reaction mixtures were analyzed by GC/MS for aldehyde
conversion. (In the case of the Cls aldehyde, the reaction time was 48
hours.) It was found that the aldehydes were completely converted. The
products were mostly the corresponding alcohols. However, some conversion
to paraffins also occurred, possibly via the main alcohol products.
73
-160-
CnH2+1CH0 H23- CnH2n+lCH20H 2 ~ CnH2n+lCH3
n 10-14
The product distributions obtained in the Examples are listed in the
following:
Ex~mple Carbon No. Product Distribution Z
Number of P~oduct Alcohl Paraffi~
66 11 87 13
67 12 87 13
6g 13 88 12
6g 14 89 11
68 32
An examination of the isomer distribution of the paraifin by-
products by GC/MS showed a higher ratio o normal to iso paraffins than the
n/i of the parent aldehydes. This indicated that the n-aldehydes and n-
alcohols were preferably hydrogenated to paraffins. Consequently, the
percentages of the n-alcohols, and the n/i ratios of n-alcohols to 2-methyl
substituted alcohols, somewhat were lower than the n-aldehyde percentages
and the aldehyde n/i ratios of the feeds. Since the hydro~enation to
paraffins was a minor side reaction, the order of decreasing concentrations
of alcohol types (normal, 2-methyl substituted, 2-ethyl and higher alkyl
substituted alcohols) remained tbe same as that of the aldehyde feeds.
The reaction mixtures of the hydrogenations were fractionally
distilled to separate the alcohol products from the paraffin by-products.
Both were obtained as colorless liquid distillates of the following
approximate boiling ranges:
9~
-161-
Boiling Ran~e__C~mm..
Carbon AlcoholParaffin.
Number ProductBv-Product
11 135-1~6-2097-132/20
12 148-158/2094-135/20
13 145-149/1096-144/10
14 147-163/10114-145/10
163-172/10117-157/10
GC/MS studies indicated that the alcohols had qualitatively the
same Lsomer distribution as the parent aldehydes. The n-alcohols and the
2-methyl branched alcohols were the main components. GC/MS showed that the
paraffins were derived from the aldehyde feed without structural
isomerization. The paraffin forming side reaction occurred a~ the highest
rate in case of the linear aldehyde component of the feed as indicated by
the predominant formation of the n-paraffin.
Semilinear DilLkyl Phthal8te PLaæticizers
The Cs to Cls semilinear alcohols of the present invention can be
converted to the corresponding dialkyl phthalate esters, via known methods.
The alcohols are reacted with phthalic anhydride, preferably in the
presence of a non-oxidizing acid catalyst such as p-toluene sulfonic acid
or an alkyl titanate. The rasulting phthalate esters have a unique
combination of plasticizer properties as illustrated by the following
examples.
Example 71
Semilinear Diundecyl Phthalate Plasticizer
The semilinear undecyl phthalate, DUP-F, and a linear undecyl
phthalate, Jayflex DUP, were compounded with a Geon 30 polyvinylchloride
and additives in the following proportions: parts per 100 wt. parts of PVC
Geon 30, 100; phthalate plasticizer 50, Calcined Clay, 10; Dythal XL, 7;
Stearic acid, 0.2. The physical properties of the resulting plasticized
~ compositions ware then tested. The data obtained are the following:
:
-162 1~9~3
DUP-F Jayflex DUP
Hardness Shore D 36 39
100X Modulus, psi 1890 2190
Tensile Strength, p9i 3040 3110
Elongation, X 325 302
The highsr hardness and modulus of the DUP-F composition
indicate decreased plasticizer effectiveness. To obtain similar physical
properties, a hi~her amount of DUP-F i3 to be used. Since the plasticizer
has a lower cost by volu~e than PVC, reduced plasticizer effectiveness
decreases the cos~ of plasticized PVC.
DUI-F and Jayflex DUP were also compared in a plastisol tese in
the following formulation: Geon 121, 100; Plasticizer, 70; Mark 7101, 2.
After aging the plastisolQ at 100F (38C) the comparative Brookfield
viscosity data were:
DUP-F J-DU~
Cp5 after 2 hours at 3 rpm 4870 1970
30 rpm 36850 15750
cps after 24 hours at 3 rpm 6120 2060
30 rpm 41800 17250
To determine processability, a hot bench gelation test and dynamic
mechanical analyse~ (at 10C/min and 1 rad./min and 1% strain) were carried
out. The comparative results were:
~ J~DUe
Gel point, C 247 264
Gel onset, C 73 81
Gel complete, C144 144
Fu ion co~plete, C 196 196
These data indicste a more facile processing for the Flexicoker alcohol
bas2d, DUP-F plasticizer.
The color stability on heating at 350F (177C) was the same for
the DUP-F and J-DUP composition. Only the low temperature properties of
the semilin~ar DUP-F were inferior to those of the linear J-DUP. In this
respec~, the properties of the semilinear DUP-F are in between those of the
corre ponding branched and linear ester compositions.
~Z,g~3
-163-
Example 72
Semilin~r Didodecyl Phthslate Plssticizer
The semilinear dodecyl phthalate, DDP-F, was compared as a
plasticizer with branched ditridecyl phthalate, J-DTDP, and branched
undecyl decyl phthalate, J-UDP. Plasticized PVC compositions were
formulated as follows: Geon~30, 100; Plasticizer, 62; Tribass EXL (lead
silicate sulfate stabilizer~; CaC03, 15; Stearic acid, 0.25; BPA
antioxid~nt, 1. After milling at 350F (177C) and molding at 360~F
(182C) the followin~ properties were found:
DD~ p~ UDP
Shore A Ha~ness, 7 day 84.7 84 84
Shore D ~ardne3s, 7 day35.5 38 37
Ori~lnal Phv~ica~s, 0.040"
Tensile Strength, psi 2483 2555 2584
100X Modulus, psi 1749 1856 1868
Elongation, Z 307 293 280
Aged Pbysicals, 0.040" 7 days
136C
Retained Tensile Stren~th, ~ 103 107 130
Retained 100X Modulus X 139 146 Too brittle
Retsined Elongation, i 64 56 Too brittle
Weight Loss, X 4.8 9.7 14.6
Clash Ber~, Tf, 0.070n, C -31 -23.3 -27
~ , 0.070n, C -28 -21.9 -22
Pad V~lu e~Q~sçlyitv 0 30 1.68 1.94
0.040~, 90-C, ohm-cm x lon
These results lndicate that the semilinear didodecyl phthalate is
a fine plaseicizer. Its reduced weight loss and lower Clash Berg and Bell
Brittlenes~ te~peratures indicate volativity and low temperatur~
charactoristics superior to related branched phthalate esters.
~ TR~ A Rl~
-164
Example 73
Semllinear Ditridecyl Phthalate Plastlcizer
The semilinear ditridecyl phthalate plasticizer, DTP-F, and a
commercial branched ditridecyl phthalate plasticizer, DTDP, were compared
in a PVC formulation described in the previous example with the following
results:
DTP-F DTDP
Shore A Hardness 92 91
lOOX Modulus, psi 1740 1770
Tensile Strength, psi 2420 2500
Elongation, X 285 304
Aged Phy$ical. 7 days/136C
Retained Tensile, X 102 105
Retained Elongation, X 77 56
Weight Loss, X 2.8 9.6
Low ~ s
Clash Berg, Tf, C -30 -23
Bell Brittleness, Tb, C -25 -22
Pad Volume_~esistlvity
40 mil, 90C, ohm-cm x 10" 2.2 9.5
The data indicate that DTP-F is a fine plasticizer with superior elongation
retention and permsnence at high temperature and better low temperature
properties th~n DTDP.
Semilinear Sur~actants
The semilinear alcohols of the present invention are converted to
novel surfactants via known methods. These methods are described in the
appropriate volumes and references therein of the Surfactant Science
Series, edited by M. J. Schick and F. M. Fowkes and published by ~arcel
Dekker, Inc., New York. Volume 7, Part 1 in 1976 by W. M. Linfield covers
"Anionic Surfactantsn. "Cationic Surfactants" are discussed in Volu~e 4 of
1970 by E. Jungermann. "Nonionic Surfactants" by M. J. Schick are in
Volume 1 of 1966.
X'
-165-
Example 74
Heptaetho~ylated Semilinear Alcohol Surfactants
Semilinear C13 and C14 alcohols of the present invention were
ethoxylated in the presence of sodium hydroxyde as a base catalyst to
provide nonionic surfactants with an average of 9 ethoxy groups per
molecule.
C13H27(0CH2cH2)9oH and C13H27(0CH2cH2)9oH
C13 - F07 C14 - F07
In contrast to the sluggish and incomplete ethoxylation of
branched aldol alcohols, these ethoxylations proceeded readily to
completlon.
r .~ These surfactants were ~hen compared with a similarly ethoxylated
linear C12 to Cls alcohol, Neodol 25-7.
The surface tension, in dynes per cm at 78F (25C), of aqueous
solutions of these surfactants at various concentrations according to the
ASTM D-1331 test method were the following:
O.OOO~X O.001% 0.2lZ
C13-F07 57 36 30
C14-F07 61 . 38 35
Neodol 25-7 5 34 30
These data indicated similar surface tension reductions at the practical
concentratlons~
The cloud points of the lX aqueous solutions of these semilinear
and linear surfact~nts by ASTM-D2024 also similar.
Cloud_Poin~
C F
C13-F07 40 104
C14-F07 44 111
Neodol 250746 116
The ambient temperature wetting times of O.lX aqueous solutions
of the semilinear surfactants were superior to those of the linear
surfactants; according to the Draves test (ASTM-D2281):
~RP~ m~
73
-166-
Wettin~LTime, Seconds
24C 4C 10C
Below Above
C~ou Cloud
C13-F07 8.5 7.4 10,0
C14-F07 6.7 11.8 12.3
Neodol 25-7 14.0 11.0 13.5
Aqueous solutions of the semilinear surfactants had a definitely
reduced foam stability according ~o the Ross-Miles test:
Foam H~ hhL, ~ 8_L~Z E_¦b~LL--
_0.1~ l.OX
Init~l 5 Mi~. Initial $ Min,
C13-F07 9 1 7 2
C14-F07 9 2 5
Neodol 250-712 6 15 12
This is advantageous in many nonfoaming applications.
Example 75
Nonsethoxylated Se~ilinear Alcohol Surfactants
Semilinear C13 and C14 alcohols were eehoxylated to provide
surfactants of incr~ased hydrophilic character with an average of 9 ethoxy
groups. These surfactants C13-FO9 and C14-FO9 were compared with a
simllarly ethoxylaeed linear alcohol, Neodol 25-9, in ehe tests of the
previous example. The results are shown by the following tabulations:
~'~
O,0001% ~Q~l~ ~l%
C13-FOg 52 40 33
C14-F09 57 36 33
Neodol 25-9 :S6 34 32
Cloud Point
t 1%
'
C13-F09 78 I73
C14-F09 74 165
~eodol 25-9 74 165
-167- ~ 73
Uettin~ ~ime. Seconds
24C 4C 10C
Below Above
_ CloudCloud
C13-F07 14 8 23
C14-F07 16 9 9
Neodol 25-7 19
Foam HeiRh~cm at 122F (50C~
. _ 1,~ 1 . ox
Initial 5 M~ Initial 5 Min.
C13-~07 15 3 21 6
C14-F07 14 4 17 5
Neodol 250-7 15 12 17 13
It is apparent from the test results that the surfactant
properties of the novel semilinear alcohols can be advantageously changed
depende~t on their carbon number and degree of ethoxylation. Since the
presen~ semLlinear alcohols can be readily produced with even and uneven
carbon numbers of choice, they can often provide surfactants of optimum
properties without added cost,
Both the semilinear alcohols and their ethoxylated derivatives
wera readily sulfated and sulonated to provide anionic surfactants of
similarly attractive surfactant properties.
This invention has been described and illustrated by means of
specific embodiments and examples; however, it must be understood that
numerous changes and modifications may be made within the invention without
d-p r~ing fr les spirlt Ind s~opn ~s deElned Ln che clalms w~ich follow.
