Note: Descriptions are shown in the official language in which they were submitted.
D-9814-1
~069540
This invention is concerned with the
manufacture o$ polyhydric alcohols, their ether and
ester de~iYatives, and oligomers of such alcohols.
This invention also produces monohydric alcohols
such as methanol, and theîr ether and ester derivatives.
It is known that monofunctional compounds such
as methanol can be obtained by reaction between
carbon monoxide and hydrogen at elevated pressures,
e.g., up to about 1000 atmospheres, and temperatures
ranging from 250C to 500C, using mixtures of copper,
chromium and zinc oxides as the catalyst therefor.
It is disclosed in U.S. Patent No. 2,451,333 that
polyhydroxyl compounds are produced by reaction of
formaldehyde, carbon noxide, and hydrogen in the
pre~ence of hydrogenation catalysts. It has also
been reported that formaldehyde can be produced by
reaction between carbon monoxide and hydrogen at
elevated pressures but repeated attempts to carry out
this synthesis of formaldehyde have invariably failed
to yield any substantial quantity of the desired pro-
- duct. It is generally recognized that the previously
disclosed processes for the synthesis of formaldehyde
from carbon monoxide and hydrogen at high pressures
are either completely inoperative or else give rise
to insignificantly small quantities of formaldehyde.
: .
~ 2.
, : : . :. . ............. - . ~:. . :. : . ...
... , ~,. ~. -. ,, .. . . , ,
~069540 D-9814-1
In British 655,237, published July 11, 1951,
there is disclosed the reaction between carbon monoxide
and hydrogen at elevated pressures and temperatures,
e.g., above 1500 atmospheres at temperatures up to
400C., using certain hydrogenation catalysts as
exemplified by cobalt-containing compounds. U. S. Patents
No. 2,534,018; 2,570,792, and 2,636,046 are substan-
tially similar in disclosure to the above said British -
patent. The only catalysts employed in the numbered
examples of said U.S. Patent 2,636,046 are those which -
; contain cobalt.
It is also well-known that nickel is predomin-
antly a catalyst for synthesis and for reforming
methane according to the reaction
'
CO 3H2 ` 4 H2O
whose equilibrium favors the right hand side of the
equation at temperatures below about 500C. and the
left hand side of the equation at higher temperatures;
see Kirk-Othmer, Encyclopedia of Chemical Technology,
Second Edition, Volume 4, pages 452-453, John Wiley
and Sons, New York (1964).
Polyhydric alcohols are presently being produced
synthetically by the oxidation of petroleum derived
materials. Owing to the limited availability of
petroleum sources, the cost of these petroleum der-
ived materials has been steadily increasing. Many
have raised the dire predlction of a significant
. ,. , , , - .
D-9814-1
~069540
oil shortage in the future. The consequence of this
has been the recognition of the need for a new low cost
source of chemicals which can be converted into such
polyhydric alcohols.
This invention is directed to the process of
making polyhydric aliphatic alcohols, and to their
ether, ester and oligomer derivatives. In particular,
this invention is concerned with the diols and triols,
containing 2 or 3 carbon atoms, their ethers, ester and
10 oligomer derivatives. A byproduct of this invention is
nevertheless, monohydric alkanols such as methanol,
ethanol and propanols, and their ether and ester
derivatives. The products of the process of this
invention contain carbon, hydrogen and oxygen.
There are described in U.S. Patent 3,833,634,
issued September 3, 1974, and U.S. Patent 3,957,857
issued May 18, 1976, processes for reacting hydrogen
and oxides of carbon in the presence of rhodium
carbonyl complex catalysts. One problem associated
20 with these processes is preventing the loss of the
catalyst during the reaction so as to avert catalyst
losses. Inasmuch as the rhodium used in the catalyst
is an extremely expensive metal, having a current dealer's
price of about $285. per troy ounce, it is particularly
desirable to avoid any significant loss of such rhodium
values during the course of the reaction.
, \ ~'
~;~
.... : : :. .
10695~0 D-9814 1
In accordance with'the'practice of t~e
present in~ention these losses of rhodium may Be
slgnificantly reduced ~hen th~e'a~orementioned
reactions of hydrogen and oxides of carbon are
conducted in the presence'of an organic sulfone
solvent.
The process of the present invention involves
the production of alkane diols and triols having
from 2 to 3 carbon atoms in the molecule by reac-
ting a mixture of hydrogen and oxides of carbonin the presence of a rhodium carbonyl complex and
dimethylsulfone or a tetramethylene sulfone solvent.
~ tetramethylene sulfone as used herein
and as embraced by the claims shall be defined
as any substituted or unsubstituted tetrahydrothio-
phene-l,l-dioxide, hereinafter referred to as
tetramethylene sulfone or sulfolane, which when
present as a solvent for the rhodium carbonyl
complex catalyzed reaction of hydrogen and an
oxide of carbon at a temperature of about 100C
to about 375C and correlated with a pressure
of from about 1000 psia to about 50,000 psia will
produce a polyhydric alcohol.
. Illustrative of tetramethylene sulfone sol-
: vents useable in practicing the present invention
,. ., .. . .. ~...... ;. . .. . -, ,.
1069540 D-9814
include sulfolanes of the formula:
R2 R3
R~ - - R4
R7 J R5
R8 \ / 6
,.
wherein each of Rl through R8 is at least one
of hydrogen; hydroxyl; straight or branched chain
alkyl, preferably having from 1 to 12 carbon atoms,
mos~ preferably 1 to 6 carbon atoms in the alkyl
chain, such as methyl, ethyl, isopropyl, butyl,
octyl, dodecyl and the like; a cycloaliphatic group
including the monocyclic and bicyclic groups such ;
as cyclopentyl, cyclohexyl, bicyclo 12.2.1] heptyl,
and the like; or an aryl, alkyl-aryl, or aralkyl
group such as phenyl, naphthyl, xylyl, tolyl,
benzyl, beta-phenylethyl and the like; an ether ~:
of the formula-~0-R) wherein R may be aryl or
lower alkyl having from 1 to 12 carbon atoms,
preferably 1 to 4 carbon atoms in the alkyl chain;
an alkylene or polyalkylene ether of the formula
-(OCnH2n~-OR wherein n has an average value of
from 1 to about 4, x has an average value of
from 1 to about 150, preferably 1 to about 20,
~0695~0 D-9814
most prefera~ly 1 to about 4, and R may be
hydrogen or alkyl having from 1 to 6 carbon atoms
in the alkyl chain, such as poly(oxyethylene),
poly(oxypropylene), poly(oxyethylene-oxypropylene),
alkylene and polyalkylene glycols and lower alkyl
ethers thereof; a carboxylate group of the formula: ~;
~CH2 ~ O~F~ t~mR !
wherein y may have any value between 0 and 12, m
and m may be zero or one provided that when
either m or m is one the other is zero, and
R may be a lower
alkyl group having from 1 to 12 carbon atoms,
preferably from 1 to 4 carbon a~oms, or aryl;
and the like. Preferably the sulfone used in
the practice of the present invention is
tetrahydrothiophene-l,l-dioxide, better known as
tetramethylene sulfone or sulfolane. In those
instances where it may be tesirable to use a
substituted sulfolane those substituted in the
3 or 3,4 positions of the ~ulfolane ring are
preferred.
The rhodium carbonyl complexes suitable for
use in the practice of the present invention
are those wherein the complex i9 at least one of
(l) rhodium in complex combination with carbon
- :, ~
1069540 D-9814
monoxide, (2) rhodium in complex combination
with carbon monoxide and hydrogen, (3) rhodium
in complex combination with carbon monoxide
and at least one Lewis base, (4) rhodium in
complex combination with carbon monoxide, hydrogen
and at least one Lewis base, and (5) mixtures
thereof.
~.
Morever, the rhodium carbonyl complexes of
this invention may be in the form of rhodium
carbonyl cluQters. P. Chini, in a review article
entitled "The Closed Metal Carbonyl Clusters"
published in Review (1968), Inorganica Chimica
Acta, pages 30-50, states that a metal cluster
compound is "a finite group of metal atoms
which are held together entirely, mainly, or at
least to a significant extent, by bonds directly
between the metal atoms even though some non-
metal atoms may be associated intimately with the
cluster". The rhodium carbonyl cluster compounds
of this invention contain rhodium bonded to
rhodium or rhodium bonded to another metal,
such as cobalt, and/or iridium. The preferred
rhodium carbonyl cluster compounds of this
invention are those which contain rhodium-
rhodium bonds. These compounds desirably contain
carbon and oxygen in the form of carbonyl (-C-0),
in which the carbonyl may be "terminal", "edge-
bridging", and/or "face-bridging". They may
. ,. . ., - , .. ... .. . .. .....
1069540 D-9814
also contain hydrogen and carbon in forms other
than carbonyl. The following are illustrative
of what is believed to be the structure of two
distinct rhodium carbonyl clus~ers and both are
suitable for use in this invention.
qr. ~:
_\ .
~c,o
. 6( )16
:~/
[Rh12 (CO) 30 ]
., ,. ., .. -
~169540
D-9814
The structures of the rhodium carbonyl
clusters may be ascertained by X-ray crystal dif-
fraction, nuclear magnetic resonance (NMR) spec-
tra, or infrared spectra as disclosed in the
article entitled "Synthesis and Properties of the
Derivatives of the [Rhl2(CO)30]2- Anion" by
; P. Chini and S. Martinengo; appearing in Inorganica
Chimica Acta, 3:2 pp299-302, June ~969). Of
particular analytical utility in the present in-
vention is the use of infrared spectroscopy which
allows for characterization of the particular
rhodium carbonyl complex present during the opera-
tion of the process of the present invention.
The rhodium carbonyl complex is, as character-
ized above, a rhodium containing compound in which
the rhodium is complexed with C0. This can be :
achieved with just carbon monoxide or in addition
to the carbon monoxide there may be included
- hydrogen and/or other organic or inorganic Lewis
base msterials to create the complex. In the
last case, "complex" means a coordination c~m-
pound formed by the union of one or more
electronically rich molecules or atoms capable
of independent existence with one or more elec-
tronically poor molecules or atoms, each of which
is also capable of independent existence. The
precise role of these Lewis bases in the reaction
10.
1069540 D-9814 ~
'~
of the present invention is not fully appreciated
at present. They may be functioning as ligands and/or
forming counter-ions under the reaction conditions
of the present process or they may be functioning
just merely as Lewis bases and neutralizing or
tying up a molecular species which if allowed to
remain "free" or in its non-base-bound state would
adversely affect the productivity of the present
invention.
Organic Lewis bases which are suitable in
the practice of the present invention contain at
least one Lewis base oxygen atom and/or one Lewis
base nitrogen atom said atoms po8sessing a pair of
electrons available for the formation of coordinate
bonds. In suitable embodiments the organic Lewis
bases contain fr~m 1 and upwards to 4 Lewis base
at~ms, preferably from 1 to 3 such atoms, and most
preferably 1 or 2 Lewis base at~ms. These organic
Lewis bases are said to be multidentate or poly-
dentate, that is to say, they are bidentate, tri-
dentate, or quadridentate, depending on whether
2, 3 or 4 Lewis base atoms are involved.
- Those organic Lewis bases which contain at
least one Lewis base nitrogen atom plus at least one
Lewis base oxygen atom will oftentimes hereinafter
be referred to as "organic aza-oxa" Lewis bases.
..;,~
D-9814
1~)69540
Suitable organic nitrogen Lewis bases most
generally contain carbon, hydrogen, and nitrogen atoms.
Suitable organic oxygen Lewis bases most generally contain
carbon, hydrogen, and oxygen atoms. Suitable organic
aza-oxa Lewis bases most generally contain carbon,
hydrogen, oxygen, and nitrogen atoms. The carbon atoms
can be acyclic and/or cyclic such as aliphatic,
cycloaliphatic, aromatic (including fused and bridged)
carbon atoms, and the like. Preferably, the organic
Lewis bases contain fram 2 to 60, most pre~erably 2 to
40 carbon at~ms. The nitrogen atoms can be in the form
of imino (-N=), amino (-N-), nitrilo (~-), etc. Desirably,
the Lewis base nitrogen atoms are in the form of imino
nitrogen and/or amino nitrogen. The oxygen atoms can be
in the form of groups such as hydroxyl (aliphatic or
O O
.. ,.
phenolic), carboxyl (-COH), carbonyloxy (-CO-), oxy (-O-),
"
carbonyl (-C-), etc., all of said groups containing
Lewis base oxygen atoms. In this respect, it is the
O
"hydroxyl" oxygen in the -COH group and the l'oxy"
oxygen in the -CO- group that are acting as the Lewis base
atoms. The organic Lewis base~ may also contain other
atoms and/or groups such as alkyl, cycloalkyl, aryl,
chloro, thiaalkyl, trialkylsilyl, and the like.
Illustrative organic oxygen Lewis bases include,
by way of illustrations, glycolic acid, meth~xyacetic
12 .
,
,- ~ - .. . . . . . . ..
1069540 D-9814
acid, ethoxyacetic acid, diglycolic acid, thiodi-
glycolic acid, diethyl ether, tetrahydrofuran, dioxane,
tetrahydropyran, pyrocatechol, citric acid, 2-methoxy-
ethanol, 2-ethoxyethanol, 2-n-propoxye~hanol, 2-n-
butylethan~ ,3-trihydroxybenzene, 1,2,4-trihydroxy-
benzene, 2,3-dihydroxynaphthalene, cyclohexane-1,2-diol,
oxetane, 1,2-dimethoxybenzene, 1,2-diethoxybenzene,
methyl acetate, ethanol, l,2-dimethoxyethane, 1,2-di-
ethoxyethane, l,2-di-n-propoxyethane, 1,2-di-n-butoxy-
ethane, pentane-2,4-dione, hexane-2,4-dione, heptane-
3,5-dione, octane-2,4-dione, l-phenylbutane-l, 3-dione,
3-methylpentane-2,4-dione; the mono- and dialkyl ethers
of propylene glycol, of diethylene glycol, of dipropylene
glycol; and the like.
Illustrative organic aza-oxa Lewis bases include,
for example, the alkanolamines, such as, ethanolamine,
diethanolamine, isopropanolamine, di-n-propanolamine,
and the like; N,N-dimethylglycine, N,N-diethylglycine;
iminodiacetic acid, N-methyliminodiacetic acid;
20 N-methyldiethanolamine; 2-hydroxypyridine, 2,4-dihydroxy- :
pyridine, 2-methoxypyridine, 2,6-dimethoxypyridine,
2-ethoxypyridine; lower alkyl substituted hydroxypyridines,
such as 4-methyl-2-hydroxypyridine, 4-methyl-2,6-di-
hydroxypyridine, and the like; morpholine, substituted - -~
morpholines, such as 4-methylmorpholine, 4-phenyl-
morpholine; plcolinic acid, methyl-substituted picolinic
acid; nitrilotriacetic acid, 2,5-dicarboxypiperazine,
13.
D-9814
1~69540
~-(2-hydroxyethyl) iminodiacetic acid, ethylene-
.diaminetetraacetic acid; 2,6-dicarboxypyridine;
8-hydroxyquinoline, 2-carboxyquinoline, cyclo-
hexane-1,2-diamine-N,N,N',N'-tetraacetic acid, the
tetramethyl ester o~ ethylenediamine-tetraacetic
acid, and the like.
Illustrative of the Lewis base nitrogen
containing compounds suitable for use in the practice
o~ the present invention are ammonia and the amines.
Any primary, secondary, or tertiary amine is suitable
in the practice of the present invention. This includes
the mono-, di-, tri-, and polyamines and those compounds
in which the Lewis base nitrogen forms part of a ring
structure as in pyridine, quinoline, pyrimidine,
morpholine, hexamethylene tetraamine, and the like.
In addition any compound capable of yielding an amino
nitrogen under the reaction conditions of the present
invention is suitable, as in the case of an amide, such
as formamide and urea, or an oxime. ~urther
illustrative of these Lewis base nitrogen compounds
are ammonia; aliphatic amines such as methylamine,
ethylamine, n-propylamine, isopropylamine,
octylamine, dodecylamine, dimethylamine, diethyl-
amine, diisoamylamine, methylethylamine, diisobutyl-
am1ne, trimethy1am1ne, methyldiethy1amine,
14.
,, . ' .,... . ..... , , . .. :.~ :, :.. : : .: .. :, ,, :. .. ... .
D-9814
1069540
triisobutylamine, tridecylamine, and the like;
aliphatic and aromatic di- and polyamines such as
1,2~ethanediamine, 1,3-propanediamine, N,N,N',NI-
tetramethylenediamine, N,N,N',N'-tetraethylethylene-
diamine, N,N,N',N' tetra-_-propylethylenediamine,
N~N~Nl~Nl-tetrabutylethylenediamine~ o-phenylene-
diamine, m-phenylenediamine, p-phenylenediamine,
_-tolylenediamine, o-tolidene, N,N,N',N'-tetra-
methyl-p-phenylenediamine, N,N,N',N'-tetraethyl-
4,4'-biphenyldiamine, and the like; aromatic amines
such as anil$ne, l-naphthyl~m1ne~ 2-naphthylamine,
p-toluidine, 0-3-xylidine, p~2-xylidine, benzylamine,
diphenylamine, dimethylaniline, diethylaniline,
N-phenyl-l-naphthylamine, bis-(1,8)-dimethylamino-
naphthalene, and the like; alicyclic amines such as
cyclohexylamine, dicyclohexylamine, and the like;
heterocyclic amines such as piperidine; substituted
piperidines such as 2-methylpiperidine, 3-methyl-
piperidine, 4-ethylpiperidine, and 3-phenylpiperidine;
pyridine; substituted pyridines such as 2-methyl-
pyridine, 2-phenylpyridine, 2-methyl-4-ethylpyridine, ~ ;~
2,4,6~-trimethylpyridine, 2-dodecylpyridine,
2-chloropyridine, and 2-(dimethylamino)pyridine;
quinoline; substituted quinolines, such as 2-(dimethyl-
amino)-6-methoxyquinoline; 4,5-phenanthroline;
1,8-phenanthroline, 1,5-phen~nthroline; piperazine;
substituted piperaz$nes such as N-methylpiperazine,
15.
1069540 D-9814
N-ethylpiperazine, 2JN-dimethylpiperazine;
2,2'-dipyridyl, methyl-sub~tituted 2,2'-dipyridyl;
ethyl-substituted 2,2'-dipyridyl; 4-triethyl-
silyl-2,2'-dipyridyl; 1, 4-diazabicyclo [2.2.2]octane
methyl substituted 1,4-diazabicyclol2.2.2]octane,
purine and the like.
Illustrative of the inorganic Lewis bases
useful in the practice of the present invention are
ammonia, hydroxides and halides, ~uch as chloride,
br~mide, iodide, or fluoride; or mixtures thereof.
Any of the above Lewis bases may be pro-
vided to the reaction in compound form or as llgands
which are in complex combination with the rhodium
carbonyl compound initially charged to the reactor.
; The precise role of the rhodium carbonyl
complexes, such as the rhodium carbonyl clusters
characterized previously, in the reaction of hydrogen
with oxides of carbon to produce polyhydric alcohols
is not fully appreciated at present. Under the re-
action conditions of the present process the carbonyl
- complexes are believed to be anionic in their active
forms. Rhodium carbonyl anions are known to be
involved in the following set of reactions as
indicated by S. M~rtinengo and ~ Chini, in Gazz.
` Chim. Ital., 10~, 344 (1972) and the references
cited therein.
:
~ .
16.
.
1~69540 D-9814-l
(I)[Rhl2(C0)34 3612 ~ 12( )30] ~` [~h6(C0)15]2- 2e* ~ [Rh6(C0)14]4-
1 lRh(CO)41- lco
[ ( ) ]2- IRh(C0)41- ~ CO ~ iRh (CO) ]3- ~ CO [Rh4(C)ll] + [Rh(C0)41
*electron
Infrared spectra under reaction conditions
of the present process have shown both the RhCC0)4
and [Rhl2(C~34_36~ anions to be present at
various concentrations at different times of the
reaction Therefore the set of reactions and
equilibria shown in I above may represent the :
10 active rhodium carbonyl species responsible for
polyhydric alcohol formation or may be merely
symptomatic of some further intermediate transitory
rhodium carbonyl structure which serves to convert
the carbon monoxide and hydrogen to the polyhydric
alcohol. :
...~
Assuming the active catalytic species is
a rhodium carbonyl complex anion, or the formation of
the active species under reaction conditions is
directly dependent on the existence of these anions,
: 20 allows one to better explain, in terms of reaction
rates, productivity and catalyst stability, the
~ role of sulfone solvents, particularly the tetra-
methylene sulfones, play in the reaction whereby
~06g540
hydrogen and an oxide of carbon are converted to
the polyhydric alcohol. It is believed that the
sulfones enhance the reactivity of these rhodium
carbonyl complex anions because a 'tnaked", reactive
anion is produced. Naked rhodium carbonyl anions
are believed to be produced under the reaction con-
ditions of the present process because the sulfone
solvent decreases any tendency of the rhodium
carbonyl anions to ion pair, the rhodium carbonyl
anions are not strongly solvated, nor is the rhodium
strongly complexed by the solvent all of which tend
to produce an anion having a higher degree of reactivity
under the reaction conditlons employed.
The novel process is suitably ef~ected over
a wide superatmospheric pressure range of from about
800 psia to about 50,000 psia. Pressures as high
as 50,000 psia, and higher can be employed but with
no apparent advantages attendant thereto which of~set
the unattractive plant investment outlay required
~or such high pressure equipment.
In one embodiment of this invention the
upper pressure limitation is approximately 12,000
psia. Effecting the present process below about
12,000 psia, especially below about 8000 psia, and
preferably at pressures below about 6000 psia,
results in cost advantages which are associated with
` low pressure equipment requirements. However,
when practicing the present invention at pressures
'.
':
18.
D-9814
1069540
below about 12,000 psia, the rate of desired
product formation is quite slow and in order to
obtain a faster reaction rate and/or higher con-
~) versions to the desired product there is provided
to the reaction a promoter which may be a salt
and/or an organic Lewis base nitrogen compound.
In those instances where the Lewis base
nitrogen compound is contained as a ligand in
the rhodium carbonyl complex charged to the -
reactor or where anion of the salt promoter charged
to the reactor is a rhodium carbonyl complex
such as cesium triacontacarbonylrhodate, it
may not be necessary to add to the reaction
any additional amounts o~ these promoters. A
suitable pressure range for effecting the
reaction in the presence of these promoters is
from about 1000 psia to about 12,000 psia, -
preferably from about 4000 to about 12,000 psia.
In a preferred embodiment of the present
` invention the pressures referred to above repre-
sent the total pressures of hydrogen and oxides
of carbon in the reactor.
Suitable salts useful in the practice
of the present invention at pressures below
: about 12,000 psia include any organic or in-
organic salt which does not adversely affect the
production of polyhydric alcohols. Experimental
work completed to date indicates that any salt
19.
D-9814
106959~0
will show this promoter effect under some, but not
all, glycol-producing conditions. Illustrative
of the salts useful in the practice of the present ;~
invention are the ammonium salts and the salts of
the metals of Group I and Group II of the Periodic
Table (Handbook of Chemistry and Physics - 50th
Edition) for instance the halide, hydroxide, alkoxide,
phenoxide and carboxylate salts such as sodium
fluoride, cesium florlde, cesium pyridtnolate,
cesium formate, cesium acetate, cesium benzoate,
cesium p-methylsulfonyl benzoate (CH3S02C~H4COO)Cs,
rubidium acetate, magnesium acetate, strontium
acetate, ammonium formate, ammonium benzoate and
the like. Preferred are the cesium and ammonium
carboxylate salts, most preferably their formate, `,-
benzoate and para-lower alkyl sulfonyl benzoate
salts.
Also useful in the practice of the
present invention are organic salts of the follow-
ing formula:
,
~:
': ,
':
.~
.':
~069540 D-9814 ~
1 1 ~
II ~ R4 N R~ Y
~ R3
quaternary ammonium salts
~ 16 1l ~
III ~5 -P=~N--P- R2 ) ;~*
bis(triorgano phosphine)iminium salts
wherein Rl through R6 in formulas (II) and (III) ~ ~:
above are any organic radicals which do not ad-
versely affect the production of polyhydric
alcohols by reacting oxides of carbon with hydro-
. gen in the presence of the aforedefined rhodium
: carbonyl complex, such as a straight or branched
chain alkyl group, having from 1 to 20 carbon
atoms in the alkyl chain, such as methyl,
; ethyl, n-propyl, isopropyI, _-butyl, octyl, 2-
- ethylhexyl, dodecyl, and the like; or a
cycloaliphatic group including the monocyclic
:. 20 and bicyclic groups cyclopentyl, cyclohexyl,
and bicyclo[2~2.l] heptyl groups, and the like
21.
;. ... ~ . . . .
D-9814-1
1069540
or an aryl, alkylaryl, or aralkyl group such as
phenyl, naphthyl, xyl~l, tolyl, t-butylphenyl, ~enzyl,
beta-phenylethyl, 3-phenylprop~l and the like; or a
~unctionally substituted alkyl such as be -hydroxy-
ethyl, ethoxymethyl, ethoxyethyl, phenoxyethyl, and
the like; or a polyalkylene ether group of the formula
~CnH2nO)x~OR wherein n has an average value from 1 to
4, _ has an average value from 2 to about 150, and R
may be hydrogen or alkyl of 1 to about 12 carbon
atoms. Illustrative of such polyalkylene ether groups
are poly(oxyethylene~, poly(oxypropylene), poly(oxy-
ethyleneoxypropylene~, poly(oxyethyleneoxybutylene),
and the like. Y in formulas II and III above may be
any anion which does not adversely affect the produc-
tion of polyhydric alcohols in the practice of the
present invention such as hydroxide; a halide, for
instance fluoride, chloride, bromide and iodide; a
carboxylate group, such as formate, acetate, propionate,
and benzoate and the like; an alkoxide group such as
methoxide, ethoxide, phenoxide, and the like; a
functionally substituted alkoxide or phenoxide group
such as methoxyethoxide, ethoxyethoxide, phenoxy-
ethoxide and the like; a pyridinolate or quinolate
group; and others. Preferably Y in formulas II and III,
above, is a carboxylate, most preferably formate,
acetate and benzoate.
A suitable method for preparing the bis(tri-
organo phosphine~iminium salts is disclosed in an
article by Appel, ~. and Hanas, A. appearing in
Z. Anorg. u. Allg. Chem., 311, 290, (1961).
22.
.. . ., - . . . - . .
D-~814-1
1069540
qther o~ganic salts useful ln the p~actice
o~ the present ~nvention include the quaterni~ed
~eterocyclic amine salts such as the pyridinlumt
piperidinium, morpholinium, quinolinium salts and the
like, e.g., N-ethylpyridinium fluoride, N-methyl-
morpholinium benzoate, N-phenylpiperidinium hydroxide
N,N'-dimethyl-2,2-bipyridinium acetate, and the like.
In one of the embod~ments of the present ;`
invention, the anion of the above salt promoters may
be any of the rhodium carbonyl anions. Suitable
rhodium carbonyl anions include ~Rh6(C0)15]
CRh6(C0)15Y] wherein Y may be halogen, such as
chlorine, bromine, or iodine, ~Rh6(C0)15(COOR")]
wherein R" i8 lower alkyl or aryl such as methyl,
ethyl, or phenyl; lRh6(C0)14~2 ; [Rh7(C0)16]3 ;
and ~Rhl2(C)30]
Under reaction conditions where a salt
promoter is employed the salt is desirably added with
the initial charge of reactants in amounts of from
about 0.5 to about 2.0 moles, preferably from about
0.8 to about 1.6 moles, and most preferably from
about 0.~ to 1.4 moles of salt for every five atoms
of rhodium present in the reaction mixture.
The Lewis base nitrogen promoters may be
any of the Lewis base nitrogen or organic aza-oxa
Lewis base compounds defined above. Preferably the
Le~is base nitrogen promoters are amines. This also
.
23.
- : :
D-9814-1
1069540
includes those compounds where the nitrogen
is part of a heterocylic ring such as the
pyridines, pyrimidines, piperidines, morpholines,
quinolines and the like. Illustrative of these
preferred Lewis base promoters are pyridine,
2,4,6-trimethylpyridine, 4-dimethylaminopyridine,
4-tridecylpyridine, isobutylamine, triethylamine,
N-methylpiperidine, N-methylmorpholine, bis-(1,8)-
dimethylaminonaphthalene, 1,4-diazabicyclo[2.2.2~-
octane, and quinuclidine.
Under reaction conditions where a Lewis
base nitrogen compound is used as a promoter it
is preferably used in amounts from about 0.02 to
about 2 equivalents of promoter, most preferably
from about 0.1 to about 1 equivalent of promoter,
for every mole of rhodium in the reaction mixture.
The number of equivalents of promoter is equal to
the number of moles of promoter times the number
of nitrogen atoms in each molecule.
Mixtures of the above salt and amine
low pressure promoters may be used in the practice -
of the present invention.
The salt and/or Lewis base nitrogen low
pressure promoters may be added to the reaction in
compound form or there may be added to the reactor
24.
- .,: , ~ .,.. .~ . . :
1069540 D-9814-1
any substance capable of generating the salt
and/or the amine promoter in si~u either prior
l:o or during the reaction conditions of the
present invention.
For instance an amide such as
formamide, urea, and the like or an oxime may
be added to the reactor in place of the amine
promoter.
Another and preferred group of low
pressure promoters include the trialkanolamine
borates, preferably those having the formula:
\ O
Rb--GN ~Rc
wherein Ra, Rb, and Rc may be at least one of
hydrogen or lower alkyl having from 1 to 12
carbon atoms in the alkyl chain. Most preferably
the trialkanolamine borates useful in the practice
of the present invention are triethanolamine
borate and triisopropanolamine borate.
25.
.
~069540 D-g8l4-1
The sulfones useful in the practice of
the present invention may be used in admixture
with other conventional miscible solvents, prefer-
ably wherein the solvent mixtures contain the
sulfone in amounts of from about 25 to 99, most
preferably from about 50 to about 99 percent by
weight of the total solvent mixture. :~
Illustrative of solvents which may be
used in admixture with the sulfone are the alkanols
such as methanol, ethanol, propanol, 2-ethylhexanol
and the like; esters such as methyl acetate,
propyl acetate, butyl acetate and the like; lactones
such as gamma-butyrolactone, delta-valerolactone,
and the like; ethers such as tetrahydrofuran,
tetrahydropyran, dimethyl ether, diethyl ether, .
1,2-diethoxybenzene, the mono- and dialkyl
ethers of alkylene and polyalkylene glycols,
such as the mono- and dimethyl and ethyl ethers
of ethylene glycol, propylene glycol, butylene
glycol, diethylene glycol, dipropylene glycol,
triethylene glycol, tetraethylene glycol,
dipropylene glycol, oxyethylene-oxypropylene ~:
glycol and the like; and water.
26.
.. . . . . , . , . .. ; ... . .. . . ..
D-9814
1069540
;~
The quantity of catalyst employed is
not narrowly critical and can vary over a wide
range. In general, the novel process is desirably
conducted in the presence of a catalytically
effective quantity o$ the active rhodium species
which gives a suitable and reasonable reaction
rate. Reaction proceeds when employing as little
as about 1 X 10 6 weight percent, and even lesser
amounts, of rhodium metal based on the total
weight of reaction mixture. The upper concentra-
tion limit can be quite high, e.g., about thirty
weight percent rhodium, and higher, and the
realistic upper limit in practicing the invention
appears to be dictated and controlled more by
economics in view of the exceedingly high cost
of rhodium metal and rhodium compounds. ~epending
on various factors such as the promoter of choice,
the partial pressures of hydrogen and oxides of
carbon, the total operative pres~ure of the system,
the operative temperature, the choice of the organic
co-diluent, and other considerations, a catalyst
concentration o$ from about 1 X 10 5 to about 5
weight percent rhodium (contained in the complex
catalyst) based on the total weight of reaction
mixture, is generally desirable in the practice o$
the invention.
27.
D-9814
1069540
The operative temperature which may be
employed can vary over a wide range of elevated
temperatures. In general, the novel process can
be conducted at a temperature in the range of from
about 100C. and upwards to approximately 375C.,
and higher. Operative temperatures outside this
stated range, though not excluded from the scope
of the invention, do not fall within certain desir- ~
able embodiments of the invention, At the lower -
end of the temperature range, and lo~er, the rate
of reaction to desired product becomes markedly
slow. At the upper temperature range, and beyond,
signs of some catalyst instability are noted. Not-
withstanding this factor, reaction continues and
polyhydric alcohols and/or their derivatives are
produced. Additionally, one should take notice
of the equilibrium reaction for forming ethylene
glycol:
2 CO + 3H ~ HOCH2CH20H
At relatively high temperatures the equilibrium
increasingly favors the left hand side of the
equation. To drive the reaction to the formation
of increased quantities of ethylene glycol,
higher partial pressures of carbon monoxide and
hydrogen are required. Processes based on
correspondingly higher operative pressures,
28.
D-9814
106954~
however, do not represent preferred embodiments
of ~he invention in view of the high investment
costs associated with erecting chemical plants
which utilize high pressure utilities and the
necessity of fabricating equipment capable of
withstanding such enormous pressures. Suitable
operative temperatures are between about 150C.
to about 300C., and desirably from about 190C.
to about 275C.
The novel process is eff~cted for a
period of time sufficient to produce the desired
polyfunctional oxygen-containing products and/or
derivatives thereof. In general, the residence
time can vary from minutes to several hours, e.g.,
; from a few minutes to approximately 24 hours, and
longer. It is readily appreciated that the resi-
dence period will be influenced to a significant
extent by the reaction temperature, the concentra-
tion and choice of the cata~yst, the total gas
pressure and the partial pre~sure exerted by its
components, the concentration, and other factors.
The synthesis of the desired product(~) by the re-
action of hydrogen with an oxide of carbon is
suitably conducted under operative conditions which
give reasonable reaction rates
The relative amounts of oxide of carbon
and hydrogen which are initially present in the
29. '
D-9814
10695~0
reaction mixture can be varied over a wide range.
In general, the mole ratio of CO:H2 is in the
range of from about 20:1 to about 1:20, suitably
from about 10:1 to about 1:10, and preferably
from about 5:1 to about 1:5.
It is to be understood, however, that
molar ratios outside the aforestated broad range
may be employed. Substances or reaction mixtures
which give rise to the formation of carbon monoxide
and hydrogen under the reaction conditions may be
employed instead of mixtures comprising carbon
monoxide and hydrogen which are used in preferred
embodiments in the practice of ~he invention.
For instance, polyhydric alcohols are obtained by
using mixtures containing carbon dioxide and
hydrogen. Mixtures of carbon dioxide, carbon
monoxide and hydrogen can also be employed. If
desired, the reaction mixture can comprise steam
and carbon monoxide.
The novel process can be executed in
a batch, semi-continuous, or continuous fashion.
The reaction can be conducted in a single reaction
zone or a plurality of reaction zones, in series
or in parallel, or it may be conducted inter-
mittently or continuously in an elongated tubular
zone or serie~ of such zones. The material of
construction should be such that it is inert
30.
1069540 D-9814-1
~ur~ng the reaction and the fabxiication of
the equipment should be'abIe to ~ithstand the'
reaction te~perature and pressure. The reaction
zone can be fltted with'internal and/or external
heat exchangerCs~ to thus control undue tempera-
ture fluctuations, or to prevent any possible
"run-awa~" reaction temperatures due to the
exothermic nature of the reaction. In preferred
emBodiments of the invention, agitation means to
vary the degree of mixing of the reaction mixture
can ~e suitably employed. Mixing induced by
vibration, shaker, stirrer, rotatory, oscillation9
ultrasonic, etc., are all illustrative of the
types of agitation means which are contemplated.
Such means are available and well-known to the art.
The catalyst may be initially introduced into the
reaction zone batchwise, or it may be continuously
or intermittently introduced into such zone during
the course of the synthesis reaction. Means to
introduce and/or adjust the reactants, either
intermittently or continuously, into the reaction
zone during the course of the reaction can be
conveniently utilized in the novel process especially
to maintain the desired molar ratios of and the
partial pressures exerted by the reactants.
D-9814-1
~069540
As intimated previously, the operative
conditions can be adjusted to optimize the con-
version o~ the desired product and/or the
economics of the novel process. In a continuous
process, for instance, when it is preferred ~o
operate at relatively low conversions, it is ~
generally desirable to recirculate unreacted ~`
synthesis gas with/without make-up carbon
monoxide and hydrogen to the reaction. Recovery
iO of the desired product can be achieved by
methods well-known in the art such as by dis-
tillatîon, fractionation, extraction, and the
like. A fraction comprising rhodium catalyst,
generally contained in byproducts and/or normally
liquid organic diluent, can be recycled to the
reaction zone, if desired. All or a portion
of such fraction can be removed for recovery
of the rhodium values or regeneration to the
active catalyst can be intermittently added to
the recycle stream or directly to the reaction
zone.
The active forms of the-rhodium carbonyl ~ !
clusters may be prepared by various techniques.
They can be preformed and then introduced into
the reaction zone. Alternatively, any of
the host of rhodium-containing substances as
well as any of the low pressures promoters
. .. . . .. ~ .. .. : .
D-9814
106~54(~ ~
can be introduced into the
reaction zone and, under the operative conditions
of the process (which of course includes hydrogen
and carbon monoxide), the active rhodium carbonyl
cluster can be generated in situ. Illustrative of
rhodium-containing substances which can be conven-
iently introduced or placed in the synthesis zone
include, for example, rhodium oxide (Rh203),
tetrarhodium dodecacarbonyl, dirhodium octacar-
bonyl, hexarhodium hexadecacarbonyl (Rh6(CO)16),rhodium(II) formate, rhodium(II) acetate, rhodium
(II) propionate, rhodium~II) butyrate, rhodLum(II)
valerate, rhodium(III) naphthenate, rhodium dicar-
bonyl acetylacetonate, rhodium tri(acetylacetonate),
rhodium trihydroxide, indenyl-rhodium dicarbonyl,
rhodium dicarbonyl (l-phenylbutane-1,3-dione),
tris(hexane-2,4-dionato)rhodium(III), tris(heptane-
2,4-dionato)rhodium(III), tris(l-phenylbutane-1,3-
dionato)rhodium(III), tris(3-methylpentane-2,4-
dionato)rhodium(III), tris(l-cyclohexylbutane-1,3-
dionato)rhodium(III), triacontacarbonyl rhodium salts
and rhodium-containing compounds deposited on porous
supports or carriers capable of providing rhodium
carbonyls in solution, and others.
The preparation of the rhodium carbonyl com-
plex compounds can be conveniently carried out in
the sulfone solvent, the co-diluent or mixtures
thereof. Tetrarhodium dodecacarbonyl, though of
limited solubility, can be added to the solven~
in a finely divided form. Any of several of the
33
1069540 D-9814-1
.
rhodium-containing compounds illustrated previously
can be employed ~n lieu of tetrarhodium dodecacar-
bonyl. The organic Lewis bases such as pyridine,
or other promoters, such as the aforedefined low
pressure salt promoters, can also be added thereto.
The rhodium carbonyl complex or cluster forming
reaction can be effected under a carbon monoxide
pressure, with or without H2, of about 1 to 15
atmospheres, and higher, using a temperature
of about 30C. to about 100C. 7 for a period of
time ranging from minutes to a few days, generally
from about 30 minutes to about 24 hours. The
resulting rhodium carbonyl complex contained in the
sulfone solvent i8 catalytically active in this
process. In preparing the aforesaid complexes,
one can suitably employ from about .01 to about 25
moles salt or Lewis base nitrogen promoters per mole
of rhodium (contained in the rhodium compound used
as a rhodium source). Ratios outside this stated
range can be employed especially when it is desirable
to use diluent quantities of the low pressure promoters.
The equipment arrangement and procedure
which provides the capability for determining the
existence of anionic rhodium carbonyl complexes
or clusters having defined infrared spectrum
characteristics, during the course of the manufacture
of polyhydric alcohols from carbon monoxide and
. . . .. : ~ .
D-9814-1
~ 069540
hydrogen, pursuant to this invention is disclosed
and schematically depicted in U.S. Patent 3,957,857
issued May 18, 1976.
A particularly desirable infrared cell
construction is described in U.S. Patent 3,886,364
issued May 27, 1975.
The "oxide of carbon" as covered by the
claims and as used herein is intended to mean carbon
monoxide and mixtures of carbon dioxide and carbon
monoxide, either introduced as such or foxmed in
the reaction. Preferably the oxide of carbon is
carbon monoxide.
The reaction of the present invention is
conducted in what is believed to be a homogeneous
liquid phase, which means that the catalyst, the
reaction products and the promoter if present are
in solution. Though the reaction to produce
; alcohols is essentially homogeneous, there may be
small amounts of insoluble catalyst particles
depending on the reaction conditions e~ployed.
The following examples are merely illus-
trative and are not presented as a definition of
the limits of the invention.
The sulfolane used in the following
examples was purified prior to use according to
D-9814
~69540 ~,
the method disclosed by E.- N. Arnett and C. F.
Douty, reported in the Journal of the American
Chemical Society, 86, 409 (1964).
The 3,4-bis (2-methoxyethoxy) sulfolane
used in the following examples was prepared by
reacting the monomethylether of ethylene glycol with
3,4-dichlorosulfolane using a sodium hydroxide
catalyst at atmospheric pressure and temperature of
20-25C for 4 hours and 40-50C for 1 hour. The
refined product had a boiling point of 153-154C at
0.25 mm of Hg and a purity of 99.8 percent.
Other materials used in the following
examples possessed the following characteristics: !
cesium benzoate (recrysta llized from H20
Analysis Found: C,32.62; H, 1.90. Calcd. for
C7H502Cs: C,33.10; H, 1.98). Ammonium acetate
and ammonium benzoate were purchased from PCR,
Inc., Gainesville, Fla. (veripur grade).
Triisopropanolamine borate (mp. 155-157.5).
36.
10~9540 D-9814-1
Example 1
A 150 ml. capacit~ stainless steeI reactor
capa~le of withstand~ng pressures up to 7,000
atmospheres was charged with a premix of 75 cubic
centimeters ~cc2 of sulfolane, 3.0 millimoles
Cmmol), .77 grams, o~ rhodium dicarbonylacety-
lacetonate, and 0.625 m~ol of pyridine. The
reactor was sealed and charged with a gaseous
mîxture, containing equal molar amounts of carbon
monoxide and hydrogen, to a pressure of 8,000
pounds per square inch (psig). Eeat was applied
to the reactor and its contents; when the temperature
of the mixture inside the reactor reached 190C., as
measured by a suitably placed thermocouple, an
additional adjustment of carbon monoxide and hydro-
gen ~H2:COzl:l mole ratio~ was made to bring the
pressure back to 8000 psig. The temperature was
maintained at 240C. for 4 hours. During this
period of time additional carbon monoxide and hydro-
gen was added whenever the pressure inside the
reactor dropped below about 7500 psig. With these
added repressurizations the pressure inside the
reactor was maintained at 8000 psig + 400 psig over
the entire 4 hour period.
After the 4 hour period, the vessel and its
` contents were cooled to room temperature,the excess
gas vented and the reaction product mixture was
removed. Analysis of the reaction product mixture
was made by gas chromatog~aphic analysis using a
Hewlett Packard FMT~ model 810 Research Chromatograph.
37.
1069S40 D-9814
Analysis of the product mixture showed 5.7
grams of ethylene glycol, 2.6 grams of methanol,
.34 grams of glycol monoformate and a rhodium
recovery of 84 percent (82% ~ 2% in wash) based on
the total rhodium charged to the reactor.
Rhodium recovery was determined by atomic
absorption analysis of the contents of the reactor
after the venting of the unreacted gases at the
end of the reaction. A further analysis was run on
a "wash" of the reactor and the results of the two
analyses were c~mbined and reported as the rhodium '-
recovered. The wash of ~he reactor consisted of
charging to the reactor 100 cc of the solvent used
for that experiment, and bringing the reactor and
its contents to a temperature of 160C and a pressure
of 14,000 to 15,000 psig and maintaining these con- ;
ditions for a period of 30 minutes. The reactor was
then cooled and the unreacted gases vented and an
atomic absorption analysis for rhodium was run on
the reactor's contents. The rhodium recovery values
therefore would be the percent rhodium based on the
total rhodium charged to the reac~or that is
soluble or suspended in the reaction mixture and
the wash after the specified reaction t~me.
Exam~le 2
Example 1 was repeated except dimethyl
sulfone was u~ed as the solvent in place of
38.
1069540 D-9814
sulfolane. Analysis of the product mixture showed
4.9 grams of ethylene glycol, 1.4 grams of methanol,
and .1 grams of ethylene glycol monoformate. l~e amount
of methanol reported represents a lower limit in that
much of the methanol was probably lost when the reaction
mixture was dumped at high temperature.
Exa_ple 3
Example 1 was repeated except that 0.75 mmol.
of bis-triphenylphosphine iminium acetate was used in
place of the pyridine. Analysis of the product mixture
showed 5.2 grams of ethylene glycol, 3.2 grams of
methanol, .1 grams of methyl formate, .03 grams of
ethanol, .1 grams of ethylene glycol monoformate and
a rhodium recovery of 83 percent(79% + 4% from wash).
Example 4
Example 3 was repeated except 3,4-bis(2-methoxy) `
ethoxy)sulfolane, CH30CH2CH20- ~ - OCH2CH20CH3
was used as the solvent in place of the sulfolane.
Analysis of the product mixture showed 5.2 grams
of ethylene glycol, 2.2 grams of methanol, and a
rhodium recovery of 88 percent (78% + 10% from wash).
Example 5
Example 3 was repested except dimethyl sulfone
was used as the solvent in place of sulfolane.
Analysis of the product mixture showed 2.2 grams of
ethylene glycol and approximately 0.9 grams of
.
~ 39
::
~-9814
~069540
methanol. (A lower limit for methanol produced as
in example 2)
.
Example 6
Example 1 was repeated except the promoter
charge consisted of 1.25 mmol of pyridine and 0.65
mmol of cesium formate and the reaction temperature
was 220C. Analysis of the product mixture showed
1.5 grams of ethylene glycol, 2.9 grams of methanol,
.19 grams of methyl formate and a rhodium recovery of
98 percent (91% + 7% from wash).
Example 7
Example 6 was repeated except 3,4-bis(2-methoxy)
ethoxy)-sulfolane was the solvent in place of sulfolane.
Analysis of the product mix~ure showed 2.7 grams of
ethylene glycol, 2.4 grams of methanol and a rhodium
recovery of 95 percent (86% + 9% from was~).
Example 8
Example 1 was repeated except the pyridine
concentration was increased to 1.25 mmol. Analysis
of the reaction product showed 5.0 grams of ethylene
glycol, 4.4 grams of methanol, .53 grams of methyl
formate,.12 grams of propylene glycol, .26 grams of
~ ethylene glycol monoformate and a rhodium recovery
- of 85 percent (80% + 5% from wash3.
Example 9
; Example 8 was repeated except the reaction
~ pressure was 6,000 psia. (pH2/pCO=l/l molar ratio)
.
40.
`'~`
D-9814
1069540
Analysis of th~ product mixture showed 2.2 grams
of ethylene glycol, 2.4 grams of methanol, .15 grams
of methyl formate, .08 grams of propylene glycol,
04 grams of ethylene glycol monoformate, .03 grams
ethanol and a rhodium recovery of 81 percent (78% + 3%
from wash).
Example 10
Example 9 was repeated except the reaction
pressure was 12,000 psia (pC0/pH2=1/1 molar ratio).
Analysis of the reaction product showed 11.7 grams
of ethylene glycol, 10.6 grams of methanol, 2.10
grams of methyl formate, .66 grams of ethylene glycol
monoformate, 16 grams of ethanol and a rhodium recovery
of 86 percent (82% + 4% from wash).
Example 11
Example 10 was repeated except the reaction
pressure was 10,000 psig (partial pressure of C0~6,000
psig and partial pressure of H2=4,000 psig). Analysis
of the reaction product showed 8.25 grams of ethylene
glycol, 7 20 grams of methanol, 1,1~ grams methyl formate,
.42 grams ethylene glycol monoformate, .11 grams of
ethanol, and a rhodium recovery of 97 percent (g3% + 4%
from wash)
Example 12
Example 11 ~as repeated except the reaction
pressure was 10,000 psig (partial pressure of C0=5,000
psig and partial pressures H2=5,000 psig).
r
, 41.
D-9814
1069540
Analysis of the reaction product showed 9.2 grams
of ethylene glycol, 8.0 grams of methanol, i.1 grams
of methyl formate, .08 grams of ethanol, .33 grams
of ethylene glycol monoformate and a rhodium recovery
of 86 percent (81% ~ 5% from wash).
Example 13
Example 8 was repeated except 1.25 mmol of
2-hydroxypyridine was used in place of pyridine.
Analysis of the reaction mixture showed 2.7 grams
of ethylene glycol, 3.8 grams of methanol and a
rhodium recovery of 67 percent (61% + 6% from wash).
Example 14
Example 13 was repeated except N,N'-dimethyl-
aniline was used in place of 2-hydroxypyridine. Analysis
of the reaction product showed 1.4 grams of ethylene
glycol, 4.1 grams of methanol and a rhodium recovery
of 6~ percent (58% + 3% from wash).
Example 15
.
Example 14 was repeated except 8-hydroxy-
quinoline was used in place of the N,N'-dimethylaniline.
Analysis of the reaction product showed 3.0 grams of
ethyleneglycol, 3.6 grams of methanol and ~ rhodium ~ ~;
recovery of 74 percent (67% + 7% from wash).
.
,
';
~ 42.
, . .
.,
D-9814
1069540
Example 16
Example 15 was repeated except bis-(1,8)~nethyl-
aminonaphthalene was used in place of the 8-hydroxy-
quinoline. Analysis of the reaction product showed
6.0 grams of ethylene glycol, 2.g grams of methanol
and a rhodium recovery of 81 percent (78% + 3% ~rom wash).
Example 17
Example 16 was repeated except N-methyl-
morpholine was used in place of the 1,8-dimethyl-
aminonaphthalene. Analysis of the reaction product
showed 5.8 grams of ethylene glycol, 3.2 grams of
methanol and a rhodium recovery of 68 percent (64% + 4%
from wa8h,
Example 18
Example 17 was repeated except 0.75 mmol
of bis(triphenylphosphine)iminium acetate was added
in addition to the N-methylmorpholine. Analysis of
the reaction product showed 6.4 grams of ethylene
glycol, 3.8 grams of methanol and a rhodium recovery ~;
- 20 of 88 percent (82% + 6% from wash).
Example 19
~ '.
Example 1 was repeated except 1.30 mmol of
4-phenylpyridine was used in place of pyridine,
a reaction temperature of 258C and 5.34 mmol of
..
,; .
'~
43.
`I `
, : ~
.. ..... . .. .. ., . . . . ~ .. . ...... .. . .... . .. . . . .
D-9814
1069540
rhodium dicarbonylacetylacetonate were used.
Analysis of the product mixture showed 6.7 grams of
ethylene glycol, 5.4 grams of methanol and a rhodium
recovery of 62 percent (59% + 3% from wash).
Example 20
Example 1 was repeated except 1.25 mmol of
4-tridecylpyridine was used in place of the pyridine
Analysis of the reaction product showed 5.2 grams of
ethylene glycol, 3.8 grams of methanol and a rhodium
recovery of 81 percent (78% + 3% from wash).
Example 21
Example 1 was repeated except 1,4-diaza-
bicyclo [2.2.2] octane was used in place of pyridine
and the reaction temperature was 220C. Analysis of
the reaction product showed 3.5 grams of ethylene
glycol, 1.3 grams of methanol and a rhodium recovery
of 88 percent (81% + 7% from wash).
Example 22
Example 21 was repeated except 0.31 mmol. of
the 1,4-diazabicyclo [2.2.2] octane was used. Analysis
of the reaction product showed 0.9 grams of ethylene
glycol, 1.4 grams of methanol and a rhodium recovery
of 74 percent (71% + 3% from wash).
Example 23
Example 22 was repeated except 1.25 mmol. of
1,4-diazabicyclo [2.2.2] octane`was used. Analysis
of the reaction product showed 2.6 grams of ethylene
glycol, 2.8 grams of methanol and a rhodium recovery
of 93 percent (8770 + 6% from wash).
.
~ 44.
, .
~069540 D-9814-1
~xamp~e~24
Example 23 was repeated except 2.50 m~ol
o~ 1,4~dlazabicyclo ~2,2.2~ 'octane'was used,
Analys~s of the reaction product showed 1.5 gra~s
of ethylene glycol, 2.:8 grams of methanol and a
rhod~um ~ecovery of 93'percent C90~/O + 3% from wash~.
' Exam'p'l'e' 25
Example 1 was repeated except 3,5-dichloropy-
ridine was used in place of pyridine and the reaction
temperature was 220C. Analysis of the product mixture ' -~showed 1.0 grams of ethylene glycol, 0.9 grams of
methanol and a rhodium recovery of 82 percent (76% + 6%
from wash).
Example 26
Example 25 was repeated except pyridine was
used in place of the 3,5-dichloropyridine. Analysis '
of the reaction product showed 3.8 grams of ethylene
glycol, 2.2 grams of methanol and a rhodium recovery
of 99 percent (91% + 8% from wash).
Example 27
,
Example 26 was repeated except 0.31 mmol of
` pyridine was used. Analysis of the reaction product
showed 0.5 grams of ethylene glycol, 1.9 grams of '
`~ methanol and a rhodium recovery of 72 percent (66% + 6%
from wash).
Example '28
i ~xample 27 was repeated except 1.25 mmol of
;,j pyridine ~as used. Anal~æis of the reaction product
showed 2.1 grams of ethylene glycol, 3.3 grams of
methanol and a rhodium recovery of 94 percent (87% + 7%
from wash).
'.` '
45.
lOG9540 D-9814
Example_29
Example 28 was repeated except 2.50 mmol
of pyridine was used. Analysis of the reaction
product showed 1.2 grams of ethylene glycol and
3.4 grams of methanol and a rhodium recovery of
104 percent (97% + 7% from wash).
Example 30
Example 1 was repeated except 0.5 mmol
of cesium formate was used in place of the pyridine. ~;
Analysis of the reaction product showed 1.5 grams
of ethylene glycol, 4.1 grams of methanol and a
rhodium recovery of 77 percent (72% + 5% from wash).
Example 31
~'
Example 30 was repeated except 0.65 mmol
of cesium formate was used. Analysis of the reaction ~ ;*
product chowed 3.6 grams of ethylene glycol, 3.8
grams of methanol and a rhodium recovery of 86
percent (80% + 6% from wash). ~-
Example 32
Example 30 was repeated except 0.75 mmol of
cesium formate was used. Analysis of the reaction
product showed 3.3 grams of ethylene glycol,
3.5 grams of methanol and a rhodium recovery of
75 percent (72% + 3% from wash).
' .
~ 46.
.
.
~069540 D-9814
Example 33
Example 31 was repeated except 1.0 mmol
of cesium formate was used. Analysis of the
reaction product showed 3.0 grams of ethylene
glycol, 4.l grams of methanol and a rhodium recovery
of 84 percent (77% + 7% from wash).
Example 34
Example 33 was repeated except 0.65 mmol of -
cesium benzoate was used instead of the cesium
formate. Analysis of the reaction product showed
4.2 grams of ethylene glycol, 3.0 grams of
methanol and a rhodium recovery of 80 percent (74% + 6%
from wash).
Example 35
Example 34 was repeated except 0.65 mmol of
cesium isobutyrate was used instead of the cesium
benzoate. Analysis of the reaction product showed
3.8 grams of ethylene glycol, 3.2 grams of
methanol and a rhodium recovery of 88 percent (82% + 6%
from wash~.
Example 36
Example 35 was repeated except 0.65 ~mol of
cesium fluoride was used instead of the cesium iso-
~! butyrate. Analysis of the reaction product showed
1.9 grams of ethylene glycol, 2.5 grams of methanol
and a rhodium recovery of 88 percent (76% ~ 12% from
wash).
:
~069540 D-9~14
Example 37
Example 1 was repeated except the solvent
(75 ml, total) used consisted of a mixture of 76
percent by volume sulfolane and 24 percent by volume
of the dimethyl ether of tetraethylene glycol
(tetraglyme). Analysis of the reaction product
showed 6.5 grams of ethylene glycol, 2.6 grams
of methanol and a rhodium recovery of 77 percent (71% +
6% from wash).
Example 38
Example 37 was repeated except the volume
ratio of sulfolane to tetraglyme was 54 to 46.
Analysis of the reaction product showed 5.3 grams .,~
of ethylene glycol, 2.7 grams of methanol and a
rhodium recovery of 72 percent (62% + 10% fr~m wash).
Example 39
Example 38 was repeated except the volume
ratio of sulfolane to tetraglyme was 36 sulfolane/
64 tetraglyme. Analysis of the reaction product
showed 5.2 grams of ethylene glycol, 2.6 grams
of methanol and a rhodium recovery of 59 percent (54%
+ 5% from wash~.
Example 40
~ .~
Example 39 was repeated except the volume
ratio of sulfolane to tetraglyme was 17 sulfolane/
83 tetraglyme. Analysis of the reaction product
showed 2.4 grams of ethylene glycol, 2.6 grams of
methanol and a rhodium recovery of 33 percent (33% +
0% from wash).
48.
1069540
D-9814
Example 41
~.
Example 1 was repeated except the 0.63
mmol of pyridine was omitted and the reaction
pressure was raised to 17,500 psia. Analysis
of the reaction product showed 8.4 grams of
ethylene glycol, 3.7 grams of methanol, 0.9
grams of water, 0.6 grams of methyl formate,
0.3 grams of propylene glycol, 0.4 grams of
ethylene glycol monoformate, 1.3 grams of
glycerine and a rhodium reco~ery of 95 percent
(88% + 7% from wash).
Example 42
Exa~ple 1 was repeated except 0.65 mmol
of ammonium benzoate was used in place of the
pyridine. Analysis of the reaction product ;
showed 6.2 grams of ethylene glycol, 3.0
grams of methanol and a rhod~um recovery of 87
percent (81% + 6% from wash).
- Example 43
Example 42 was repeated except 0.75 mmol of
ammonium bencoate was charged to the reactor.
Analysis of the reaction product showed 5.2 grams
of ethylene glycol, 2.4 grams of methanol and a
rhodium reco~ery of 83 percent (78% + 5% from wash).
.
49. ~
,:
1069540
Example 44
Example 43 was repeated except the 0.85
mmol of ammonium benzoate was charged to the
reactor. Analysis of the reaction showed 5.4
grams of ethylene glycol, 2.7 grams of methanol
and a rhodium recovery of 90 percent (84% + 6%
from wash).
Example 45
.;~
Example 44 was repeated except 0.65 mmol
of ammonium acetate was u~ed in place of the ~r
ammonium benzoate. Analysi~ of the reaction
product showed 6.1 grams of ethylene glycol,
2.8 grams of methanol and a rhodium recovery
of 88 percent (80% + 8Z from wash).
ExamPle 46
Example 45 was repeated except 0.80 mmol
of ammonium acetate wa~ charged to the reactor.
Analysi~s of the reaction product qhowed 7.1 grams
; of ethylene glycol, 3.4 grams of methanol and
a rhodium recovery of 91 percent (83% + 8% from
wash).
Example 47
Example 1 was repeated except 2.50 mmol of
triisopropanolamine borate wereused in place of
50.
1069~40
the pyridine. Analysis of the reaction product
showed 5.3 grams of ethylene glycol, 3.3
grams of methanol and a rhodium recovery of 67
percent (62% + 5R~ fr~m wash).
Example 48
Ex~mple 47 was repeated except that 0.50 ;
~mol of cesium formate in addition to the
triisopropanolamine borate was charged to the
reactor. Analysis of the reaction product showed
5.6 grams of ethylene glycol, 4.2 grams of
methanol and a rhodium recovery of 80 percent
(77% + 3% from wash~.
Example 49
Example 48 was repeated except that 0.65 -
mmol of cesium formate was used in addition
to the borate. Analysis of the reaction product ~ ;
.
, showed 6.1 grams of ethylene glycol, 4.4 grams
of methanol and a rhodium recovery of 88 percent
(847. ~ 4% from wash).
Example 50
Example 49 was repeated except that 0.875
mmol of cesium formate was used in addition to
the borate. Analysis of the reaction product
showed 5.6 gram~ of ethylene glycol, 4.3 grams
of methanol and a rhodium recovery of 83 percent
(79% + 4% fram wash).
51.
1069540 ~-
Example 51
Ex~mple 1 was repeated except 0.65 mmol
of cesium para-methylsulfonylbenzoate, CH3SO2C6H4COOCs,
was used in place of the pyridine. Analysis of the
reaction product showed 5.3 grams of ethylene
glycol, 2.5 grams of methanol and a rhodium
recovery of 88 percent (83% + 5% from wash). - ~`
Example 52 r
Example 51 was repeated except 0.85 mmol
of cesium para-methylsulfonylbenzoate was used.
Analysis of the reaction product showed 6.2 grams
of ethylene glycol, 2.9 grams of methanol and
a rhodium recovery of 87 percent (81% + 6% from
wash).
Example 53
Example 52 was repeated except that 1.0 mmol
of cesium para-methylsulfonylbenzoate was used.
Analy~is of the reaction product showed 5.9 grams
of ethylene glycol, 3,4 grams of methanol and a
rhodium recovery of 96 percent (87% + 9% from wash).
