Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR MAKING LONG CHAIN INTERNAL FATTY TERTIARY
AMINES
FIELD OF THE INVENTION
The present invention relates to an aminomethylation process for making long
chain
internal fatty tertiary amine, quaternized amines and the corresponding amine
oxides.
BACKGROUND OF THE INVENTION
Linear tertiary amines with chain lengths between 8 and 24 carbon atoms are
com-
monly referred to as fatty tertiary amines. According to Ullman's Encyclopedia
of
Chemical Technology, 5th edition, Volume A2, these materials, and their
derivatives
such as the corresponding quaternary ammonium compounds, are widely used in ap-
plications such as fabric softeners, drilling muds, surfactants, asphalt
emulsifiers, and
bactericides/disinfectants.
For fabric softeners, the most effective are the fatty quaternary ammonium
compounds
dialkyldimethyl ammonium chloride or the corresponding methyl sulfate. For
drilling
muds, methyl or benzyl quaternary ammonium chlorides produced from dialkyl
methyl amine are useful. For surfactants, C12 or C14 based dimethylalkyl amine
oxide
is commonly used. For bactericides and disinfectants, alkyl(benzyl)dimethyl
and alky
trimethyl compounds in which the fatty alkyl group contains 12 to 14 carbon
atoms
are most effective against a broad range of organisms. Alternatively, the
dialkyl di-
methyl compounds are most effective when the fatty alkyl group contains 8-10
carbon
atoms.
Fatty amines are commonly produced from natural fats and oils or from
conventional
petrochemical raw materials. Three primary feedstocks are used to make fatty
tertiary
amines: fatty nitriles, fatty alcohols or aldehydes, and long chain olefins.
Fatty nitriles, which are formed from fatty acids and ammonia over dehydrating
cata-
lysts in liquid phase reactors or liquid and vapor-phase reactors at 280 to
360 C, are
reacted either with dimethylamine or with formaldehyde and formic acid to
produce
N,N-dimethylalkylamines (see US 4,248,801 to Lion Fat & Oil Co. and US
3,444,205
to Hoechst).
CONFIRMATION COPY
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Fatty alcohols and aldehydes can be converted into the same product via direct
amina-
tion in the presence of dimethylamine or other primary or secondary amines at
230 C
at atmospheric pressure (0.1 - 0.5 MPa) using copper chromite catalysts (for
alcohol
feedstocks) or noble metal, copper chelate, or copper carboxylate catalysts
(for alde-
hydes) (see US 4,251,465 to Gulf Research and Development Co., US 4,13 5,437
to
Hoechst, and both US 4,254,060 and US 4,210,605 to Kao).
These processes, however, produce a high content of terminal amines, typically
91
wt% or greater. As used herein "terminal amines" means that the amine moiety
is
connected on a a or 0 carbon of the long chain alkyl chain of the amine.
For the case of amine oxide surfactants, this is done to provide good cleaning
with
high suds stability. However, sometimes it is desirable to produce with a high
content
(10 wt% or more) of internal amine. This would be useful for branched chain
surfac-
tants with improved cold water cleaning, moderate suds stability, and improved
wet-
ting properties.
Therefore, there is a need for a commercially feasible process for making long
chain
fatty tertiary amines and amine oxides which provide the desired content of
internal
amines, using hydrocarbons from a variety of sources. A secondary objective is
to
produce these amines via a low cost, economical process.
SUMMARY OF THE INVENTION
The present invention relates to a process comprising the steps of
(a) providing a long chain internal olefin source selected from the group
consisting of
oligomerized C2 to C11 olefins, metathesized C5 to Clo olefins, Fischer-
Tropsch ole-
fins, dehydrogenated long chain paraffin hydrocarbons, thermally cracked
hydrocar-
bon waxes, or dimerized vinyl olefins and mixtures thereof;
(b) reacting via aminomethylation the internal olefin source with a primary
amine or a
secondary amine to produce a long chain internal fatty tertiary amines;
(c) optionally separating any unconverted hydrocarbons and color or odor
bodies from
the long chain fatty tertiary amines resulting in a purified long chain fatty
tertiary
amine product;
(d) optionally (with or without step (c)) oxidizing the long chain fatty
tertiary amine
to the corresponding amine oxide, and
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(e) optionally (with or without step (c) and/or (d)) quaternizing the long
chain fatty
tertiary amine into a quaternary long chain internal fatty tertiary amine
product.
DETAILED DESCRIPTION OF THE INVENTION
As used herein "long chain internal olefin" means an olefin with 8 to 22
carbon atoms
and greater than 10% of the carbon-carbon double bonds being in a position
other than
the terminal (a and/or 0 carbon) position on the olefin. Preferably more than
50%,
70%, 90% and up to 100% of the carbon-carbon double bonds are in a position
other
than the terminal (a and/or 0 carbon) positions on the olefin. The long chain
internal
olefin may be linear or branched. If the long chain internal olefin is
branched, a C 1-C5
carbon branch is preferred.
As used herein "internal amine" mean an amine having the amine moiety attached
to
the alkyl moiety in greater than 10%, 50%, 70%, 90% and up to 100% in a
position
other than the terminal ((x and/or 0 carbon) position on the alkyl moiety.
Incorporated and included herein, as if expressly written herein, are all
ranges of
numbers when written in a "from X to Y" or "from about X to about Y" format.
It
should be understood that every limit given throughout this specification will
include
every lower or higher limit, as the case may be, as if such lower or higher
limit was
expressly written herein. Every range given throughout this specification will
include
every narrower range that falls within such broader range, as if such narrower
ranges
were all expressly written herein.
Without being limited by theory, it is believed that low cost production of
long chain
internal fatty tertiary amines is best accomplished by a process which uses
low cost
feedstocks, as manufacturing costs for a high volume, efficient chemical
process are
generally dominated by raw materials costs. Of the feedstocks available to
produce
long chain fatty tertiary amines, olefins are generally among the lowest cost
materials.
While alpha olefins are used to make terminal tertiary amines, long chain
internal
amines require a source of long chain internal olefins.
Long chain internal olefin sources can be obtained from a variety of different
proc-
esses, including C2 to C11 olefin oligomerization processes, C5 to C 10 olefin
metathesis
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processes, Fischer-Tropsch processes, catalytic dehydrogenation of long chain
paraf-
fin hydrocarbons, thermal cracking of hydrocarbon waxes, and dimerized vinyl
olefin
processes.
The long chain internal olefins from any of the above described processes are
then re-
acted with primary or secondary amines to produce long chain fatty tertiary
amines
using commercially feasible processes such as aminomethylation. Any
unconverted
hydrocarbons and color or odor bodies are subsequently separated from the long
chain
internal fatty tertiary amines using distillation or other commercial
techniques.
In the optional final step of the present process, the long chain internal
fatty tertiary
amines are converted into the corresponding amine oxide via oxidation.
The processes and methods herein may include a wide variety of other
variations. The
processes and methods of the present invention are described in detail
hereinafter.
The present process relates to converting long chain internal olefins to long
chain in-
ternal fatty tertiary amines and optionally, long chain internal amine oxides.
Long Chain Internal Olefin Sources
Oligomerized C2-C I 1 Olefins
Long chain internal olefin sources from oligomerized C2 to Ci 1 olefins are
readily
available from a variety of sources, including natural gas, naptha, and gas
oil frac-
tions. Oligomerized ethylene is available from suppliers such as Shell
Chemicals,
Exxon Chemicals, BP Amoco and Chevron Phillips.
The oligomerized C2 to C11 olefins may be derived from C2 to C11 olefins in
the pres-
ence of either organoaluminum compounds, transition metal catalysts or acidic
zeo-
lites to produce a wide range of chainlengths that is further purified by
various known
means, preferably distillation (see US 3,647,906, 4,727,203, and 4,895,997 to
Shell
Oil Co., US 5,849,974 to Amoco Corp., and US 6,281,404 to Chevron Chemicals
which disclose suitable catalysts and processing conditions for ethylene
oligomeriza-
tion).
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Oligomerization includes the production of dimers, trimers, or tetramers using
cata-
lysts such as acidic zeolites, nickel oxides, or metallocene cataylsts. For
example, US
5,026,933 discloses the use of ZSM-23 zeolite for propylene oligomerization.
Other
suitable catalysts include AMBERLYST 36 and acidic zeolites including
mordenite,
offretite and H-ZSM-12 in at least partially acidic form (see also
Comprehensive Or-
ganic Transformation, 2 nd Edition, Larock, Richard C., pages 633-636; and
Vogel's
Textbook of Practical Organic Chemistry, 5th Edition, Furniss, Brian S.,
Hannaford,
Antony J., Smith, Peter W.G., and Tatchell, Austin R., pages 574- 579).
Depending on the supplier and the process used, either a-olefins or internal
olefins are
generated from the oligomerization processes. For the case of a-olefin
feedstocks or
mixed a-olefin and internal olefin feedstock, an isomerization step is
required to gen-
erate the desired long chain internal olefins. The isomerization step results
in random
placement of the double bond along the carbon chain. Suitable isomerization
catalysts
include homogeneous or heterogeneous acidic catalysts, supported metal oxides
such
as cobalt oxide, iron oxide, or manganese oxide, and metal carbonyls such as
cobalt
carbonyl and iron carbonyl, see US 3,647,906, US 4,727,203, and US 4,895,997
to
Shell Oil Co., US 5,849,974 to Amoco Corp., and US 6,281,404 to Chevron Chemi-
cals which disclose suitable catalysts and processing conditions for double
bond isom-
erization.
Metathesis of C5-Clo Olefins
Cross-metathesis of C5-Clo olefins with other olefins or even with
oleochemicals can
be used to produce suitable long chain internal olefins for the present
process. For ex-
ample, two octene molecules can be reacted to form tetradecene and ethylene.
Or the
methyl ester of oleic acid can be reacted with hexene to form dodecene and the
methyl
ester of lauric acid. Common homogeneous catalysts include the ruthenium based
Grubb's catalyst as well as the Schrock catalyst. Cross metathesis is furtlier
described
in the text Olefin Metathesis and Metathesis Polymerization by Ivin and Mol
(1997),
and also the journal Chemical and Engineering News, vol. 80, no. 51, Dec 23,
2002,
pp. 29-33.
Other Internal Olefins
Alternative processes for olefins are from the
isomerization/disproportionation olefin
process and/or SHOP process from Shell Chemical. These are commercially avail-
able materials under the tradename NEODENE .
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Fischer-Tropsch Olefins and Paraffins
Long chain internal olefin sources from Fischer-Tropsch involves converting a
source
of carbon such as coal, methane, or natural gas to a wide distribution of
carbon
chainlengths and then isolating a narrow hydrocarbon fraction, using
techniques such
as distillation or liquid-liquid extraction.
Two different catalysts are commercially used: iron and cobalt, with iron
generally
producing a higher yield of olefins and cobalt producing a higher yield of
paraffins.
Hydrocarbons recovered from the Fischer-Tropsch reaction may be a mixture of
linear
and branched chains, olefins and paraffins, having both terminal and internal
double
bonds. Straight run Fischer-Tropsch olefin and paraffins from jet and/or
diesel frac-
tions may be utilized in the present process.
As disclosed above, double bond isomerization catalysts can be employed to
convert
oc-olefins to internal olefins. Paraffins present in the internal olefin feed
stream may
be left with the internal olefins until amination is complete.
For the iron based Fischer-Tropsch reaction product, it may be desirable for
oxygen-
ates to be separated out from the hydrocarbons prior to amination. Oxygenates
refer to
carboxylic acids, alcohols, aldehydes, and ketones, which chainlengths from C1
to Cig.
Oxygenates impart undesirable color, odor, and performance impurities to
tertiary
amines and must be removed from the hydrocarbons prior to amination or from
the
crude tertiary amine after amination.
There are several methods to separate oxygenates from Fischer-Tropsch crude
prior to
amination. Liquid-liquid extraction is the preferred process for separating
oxygenates
from hydrocarbons. Liquid-liquid extraction is effective in removing both
alcohols
and carboxylic acids from hydrocarbons and can be achieved with more
reasonable
capital investment than distillation or adsorption. Caustic treatment,
followed by cen-
trifuging, water washing, or filtration is effective in neutralizing and
separating car-
boxylic acids, but has no effect on alcohols.
Use of liquid-liquid extraction to remove oxygenates can be done with a wide
variety
of solvents. For example, diethylene glycol is reported to be a solvent for
removal of
aromatics from reformate, and propane is reported to be a solvent for removal
of fatty
acids from natural oils. See Packed Tower Design and Applications, 2nd Ed.,
Strigle,
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page 294. A wide variety of factors must be considered in the choice of the
proper
solvent, including solubilities, interfacial tension, differences between
phase densities,
viscosity, corrosion, and cost. Solvent polarity index is an important
indicator of the
solubility of the oxygenates as well as insolubility of the hydrocarbons. For
a descrip-
tion of polarity index see Practical HPLC Development, 2 d Ed., Snyder,
Kirkland,
and Glajch, page 723; and Introduction to Modern Liquid Chromatography, 2d
Ed.,
Snyder and Kirkland, pages 258-260. Applicants have found that it is preferred
to use
solvents with Fischer-Tropsch with a polarity index of 5.6 to 6Ø One
suitable solvent
is an 80/20 wt% mixture of ethanol/water. Temperature of operation for liquid
extrac-
tion is from 20 C to just below the boiling point of the solvent selected.
Solvent to
feed ratios of 0.1 to 3 are preferred.
Extraction can be carried out in three classes of equipment: mixer-settlers,
contacting
columns, or centrifugal contactors. When only one stage of separation is
required for
the extraction step, a mixer-settler may used. Spray columns may be used when
the
density difference between the phases is large. When more than three stages of
separa-
tion are needed, packed or tray columns with countercurrent flow are the
preferred de-
vices. Centrifugal contactors may also used if the liquid phases have small
density dif-
ference and a large number of equilibrium stages are needed. When ten to
twelve equi-
librium stages are required, a mechanical contactor with rotating disks or
impellers is
often used, as these have higher efficiencies than the packed contactors. The
preferred
number of equilibrium stages is one to twelve.
In theory, distillation can be used to separate oxygenates from hydrocarbons,
but the
boiling points of oxygenates and hydrocarbons can overlap so that distillation
is not
preferred. Bulk separation by adsorption using molecular sieves is also
possible, but
expensive from a capital investment standpoint.
Dehydrogenation of Long Chain Hydrocarbons
Long chain internal olefin sources may also be obtained from the catalytic
dehydroge-
nation of long chain paraffins or paraffin/olefin mixtures which yields long
chain ole-
fins with the same number of carbon atoms and with random locations of a
double
bond along the chain. As disclosed above, double bond isomerization catalysts
can be
employed to convert a-olefins to internal olefins. Paraffins present in the
internal ole-
fin feed stream may be left with the internal olefins until amination is
complete.
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Sources include the kerosene fraction from petroleum refineries and Fischer-
Tropsch
paraffins or paraffin/olefin mixtures. See US 3,531,543 to Chevron Research
and US
3,745,112, US 3,909,451, and 4,608,360 to UOP which discuss suitable catalysts
and
processing conditions for paraffin dehydrogenation. Straight run Fischer-
Tropsch ole-
fin and paraffins from jet and/or diesel fractions may be utilized in the
catalytic dehy-
drogenation process. The UOP PACOL process operates at 450 C to 510 C and
0.3
MPa using a platinum on alumina catalyst, promoted by lithium, arsenic, or
germa-
nium. To minimize by-products, low conversion rates of 10 to 15 wt % are used.
Use
of the low conversion rate results in paraffin-olefin mixtures that may be
further sepa-
rated and purified by the UOP OLEX process or reacted together with amine
before
paraffin separation is done.
Thermally Cracked Hydrocarbon Waxes
Long chain internal olefins may also be derived from thermal cracking of
hydrocarbon
waxes from either petroleum streams or the Fischer Tropsch reactions,
including
Fischer Tropsch paraffin waxes. The chainlength of these waxes is generally
greater
than C22. Thermal cracking is a non-catalytic, free radical process conducted
at high
temperatures in the presence of steam, followed by distillation to separate
and recycle
the unreacted wax to the cracking furnace.
A tubular furnace is preferably used for the cracking reaction. The
temperature for the
thermal cracking ranges from 400 to 600 C. Selection of higher temperatures
are not
desired as higher temperatures results in the formation of shorter chain
olefins
(chainlength < CS), higher levels of polyolefins, as well as more gas
products. Selec-
tion of lower temperatures are not desired as lower temperatures reduce the
conver-
sion of long chain internal olefins per pass, which is undesirable from a
capital cost
standpoint.
The pressure in the thermal cracking reaction zone is 0.1 to 1 MPa. Higher
pressure
generally leads to an increase in the yield of liquid products, with a
corresponding re-
duction in a-olefin content. Space velocity is 1.25 to 5.0 volume of
feed/volume of
reactor/hour. This corresponds approximately to a vapor residence time in the
reactor
of 2.5 to 10 seconds. Higher residence time is undesirable as it leads to
increased de-
composition and secondary by-products verses the desired long chain internal
olefins.
The conversion per pass in the reaction is 10 to 25 wt %.
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Gas and liquid products from the thermal cracking reactor are separated by a
distilla-
tion step using a pressure of 10 to 2500 Pa and a temperature of 100 C- 280
C. Any
unreacted wax is taken as a bottom fraction from the distillation step and
recycled
back to the thermal cracking furnace and mixed with fresh hydrocarbon waxes.
As
disclosed above, double bond isomerization catalysts may be employed to
convert any
a-olefins present to long chain internal olefins.
Internal Vinylidenes
Internal vinylidenes may also be utilized as the long chain internal olefin
source of the
present process. Vinylidenes may be produced via a process involving
dimerizing vi-
nyl olefin with at least one trialkylaluminum compound. Further conditions may
be
found in US 5,625,105. Vinylidenes may also be produced via a process of
dimerizing
a vinyl-olefin monomer in the presence of a tri-alkyl aluminum catalyst as
described
in US 4,973,788.
Reaction Of Long Chain Internal Olefins With Primary Or Secondary Amines Using
Aminomethylation Conditions:
The long chain fatty tertiary amines desired in the present process are
produced by the
reaction between the long chain internal olefins as described above and either
a pri-
mary or secondary alkyl amine. If a primary alkyl amine such as
monomethylamine is
used, then two long chain internal olefin molecules are added to the primary
alkyl
amine to produce a di-long chain fatty tertiary monoalkyl amine product. If a
secon-
dary alkyl amine such as dimethylamine is used, then one long chain internal
olefin
molecule is added to the secondary alkyl amine to produce a mono-long chain
fatty
tertiary dialkyl amine product.
Tertiary amine products that are produced by the process of the present
invention have
an internal amine content of from 10 wt% to 100 wt%, a linear olefin content
of from
about 1 wt% to 100 wt%, and a paraffin content of from 0 wt% to about 90 wt%.
Examples of desirable tertiary amine products include but are not limited to
trioc-
tylamine, tridecylamine, tridodecylamine, didodecylmethylamine,
ditetradecylmethyl-
amine, dihexadecylmethylamine, dioctadecylmethylamine, decyldimethylamine, do-
decyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, and
octade-
cyldimethylamine. The amine moiety of these materials is located on the long
chain
alkyl in an internal position. An internal position refers to a carbon other
than the a or
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(3 carbon of the long chain alkyl. Aminating the internal olefins for the
present process
includes hydrocarbonylation and is further described below.
In one embodiment of the present process, the aminomethylation reaction with
an in-
ternal long chain olefin such as those feedstocks described above produces a
tertiary
amine with the following structure:
RI\ H3
R2 ~
CH3
wherein RI and R2 are linear or semilinear hydrocarbons with a hydrocarbon
content
of chainlength of 1 to 19 carbon atoms. As used herein "semi-linear" means
that R1
and/or R2 comprise between 1 and 4 Cl to C3 alkyl branches randomly
distributed or
consistently distributed. The amine structure is such that an alkyl portion
has a total
sum of carbons from 8 to 22 carbon atoms. As used herein, the alkyl portion is
RI +
R2 + 2 carbon atoms between the nitrogen and Ri and R2 in the above referenced
structure.
In a preferred embodiment, the total sum of carbons in the alkyl portion (R1 +
R2 + 2
carbons) is from 10 to 22 carbon atoms, preferably from 12 to 20, more
preferably
from 10 to 14. The number of carbon atoms for R1 may be approximately the same
number of carbon atoms for R2 such that R1 and R2 are symmetric. As used
herein
"symmetric" means that for carbon atoms, I Rl - R2 I is less than or equal to
5 carbon
atoms in at least 50 wt%, more preferably at least 75 wt% to 100 wt% of the
long
chain fatty internal amine produced herein. In another embodiment I Rl - R2 I
is less
than 4.
Without being limited by a theory, it is believed that the symmetric structure
of the
long chain fatty internal amine oxides improve surface wetting ability of the
amine
oxide that aids in the removal of grease deposits from surfaces at lower wash
tempera-
ture verses asymmetric branched amine oxides. As used herein "asymmetric"
means
R1 - R2 I is greater than 5 carbon atoms. However, mixtures contain non
symmetric
and symmetric structures of the long chain fatty internal amine oxides may
also be de-
sirable for the purpose but are not preferred.
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According to a preferred embodiment of the present invention the process
comprises
the step of reacting the olefins with synthesis gas (H2 and CO), preferably in
a
stoichiometric ratio, and a primary or secondary amine in the presence of a
catalyst,
preferably a heterogeneous catalyst, to form a tertiary amine product.
Preferred proc-
ess conditions are a temperature of 60 to 200 C pressure of 2.8 to 21 MPa
(400 to
3000 psig), H2:CO molar ratio of 0.5 to 3.0, and reaction time of 0.1 to 10.0
hours.
The catalyst suitable for use in the present process include noble metal
catalysts such
as rhodium oxide, rhodium chloride, or ruthenium chloride, at a catalyst level
of 50 to
1000 ppm by weight of the olefin. Ligands such as triphenylphosphine may
optionally
be used to stabilize the preferably heterogeneous noble metal catalyst.
Preferred levels
of triphenylphosphine are 100 to 5000 ppin by weight of the olefin.
Optional Purification of the internal fatty tertiary amines using thermal
separation
techniques
The process of the present invention further comprises the step of purifying
the long
chain internal fatty tertiary amine product from the previous step to form a
purified
long chain internal fatty tertiary amine product. Preferred purity of the
purified long
chain internal fatty tertiary amine product is from about 95 wt% or greater,
more pref-
erably from about 97 wt% or greater, most preferably from about 98 wt% to
about 100
wt% by weight of the purified long chain internal fatty tertiary amine product
after the
purification step.
The long chain internal fatty tertiary amine products may be mixed with
paraffins, un-
reacted olefins, color and odor bodies, and small quantities of oxygenates
such as al-
cohols or carboxylic acids among other impurities.
Each of the impurities listed above may be removed via thermal separation tech-
niques. A preferred purification step is via flash stills and/or topping
columns. Equip-
ment for the flash still and the topping column includes falling film
evaporators,
wiped film evaporators, reboiler flash units, and multistage distillation
columns. All
equipment is known to one of skill in the art and available from suppliers
such as
Pfaudler, Lewa, and Koch. Heavy impurities such as polyalkylamines, salts, and
color
bodies may be removed in a bottom stream of a flash still operating under a
pressure
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of 10 to 2500 Pa (0.1 to 20 mm Hg) and a temperature of 90 to 205 C. Light
impuri-
ties such as residual hydrocarbons (olefin or paraffin) and color bodies may
be re-
moved in the overheads stream of a topping column operating under a pressure
of 10
to 2500 Pa (0.1 to 20 mm Hg) and a temperature of 150 to 250 C.
Optional Oxidation Step Of The Purified Internal Fatty Tertiary Amines
The process of the present invention further comprises the optional step of
oxidizing
the purified long chain internal fatty tertiary amine to give an oxidation
product of the
corresponding long chain internal fatty amine oxide. The purified long chain
internal
fatty tertiary amine may optionally be converted into using materials such as
5-70
wt% hydrogen peroxide. As described in US 6,294,514 to Procter & Gamble Co.,
pu-
rified long chain internal fatty tertiary amines are typically combined with 5
to 70
wt% hydrogen peroxide, 0.3 to 2.5% of a bicarbonate material such as sodium
bicar-
bonate or potassium bicarbonate, and optionally water, to result in an
oxidation prod-
uct which is 30-38 wt% by weight of the oxidation product of the corresponding
long
chain internal fatty amine. The amount of hydrogen peroxide is 100 to 115% of
stoichiometric to the amount of amine present. The oxidation step target
temperature
is about 40 to 100 C (60 to 70 C preferred), and pressure is 0.1 MPa.
The oxidation step is complete when the residual hydrogen peroxide level is
below
1%, preferably below 0.1 wt% of the final product composition. Reaction time
is gen-
erally 4 to 24 hours. Residual hydrogen peroxide is typically decomposed by
holding
the material at reaction temperature. If necessary, 0.1 to 5 wt% by weight of
the re-
agents of platinum on alumina may be used as an adsorbent to remove residual
hydro-
gen peroxide from the oxidation product.
Optional Quatemization Step of the Purified Internal Fatty Tertiary Amines
The process of the present invention may further comprise the optional step of
quater-
nizing the purified long chain internal fatty tertiary amine to give a
quaternary long
chain internal fatty tertiary amine product. Quaternization may be achieved by
a reac-
tion of the purified long chain internal fatty tertiary amine with methyl
chloride or di-
methyl sulfate. Quaternization with methyl chloride is achieved by reaction
with 1.0
to 1.3 mole equivalents of methyl chloride relative to the purified long chain
internal
fatty tertiary amine in an autoclave with temperature range of room
temperature
(20 C) to 8 0 C under nitrogen pressure from 101 to 10100 kPa (1 to 100 atm).
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Dimethyl sulfate is reacted at 1.0 to 1.1 mole equivalents relative to the
purified long
chain internal fatty tertiary amine in a flask blanketed with nitrogen at 10
to 70 C to
form the desired quaternary long chain internal fatty tertiary amine product.
Examples
The following examples further describe and demonstrate embodiments within the
scope of the present invention. These examples are given solely for the
purpose of il-
lustration and are not to be construed as limitations of the present
invention, as many
variations thereof are possible without departing from the invention.
Example 1- Thermal Cracking Of Paraffin Wax, Isomerization, And Aminomethyla-
tion
Step 1
Melt a paraffin wax with a melt point range of 52 to 58 C and a linear
hydrocarbon
chainlength of C21 to C36 in an 800 mL glass beaker. Use the following
equipment for
the thermal cracking reaction:
- FMI piston pump (model QSY-1) to meter melted paraffin wax into a tubular
reactor
- 3.35 m(11 foot) long by 4.57 mm (0.18 inch) diameter stainless steel coil,
heated in a muffle furnace (preheater)
- 3.66 m (12 foot) long by 4.57 mm (0.18 inch) diameter coil, placed inside a
second muffle furnace (reactor)
- 9.14 m(30 foot) long by 4.57 mm (0.18 inch) diameter coil, placed inside a 2
liter beaker filled with water (quench cooler)
- 1 liter beaker for containing a quenched liquid product
- Stainless steel tubing, electric traced, with thermocouples before & after
reac-
tor coil
Crack the melted paraffin wax using a mass flowrate of 2.6 g/min. with a
residence
time of 3.4 volumes liquid feed/volume of reactor/hour, and a reactor
temperature of
575 C. Meter 652 grams of melted paraffin wax into the tubular reactor and
recover a
product comprising about 579 grams of liquid product with the balance of the
product
of non-condensable vapor and gas.
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Collect the product from the reactor, the product includes cracked olefins as
well as
unreacted paraffins. Separate the olefins from the unreacted paraffins in a
flash still at
667 Pa (5 mm Hg) and a temperature of 200 C, then analyze using a Hewlett
Packard
6890 Series gas chromatograph. About 67 grams of distillate may be recovered.
The distillate composition was as follows:
Clo-C20 a-olefin 93.1 wt%
Clo-C2o di-olefin 2.5 wt%
Clo-C20 paraffin 2.8 wt%
CIO-C20 other 1.6 wt%
internal olefin 0 wt%
branched olefin 0 wt%
aromatics 0 wt%
The carbonyl value (expressed as C=O) is 32 ppm, indicating minimal oxidation
of the
hydrocarbons.
Step 2
Place 50 grams of C10 to C20 distillate composition from Step 1 above in a 300
ml Parr
autoclave and combine with 0.025 grams of iron carbonyl, Fe2(CO)9 to isomerize
any
double bonds present to result in internal olefins. Purge the reactor with
349.35 kPa
(50 psig) nitrogen gas and then heat the distillate composition and iron
carbonyl to
180 C for one hour with agitation.
Cool the reactor to 40 C and add 0.052 grams of rhodium oxide with 0.131
grams of
triphenylphosphine ligand. Purge the reactor ten times with 349.35 kPa (50
psig) ni-
trogen gas, then purge twice with 3493.5 kPa (500 psig) synthetic gas
(syngas). Add
13.5 grams of dimethylamine to the reactor. Pressurize the reactor to 7685.7
kPa
(1100 psig) with syngas using a 0.5 molar ratio of H2:CO. Conduct the reaction
for 3
hours at 150 C, and then cool to 40 C and depressurize the reactor to result
in a
crude product. GC-MS analysis should indicate a majority of the crude product
from
the reactor was linear and branched monoalkyldimethyl amine.
Example 2 - Isomerization of a-olefins, followed by aminomethylation and
oxidation.
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Step 1
Add 18.6 kg (41 pounds) of Clo a-olefin and 7.71 kg (17 pounds) of C12 a-
olefin to a
75.7 L (20 gallon) agitated reactor along with 25 grams iron carbonyl as an
isomeriza-
tion catalyst. Pressurize the reactor to 139.74 kPa (20 psig) with nitrogen
gas, then
heat the reactor to 180 C for one hour to allow double bond isomerization to
take
place.
Alternative Step 1:
Add from a container a mixture of 15.1 g of NEODENE 10, 136.6 g of NEODENE
12 and 109.1 g of 1-tridecene to a 7.57 L (2 gallon) stainless steel, stirred
autoclave
along with 70 g of a shape selective catalyst (acidic beta zeolite catalyst
ZEOCATTM
PB/H). NEODENE 10 and 12 are commercially available olefins from the Shell
Chemical Company. Wash the residual olefin and catalyst in the container into
the
autoclave with 200 mL of n-hexane and seal the autoclave. Purge the autoclave
twice
with 1724.25 kPa (250 psig) nitrogen gas, and then charged to 413.82 kPa (60
psig)
nitrogen gas. Stir and heat the mixture to 170 C to 175 C for about 18 hours
then cool
to 70 C-80 C. Open the valve leading from the autoclave to a benzene condenser
and
collection tank. Heat the autoclave to about 60 C then continue to heat to 120
C with
continuous collection of hexane in collection tank. No more hexane should be
col-
lected by the time the reactor reaches 120 C. Cool the reactor to 40 C and
pump with
mixing 1 kg of n-hexane into the autoclave. Drain the autoclave to remove the
reac-
tion mixture product. Filter the reaction mixture product to remove catalyst
and
evaporate the n-hexane under low vacuum. Distill the reaction mixture product
under
high vacuum (133 Pa - 667 Pa [1-5 mm of Hg]) to give an internal olefin
mixture.
Collect about 210 g of the internal olefin mixture at a temperature of 85 C -
150 C.
Cool the reactor to 50 C, depressurize the reactor, and then add the
following ingre-
dients to the reactor: 26 grams rhodium oxide, 65 grams triphenylphosphine,
and 7.71
kg (17.6 pounds) of dimethylamine. Pressurize the reactor to 6987 kPa (1000
psig)
with syngas (the syngas having a CO:H2 molar ratio of 1:1) and then heat to
150 C
for three hours resulting in a mixed product having a unreacted dimethlamine
phase
and a tertiary amine phase. A GC analysis indicated that the mixed product was
61
wt% tertiary amine and 39 wt% unreacted olefin. Cool the reactor and pour the
mixed
product into 18.0 L (5 gallon) plastic buckets. Settle any unreacted
dimethylamine
(DMA) phase into a separate phase and decant the tertiary amine phase off the
top to
give a crude tertiary amine product.
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Use batch distillation to remove DMA and any unreacted olefin from the
tertiary
amine crude product in a 7.62 cm (3 inch) glass batch still with 7 stages of
separation
and reflux. Add 31.1 kg (68.5 pounds) of the crude tertiary amine to a
stillpot and dis-
till under vacuum using the following conditions:
Beginning of Distillation End of Distillation
Top pressure 1.51 kPa (11.3 mm Hg) 1.15 kPa (8.6 mm Hg)
Bottom pressure 1.96 kPa (14.7 mm Hg) 1.83 kPa (13.7 mm Hg)
Top temperature 600 C 132 C
Bottom temperature 85 C 144 C
As used herein "reflux ratio" is defined as the mass flow of distillate sent
back to col-
umn divided by mass flow of distillate removed from the column. The reflux
ratio
may be varied from 1.0 to 4Ø Recover a number of distillate fractions with
various
levels of unreacted olefin and unreacted amine. Cease column boilup and stop
the dis-
tillation and cool. Recover about 2.13 (4.7 pounds) of still bottoms.
Combine the distillate fractions with the highest purity of tertiary amine in
a blend
with greater than 99 wt% C11 and C13 amines and less than 1 wt% C10 and C12
olefins.
Use a lab distillation to recover pure C11 amine using a 5.08 mm (2 inch)
glass Older-
shaw column with 10 trays. As used here, "pure C 11 amine" means that the
weight
percent of Ci 1 amine is greater than 99 wt%. Add 2230 grams of the distillate
to the
stillpot and distill under vacuum using the following conditions:
Beginning of Distillation End of Distillation
Top pressure 667 Pa (5 mm Hg) 800 Pa (6 mm Hg)
Bottom pressure N/A N/A
Top temperature 82 C 88 C
Bottom temperature 125 C 131 C
Set the reflux ratio at 6.0 throughout the distillation. Stop the distillation
after several
distillate fractions are collected with C11 tertiary amine present. Collect
about 600
grams of distillate and leave about 1630 grams of still bottoms in the
stillpot.
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An oxidation step may be done in a 3 liter agitated flask. Add 600 grams of CI
1 terti-
ary amine, 506 grams of 50 wt% hydrogen peroxide, 1049 grams of water, and
0.44
grams of DEQUEST 2066 chelant to a glass flask and heat to 65 C with
agitation.
After 10 hours of mixing, the composition of the mix should result in about
1.1 wt%
residual peroxide, 2.1 wt% petroleum ether extract, no detectible free amine,
and 28
wt% active amine oxide.
Adsorb the residual peroxide with an adsorbent of a 0.5% platinum on alumina
over
five successive batch additions and filtrations using a Buchner funnel with
filter pa-
per. Treat a total of about 2150 grams of amine oxide with a total of 32 grams
of the
adsorbent. The final product should result in about 0.09 wt% residual
peroxide, 2.1
wt% petroleum ether extract, no detectible free amine, and 28 wt% active amine
ox-
ide. Color measured using a spectrophotometer with a 1 mm cell referenced to
water
results in a % transmittance of 96.4% at 470 nm.
Example 3 - Metathesis of a-olefins, followed by aminomethylation.
Step 1
6-Dodecene was prepared via metathesis of 1-heptene using Grubbs Catalyst [1St
gen-
eration, benzylidene-bis(tricyclohexylphosphine)dichlororuthenium]. The 6-
dodecene
was purified from the reaction mixture using fractional vacuum distillation.
Step 2
The 6-dodecene produced in Step 1 was aminomethylated using the following
experi-
mental procedure:
Rh203 (0.525mM) 10.25 mg
TPP (P:Rh = 1.2:1) 26 mg
6-Dodecene 13 ml
Me2NH 3.0 g
Rh203, TPP and the olefin were heated under nitrogen (-1 bar) to 150 C. Me2NH
was
injected using syngas (H2:CO 2:1) 76bar and syngas was fed at this pressure
for 20h.
GC and GCMS analysis showed the following product distribution:
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olefin conversion 90%
aldehydes 17.2%
enamines 11.4%
alcohols 8.3%
amines 63%
The amine product distribution was as follows:
a 2-Pentyloctyldimethylamine 32.7%
b 2-Butylnonyldimethylamine 27.3%
c 2-Propyldecyldimethylamine 12.2%
d 2-Ethylundecyldimethylamine 9.5%
e 2-Methyldodecyldimethylamine 13.6%
f Linear-tridecyldimethylamine 4.8
Example 4 - Dehydrogenation of long chain paraffin hydrocarbons, followed by
ami-
nomethylation.
A commercially available Ci1C12 olefin feed derived from Pacol dehydrogenation
of a
C11C12 paraffin mixture (olefin composition C11 - 44.5%, C12 - 55.5%) was
converted
to amines using the following experimental procedure:
Rh203 (0.525mM) 10.2 mg
TPP (P:Rh = 1.2:1) 26 mg
C11C12 Pacol olefins 13 ml
Me2NH 3.43 g
Rh203, TPP and the olefin were heated under nitrogen (-1 bar) to 150 C. Me2NH
was
injected using syngas (H2:CO 2:1) 76bar and syngas was fed at this pressure
for 20h.
GC analysis showed: (small amounts of products from C10 & C13 olefins as well
as
aromatics in the feed were ignored at this stage).
conversion 82%
alcohols -5%
aldehydes -3 8.5%
enamines -21.4%
amines -3 5.1 %
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The amine distribution was as follows:
C13 amines from C12-olefins
a 2-Pentyloctyldimethylamine 13.2%
b 2-Butylnonyldimethylamine 16.6%
c 2-Propyldecyldimethylamine 2.5%
d 2-Ethylundecyldimethylamine 3.0%
e 2-Methyldodecyldimethylamine 5.3%
f Linear-tridecyldimethylamine 7.4%
C12 amines from Cl l-olefins
g 2-Pentylheptyldimethylamine 1.2%
h 2-Butyloctyldimethylamine 2.3%
i 2-Propylnonyldimethylamine 9.5%
j 2-Ethyldecyldimethylamine 17.6%
k 2-Methylundecyldimethylamine 13.1%
1 Linear-dodecyldimethylamine 8.3%
Example 5 - Dimerisation of a-olefins to vinylidene olefins, followed by ami-
nomethylation.
Step 1
1-Hexene was dimerized using zirconocene dichloride (Cp2ZrC12) and
methylalumox-
ane (A1:Zr:olefin 50:1:1000) and purified via fractional vacuum distillation.
The major
product was 2-butyl-l-octene (C 12-vinylidene).
The hydroaminomethylation of 2-butyl-l-octene (C12-vinylidene) was done using
the
following experimental procedure:
Rh203 (0.525mM) 10.2mg
TPP (P:Rh = 1.2:1) 26mg
2-Butyl-l-octene 13m1
Me2NH 3.38g
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Rh203, TPP and the olefin were heated under nitrogen (-1 bar) to 150 C. Me2NH
was
injected using syngas (H2:CO 2:1) 76bar and syngas was fed at this pressure
for 20h.
NMe2
~~
MeZNH
3-Butylnonyldimethylamine
GC analysis indicated:
conversion 83%
paraffins 5%
enamines 38%
aldehydes 18%
amines 39%.
The amine distribution was >97% to the required 3-butylnonyldimethylamine
isomer.
All documents cited in the Detailed Description of the Invention are, are, in
relevant
part, incorporated herein by reference; the citation of any document is not to
be con-
strued as an admission that it is prior art with respect to the present
invention.
While particular embodiments of the present invention have been illustrated
and de-
scribed, it would be obvious to those skilled in the art that various other
changes and
modifications can be made without departing from the spirit and scope of the
inven-
tion. It is therefore intended to cover in the appended claims all such
changes and
modifications that are within the scope of this inventio
35
