WO1998038149A1 - Process for the manufacture of carboxylic acids - Google Patents
Process for the manufacture of carboxylic acids Download PDFInfo
- Publication number
- WO1998038149A1 WO1998038149A1 PCT/EP1998/001128 EP9801128W WO9838149A1 WO 1998038149 A1 WO1998038149 A1 WO 1998038149A1 EP 9801128 W EP9801128 W EP 9801128W WO 9838149 A1 WO9838149 A1 WO 9838149A1
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- WO
- WIPO (PCT)
- Prior art keywords
- acid
- process according
- branched
- carbon monoxide
- olefin
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 150000001735 carboxylic acids Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 claims abstract description 29
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 8
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011973 solid acid Substances 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- -1 poly (tetrafluoro- ethylene) Polymers 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 150000001243 acetic acids Chemical class 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 6
- 229920001429 chelating resin Polymers 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
Definitions
- the invention relates to a process for the manufacture of carboxylic acids. More in particular the invention relates to a process for the manufacture of branched carboxylic acids by means of a Koch synthesis using carbon monoxide as reagent and a solid acid catalyst .
- the cationic resin was specified to have an acidity of at least equivalent to that of a 65 wt% sulphuric acid.
- EP-A-0249976 was known a process for the manufacture of branched carboxylic acids, by catalytic conversion of olefins with carbon monoxide and water in the presence of zeoliths as catalysts at temperatures of from 200 to 500 °C and at pressures of 200 to 700 bar. More in particular zeoliths of the pentasil type are used as catalysts. According to the exemplified embodiments only high temperatures (300 °C) and pressures (300-500 bar) are used.
- An object of the present invention is providing an improved manufacturing process for branched carboxylic acids, which process uses relatively mild conditions on the one hand and which shows high conversion and high selectivity to branched acids on the other hand. As a result of extensive research and experimentation such an improved process aimed at has been surprisingly found .
- the invention relates to a process for manufacture of branched carboxylic acids from branched olefins by means of reaction with carbon monoxide and a solid acid catalyst, characterized in that a branched olefin, or a precursor thereof, is reacted in a continuously backmixed reactor, wherein sufficient stirring of the feed components and product occurs to obtain an efficient backmixing ,with continuously supplied carbon monoxide and water, while continuously an effluent is withdrawn comprising branched carboxylic acid, non-converted olefin, carbon monoxide and water in the presence of an acidic ion exchanger, having sufficient acid groups to provide requisite protons for conversion of said olefin or a precursor of it, and carbon monoxide into branched carboxylic acids.
- R3 wherein each symbol R represents a radical having 1 to 10 carbon atoms.
- the total number of carbon atoms in the trialkylacetic acids ranges from 5 to 19 and most preferably from 5 to 14, derived from C4 ⁇ C ⁇ _4 olefins.
- branched olefin or a precursor thereof as used throughout the present specification is meant that branched olefin itself as well as alcohols, esters or ethers, from which the specific olefin can be easily derived, can be used as starting materials for the present manufacturing process, which makes this process much more flexible than conventional prior art processes.
- all olefins containing at least one tertiary carbon atom or precursors therefor can be converted by the present process.
- Suitable examples of the continuously backmixed reactor are continuously stirred tank reactors (CTSTR) , fluidized bed reactors or recycle reactors .
- CSTR continuously stirred tank reactors
- the hereinbefore mentioned reactor types are known from e.g. Chemical Reaction Engineering second edition,
- the continuously stirred tank reactors or the recycle reactors are the preferred ones.
- An important advantage of the process of the present invention is that it shows an improved combination of high conversion degree and high selectivity as to the desired branched carboxylic acid, in comparison to these conventional prior art processes, while operated at relatively mild conditions .
- the catalyst to be used for the process of the present invention is a solid acidic ion exchanger, showing a sufficient amount of acid active sites per volume unit catalyst and a strong acid activity of each acid site.
- the catalyst can be selected from the group consisting of resins, bearing sulphonic, phosphonic or trihalo acetic acid groups.
- resins bearing sulphonic, phosphonic or trihalo acetic acid groups.
- sulfonated resins are applied. More preferably sulfonated resins are used, wherein the resins are copolymers of styrene and divinylbenzene, phenol based resins, poly (tetrafluoroethylene) polymers or siloxane polymers.
- the resin is treated to give a sulfonic acid cation-exchange resin capable of providing sufficient protons, i.e. the resin having per active site an acid strength equivalent to at least 65 wt% sulphuric acid and preferably to at least 70 wt% sulphuric acid.
- Catalyst solid resins comprising sulfonic acid groups and derived from copolymers from styrene, divinylbenzene and phenol or derived from (tetrafluoroethylene) polymers or from siloxane polymers are preferred.
- catalysts which are sulfonated copolymers, derived from styrene and divinylbenzene, having a sulfon group density of >2 meq/ml dry resin, and preferably >3 meq/ml dry resin, while the copolymer has a divinylbenzene content in the range of from 4 to 30 wt% and preferably from 8 to 18 wt%.
- AMBERLYST 36 or 38 Specific more preferred examples of commercial effective catalysts are AMBERLYST 36 or 38, NAFION or DELOXAN catalysts (AMBERLYST 36 or 38 or NAFION and DELOXAN are Trade Marks) . Most preferred are the AMBERLYST 36 or 38 or NAFION type catalysts.
- the reaction temperature in the CSTR is in the range of from 25 °C to 200 °C and preferably from 100 to 150 °C.
- the pressure in the reactor is in the range of from 10 to 200 bar and preferably from 50 to 100 bar.
- an inert organic solvent can be used, which does not interfere with the desired reaction, preferably a solvent which can easily be separated from the other reaction mixture components and recirculated.
- organic solvents can be used apolar as well as polar solvents such as ketones, ethers, substituted aromatics, esters and carboxylic acids .
- the branched acid primarily to be produced is present as solvent in the reactor, and is regularly discharged from it together with water, CO, non-converted olefin and by-products, to keep the liquid level in the reactor constant.
- the CSTR is filled with solvent and catalyst with a catalyst/solvent wt ratio of in the range of from 0.1 to 0.5 w/w and preferably 0.2-0.3 w/w.
- the respective reactants are continuously introduced into the reactor and reaction mixture is continuously discharged.
- the feed of starting olefin is in the range of from 0.01 to 10 g/g/hr, while the water/olefin molar ratio is in the range of from 0.5 to 2 mole/mole and preferably about 1 and the CO/olefin molar ratio is in the range of from 0.5 to 1000 mole/mole and preferably from 1 to 100.
- AMBERLYST 15 20 g of AMBERLYST 15 were loaded in a stirred batch rector, dried for 2 h at 110 °C under vacuum, suspended in a solution of 50 g propanoic acid (solvent), 6 g propylene trimer 3 and 0.8 g water and, finally, heated to 150 °C under 80 bar CO for 65 h.
- Example 1 was run with 20.4 g DIBC being added at once in the stirred reactor (i.e. batch) before pressurizing it to 70 bar CO and raising the temperature to 150 °C. The reaction was again carried out for 17 h. Under these conditions the reaction proceeded with nearly 100% conversion and -13% selectivity to branched carboxylic acid, having 10 carbon atoms (VERSATIC acid 10) .
- EXAMPLE 4
- Example 1 was run using now AMBERLYST 36 as catalyst.
- the amounts of catalyst, feed and solvent were abo ⁇ t 4 times smaller, namely 3.1, 7.4 and 19 g, respectively.
- Comparative example 2 was run as batch process with 4 times amounts of catalyst, feed and solvents, namely with 12.1, 20.3, 79 g, respectively. But the feed was added at once before pressurizing the reactor to 70 bar CO and raising the temperature to 150 °C.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for manufacture of branched carboxylic acids from branched olefins by means of reaction with carbon monoxide and a solid acid catalyst, characterized in that a branched olefin, or a precursor thereof, is reacted in continuously backmixed reactor, with continuously supplied carbon monoxide and water, while continusously an effluent is withdrawn comprising branched carboxylic acid, non-converted olefin, carbon monoxide and water, in the presence of an acidic ion exchanger, having sufficient acid groups to provide requisite protons for conversion of said olefin or a precursor of it, and carbon monoxide into branched carboxylic acids.
Description
PROCESS FOR THE MANUFACTURE OF CARBOXYLIC ACIDS
The invention relates to a process for the manufacture of carboxylic acids. More in particular the invention relates to a process for the manufacture of branched carboxylic acids by means of a Koch synthesis using carbon monoxide as reagent and a solid acid catalyst .
The up to now available processes are characterized by the fact that no solid acid catalyst could be used, unless said catalyst is operated under unattractively severe conditions or unless said catalyst is combined with corrosive Lewis acid cocatalyst or unless said catalyst is used in a non-aqueous reaction system.
In particular from International Application WO 96/20154 was known a process for the production of trialkylacetic acids from branched olefins and carbon monoxide in a non-aqueous reaction system using a solid resin catalyst comprising a cationic resin, having sufficient acid groups to provide requisite protons for conversion of branched olefin and carbon monoxide to trialkylacetic acids.
In particular the cationic resin was specified to have an acidity of at least equivalent to that of a 65 wt% sulphuric acid.
It will be appreciated by an average person skilled in the art that the said process can only be performed in two steps, in the first step of which stoichiometric amounts of branched olefin and water will not lead to the desired products in an acceptable yield. Moreover, said process cannot produce more than 1 mole of
converted olefin per mole active proton on the solid catalyst in one cycle of two steps.
On the other hand from WO 92/18592 was known a process for the manufacture of trialkylacetic acids and particularly of pivalic acid, from branched olefins and particularly isobutene, and Carbon monoxide, using a solid acid catalyst together with minor amounts of a Lewis acid, such as boron trifluoride.
In addition from EP-A-0249976 was known a process for the manufacture of branched carboxylic acids, by catalytic conversion of olefins with carbon monoxide and water in the presence of zeoliths as catalysts at temperatures of from 200 to 500 °C and at pressures of 200 to 700 bar. More in particular zeoliths of the pentasil type are used as catalysts. According to the exemplified embodiments only high temperatures (300 °C) and pressures (300-500 bar) are used.
It will be appreciated that said disclosed reaction conditions will give rise to higher operation costs due to required measures as to safety and environment.
Therefore there is still a strong need for further improvement of the manufacturing process of branched carboxylic acids, starting from branched olefins and carbon monoxide.
An object of the present invention is providing an improved manufacturing process for branched carboxylic acids, which process uses relatively mild conditions on the one hand and which shows high conversion and high selectivity to branched acids on the other hand. As a result of extensive research and experimentation such an improved process aimed at has been surprisingly found .
Accordingly the invention relates to a process for manufacture of branched carboxylic acids from branched olefins by means of reaction with carbon monoxide and a solid acid catalyst, characterized in that a branched olefin, or a precursor thereof, is reacted in a continuously backmixed reactor, wherein sufficient stirring of the feed components and product occurs to obtain an efficient backmixing ,with continuously supplied carbon monoxide and water, while continuously an effluent is withdrawn comprising branched carboxylic acid, non-converted olefin, carbon monoxide and water in the presence of an acidic ion exchanger, having sufficient acid groups to provide requisite protons for conversion of said olefin or a precursor of it, and carbon monoxide into branched carboxylic acids.
More in particular the invention relates to an improved manufacturing process of trialkylacetic acids of the formula
1 n
R2—C—C—OH
I
R3 wherein each symbol R represents a radical having 1 to 10 carbon atoms.
More preferably the total number of carbon atoms in the trialkylacetic acids ranges from 5 to 19 and most preferably from 5 to 14, derived from C4~Cι_4 olefins. With the term "branched olefin or a precursor thereof" as used throughout the present specification is meant that branched olefin itself as well as alcohols, esters or ethers, from which the specific olefin can be easily derived, can be used as starting materials for the present manufacturing process, which
makes this process much more flexible than conventional prior art processes.
In general all olefins containing at least one tertiary carbon atom or precursors therefor, can be converted by the present process.
Suitable examples of the continuously backmixed reactor, referred to hereinbefore, are continuously stirred tank reactors (CTSTR) , fluidized bed reactors or recycle reactors . The hereinbefore mentioned reactor types are known from e.g. Chemical Reaction Engineering second edition,
1962, 0 Levenspiel.
The continuously stirred tank reactors or the recycle reactors are the preferred ones. An important advantage of the process of the present invention is that it shows an improved combination of high conversion degree and high selectivity as to the desired branched carboxylic acid, in comparison to these conventional prior art processes, while operated at relatively mild conditions .
The catalyst to be used for the process of the present invention is a solid acidic ion exchanger, showing a sufficient amount of acid active sites per volume unit catalyst and a strong acid activity of each acid site.
The catalyst can be selected from the group consisting of resins, bearing sulphonic, phosphonic or trihalo acetic acid groups. Preferably sulfonated resins are applied. More preferably sulfonated resins are used, wherein the resins are copolymers of styrene and divinylbenzene,
phenol based resins, poly (tetrafluoroethylene) polymers or siloxane polymers.
In the preferred catalysts, bearing active sulfonic acid groups, the resin is treated to give a sulfonic acid cation-exchange resin capable of providing sufficient protons, i.e. the resin having per active site an acid strength equivalent to at least 65 wt% sulphuric acid and preferably to at least 70 wt% sulphuric acid. Catalyst solid resins, comprising sulfonic acid groups and derived from copolymers from styrene, divinylbenzene and phenol or derived from (tetrafluoroethylene) polymers or from siloxane polymers are preferred. More preferred are catalysts, which are sulfonated copolymers, derived from styrene and divinylbenzene, having a sulfon group density of >2 meq/ml dry resin, and preferably >3 meq/ml dry resin, while the copolymer has a divinylbenzene content in the range of from 4 to 30 wt% and preferably from 8 to 18 wt%.
Specific more preferred examples of commercial effective catalysts are AMBERLYST 36 or 38, NAFION or DELOXAN catalysts (AMBERLYST 36 or 38 or NAFION and DELOXAN are Trade Marks) . Most preferred are the AMBERLYST 36 or 38 or NAFION type catalysts. The reaction temperature in the CSTR is in the range of from 25 °C to 200 °C and preferably from 100 to 150 °C.
The pressure in the reactor is in the range of from 10 to 200 bar and preferably from 50 to 100 bar.
During the reaction an inert organic solvent can be used, which does not interfere with the desired reaction, preferably a solvent which can easily be
separated from the other reaction mixture components and recirculated. As organic solvents can be used apolar as well as polar solvents such as ketones, ethers, substituted aromatics, esters and carboxylic acids .
According to a more preferred embodiment of the present process, the branched acid primarily to be produced, is present as solvent in the reactor, and is regularly discharged from it together with water, CO, non-converted olefin and by-products, to keep the liquid level in the reactor constant.
According to one of the preferred embodiments, the CSTR is filled with solvent and catalyst with a catalyst/solvent wt ratio of in the range of from 0.1 to 0.5 w/w and preferably 0.2-0.3 w/w. The respective reactants are continuously introduced into the reactor and reaction mixture is continuously discharged.
The feed of starting olefin is in the range of from 0.01 to 10 g/g/hr, while the water/olefin molar ratio is in the range of from 0.5 to 2 mole/mole and preferably about 1 and the CO/olefin molar ratio is in the range of from 0.5 to 1000 mole/mole and preferably from 1 to 100.
It will be appreciated that, when using water amounts significantly below the hereinbefore specified amounts, the process becomes unattractive due to too low selectivity and that the selectivity and conversion have surprisingly been improved when using stoichiometric water:olefin = 1:1 feed. The invention is further illustrated by the following examples, however without restricting its scope to these specific embodiments.
EXAMPLE 1
56 g of dried AMBERLYST 15 were loaded in a 300 ml CSTR reactor, suspended in 145 ml of n-hexanoic acid (solvent], and activated upon heating up to 155 °C under 10 bar CO with regular purge of the gas cap followed by 1 h at 155 °C under a 80 bar CO flow of 50 g/h. A feed containing propylene trimer water and CO the molar ratio of water: trimer being 1:1 was then admitted to the reactor with a velocity of 8.5, 1.2 and 50 g/h (WHSV of 0.15, 0.021 and 0.9 g/g/h) under continuous stirring of 1100 rpm, the liquid level of the reactor being kept constant by continuously removing the excess liquid product.
Under these conditions the reaction proceeded with about 75-85% conversion and 93-95% selectivity to the branched carboxylic acid having 10 carbon atoms (VERSATIC acid 10), for some 24 h. COMPARATIVE EXAMPLE 1
20 g of AMBERLYST 15 were loaded in a stirred batch rector, dried for 2 h at 110 °C under vacuum, suspended in a solution of 50 g propanoic acid (solvent), 6 g propylene trimer 3 and 0.8 g water and, finally, heated to 150 °C under 80 bar CO for 65 h.
Under these conditions the reaction proceeded with about 91% conversion and 8% selectivity to the branched carboxylic acid having 10 carbon atoms (VERSATIC acid 10) . EXAMPLE 2
In the same way as described in example 1 NAFION NR 50 catalyst (59 g) , dissolved in 120 ml hexanoic acid was used for the conversion of propylene trimer with CO and H2O into branched carboxylic acids,
containing 10 carbon atoms, under the following conditions propylene trimer 8.8 g/h (WHSV = 0.16 g/g/h) water _ 1.2 g/h (WHSV = 0.021 g/g/h) CO 52 g/h (WHSV = 0.9 g/g/h) temperature 155 °C pressure 80 bar
The conversion was 88 mol% and the selectivity was 91 mol% EXAMPLE 3
13.6 g of dried AMBERLYST 38 were loaded in a 240 ml stirred autoclave, dried for 2 h at 150 °C under vacuum, cooled to room temperature, suspended in 74 g of pivalic acid (solvent) , pressurized under 70 bar CO and heated up to reaction temperature of 150 °C. During the heating period, 23.4 g of DIBC (di-isobutyl- carbinol) were slowly and continuously introduced into the autoclave over 17 h. At the end of the run, the reactor was cooled down and emptied for analysis. Under these conditions the reaction proceeded with nearly 100% conversion and -56% selectivity to branched carboxylic acid, having 10 carbon atoms (VERSATIC acid 10) . COMPARATIVE EXAMPLE 2 Example 1 was run with 20.4 g DIBC being added at once in the stirred reactor (i.e. batch) before pressurizing it to 70 bar CO and raising the temperature to 150 °C. The reaction was again carried out for 17 h. Under these conditions the reaction proceeded with nearly 100% conversion and -13% selectivity to branched carboxylic acid, having 10 carbon atoms (VERSATIC acid 10) .
EXAMPLE 4
Example 1 was run using now AMBERLYST 36 as catalyst. The amounts of catalyst, feed and solvent were aboμt 4 times smaller, namely 3.1, 7.4 and 19 g, respectively.
Under these conditions the reaction proceeded with -85% conversion and -32% selectivity to branched carboxylic acid, having 10 carbon atoms (VERSATIC acid 10) . COMPARATIVE EXAMPLE 3
Comparative example 2 was run as batch process with 4 times amounts of catalyst, feed and solvents, namely with 12.1, 20.3, 79 g, respectively. But the feed was added at once before pressurizing the reactor to 70 bar CO and raising the temperature to 150 °C.
Under these conditions the reaction proceeded with -93% conversion and -2.7% selectivity to branched carboxylic acid, having 10 carbon atoms (VERSATIC acid 10) .
Claims
1. A process for manufacture of branched carboxylic acids from branched olefins by means of reaction with carbon monoxide and a solid acid catalyst, characterized in that a branched olefin, or a precursor thereof is reacted in continuous backmixed reactor, wherein sufficient stirring of the feed components and product occurs to obtain an efficient backmixing with continuously supplied carbon monoxide and water, while continuously an effluent is withdrawn comprising branched carboxylic acid, non-converted olefin, carbon monoxide and water, in the presence of an acidic ion exchanger, having sufficient acid groups to provide requisite protons for conversion of said olefin or a precursor of it, and carbon monoxide into branched carboxylic acids.
2. A process according to claim 1, characterized in that trialkylacetic acids of the formula
R2ΓÇöCΓÇöCΓÇöOH I
R3 are produced, wherein each symbol R represents a radical having 1 to 10 carbon atoms.
3. A process according to claim 1 or 2, characterized in that the total number of carbon atoms in the trialkyl acetic acids ranges from 5 to 19.
4. A process according to claim 3, characterized in that the total number of carbon atoms in the trialkylacetic acids ranges from 5 to 14.
5. A process according to claims 1-4, characterized in that as solid acid catalyst is used a solid acidic ion exchanger, selected from the group consisting of sulfonated resins, sulfonated poly (tetrafluoro- ethylene) and sulfonated siloxane polymers.
6. A process according to claims 1-5, characterized in that as catalyst is used an acidic ion exchanger selected from sulfonated copolymers of styrene and divinylbenzene or phenolic base resins.
7. A process according to claims 5-6, characterized in that the resin is treated to give a sulfonic acid cation-exchange resin, such that the resin having per active site an acid strength equivalent to at least 65 wt% sulphuric acid and preferably to at least 70 wt% sulphuric acid.
8. A process according to claims 1-7, characterized in that as catalyst a sulfonated copolymer derived from styrene and divinylbenzene, having a sulfon group density of >2 meq/ml dry resin and preferably >3 meq/ml dry resin, while the copolymer has a content of divinylbenzene in the range of 4 to 30 wt% and preferably from 8 to 18 wt%.
9. A process according to claims 1-8, characterized in that the pressure in the reactor is in the range of from 50 to 100 bar.
10. A process according to claims 1-9, characterized in that during the reaction a branched acid primarily to be produced, is present as solvent in the reactor.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-1999-7007721A KR100497943B1 (en) | 1997-02-25 | 1998-02-24 | Process for the manufacture of carboxylic acids |
| CA002282350A CA2282350A1 (en) | 1997-02-25 | 1998-02-24 | Process for the manufacture of carboxylic acids |
| JP53732398A JP4025373B2 (en) | 1997-02-25 | 1998-02-24 | Method for producing carboxylic acid |
| AU64001/98A AU726899B2 (en) | 1997-02-25 | 1998-02-24 | Process for the manufacture of carboxylic acids |
| AT98909484T ATE219043T1 (en) | 1997-02-25 | 1998-02-24 | METHOD FOR PRODUCING CARBOXYLIC ACIDS |
| NZ336802A NZ336802A (en) | 1997-02-25 | 1998-02-24 | Process for the manufacture of carboxylic acids |
| PCT/EP1998/001128 WO1998038149A1 (en) | 1997-02-25 | 1998-02-24 | Process for the manufacture of carboxylic acids |
| EP98909484A EP0968166B1 (en) | 1997-02-25 | 1998-02-24 | Process for the manufacture of carboxylic acids |
| DE69805980T DE69805980T2 (en) | 1997-02-25 | 1998-02-24 | METHOD FOR PRODUCING CARBONIC ACIDS |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97200537.5 | 1997-02-25 | ||
| PCT/EP1998/001128 WO1998038149A1 (en) | 1997-02-25 | 1998-02-24 | Process for the manufacture of carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998038149A1 true WO1998038149A1 (en) | 1998-09-03 |
Family
ID=8166882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1998/001128 WO1998038149A1 (en) | 1997-02-25 | 1998-02-24 | Process for the manufacture of carboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO1998038149A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000017146A1 (en) * | 1998-09-21 | 2000-03-30 | Resolution Research Nederland B.V. | Process for the manufacture of quaternary carboxylic acids |
| WO2000024700A1 (en) * | 1998-10-22 | 2000-05-04 | Resolution Research Nederland B.V. | PROCESS FOR THE MANUFACTURE OF α,α-BRANCHED CARBOXYLIC ACIDS |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0249976A1 (en) * | 1986-06-19 | 1987-12-23 | BASF Aktiengesellschaft | Process for the production of carboxylic acids |
| US5250726A (en) * | 1992-08-24 | 1993-10-05 | E. I. Du Pont De Nemours And Company | Process for the preparation of 3-pentenoic acid from butadiene |
| WO1996020154A1 (en) * | 1994-12-28 | 1996-07-04 | Exxon Chemical Patents Inc. | Production of trialkylacetic acids using a solid cationic resin catalyst system |
-
1998
- 1998-02-24 WO PCT/EP1998/001128 patent/WO1998038149A1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0249976A1 (en) * | 1986-06-19 | 1987-12-23 | BASF Aktiengesellschaft | Process for the production of carboxylic acids |
| US5250726A (en) * | 1992-08-24 | 1993-10-05 | E. I. Du Pont De Nemours And Company | Process for the preparation of 3-pentenoic acid from butadiene |
| WO1996020154A1 (en) * | 1994-12-28 | 1996-07-04 | Exxon Chemical Patents Inc. | Production of trialkylacetic acids using a solid cationic resin catalyst system |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000017146A1 (en) * | 1998-09-21 | 2000-03-30 | Resolution Research Nederland B.V. | Process for the manufacture of quaternary carboxylic acids |
| JP2002526464A (en) * | 1998-09-21 | 2002-08-20 | レゾリューション・リサーチ・ネーデルランド・ベー・ウィ | Method for producing quaternary carboxylic acid |
| WO2000024700A1 (en) * | 1998-10-22 | 2000-05-04 | Resolution Research Nederland B.V. | PROCESS FOR THE MANUFACTURE OF α,α-BRANCHED CARBOXYLIC ACIDS |
| US6211406B1 (en) | 1998-10-22 | 2001-04-03 | Shell Oil Company | Process for the manufacture of α, α-branched carboxylic acids |
| JP2002528428A (en) * | 1998-10-22 | 2002-09-03 | レゾリューション・リサーチ・ネーデルランド・ベー・ウィ | Method for producing α, α-branched carboxylic acid |
| KR100633971B1 (en) * | 1998-10-22 | 2006-10-16 | 레졸루션 레사아치 네덜란드 비.브이. | Method for preparing alpha, alpha-side chain carboxylic acid |
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