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WO1998038149A1 - Procede pour la fabrication d'acides carboxyliques - Google Patents

Procede pour la fabrication d'acides carboxyliques Download PDF

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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
Authority
WO
WIPO (PCT)
Prior art keywords
acid
process according
branched
carbon monoxide
olefin
Prior art date
Application number
PCT/EP1998/001128
Other languages
English (en)
Inventor
Anthonius Johannes Maria Breed
Rene Johan Haan
Jean-Paul Lange
Leonardus Petrus
Original Assignee
Shell Internationale Research Maatschappij B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to KR10-1999-7007721A priority Critical patent/KR100497943B1/ko
Priority to CA002282350A priority patent/CA2282350A1/fr
Priority to JP53732398A priority patent/JP4025373B2/ja
Priority to AU64001/98A priority patent/AU726899B2/en
Priority to AT98909484T priority patent/ATE219043T1/de
Priority to NZ336802A priority patent/NZ336802A/en
Priority to PCT/EP1998/001128 priority patent/WO1998038149A1/fr
Priority to EP98909484A priority patent/EP0968166B1/fr
Priority to DE69805980T priority patent/DE69805980T2/de
Publication of WO1998038149A1 publication Critical patent/WO1998038149A1/fr

Links

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

L'invention a pour objet un procédé pour la fabrication d'acides carboxyliques ramifiés à partir d'oléfines ramifiées par une réaction avec du monoxyde de carbone et un catalyseur acide solide. Ce procédé se caractérise en ce qu'une oléfine ramifiée, ou un précurseur de cette dernière, est soumise à une réaction dans un réacteur de mélange continu à contre-courant, avec du monoxyde de carbone et de l'eau fournis en continu. En outre, un effluent à base d'acide carboxylique ramifié, d'oléfine non transformée, de monoxyde de carbone et d'eau est retiré en continu, en présence d'un échangeur d'ions acides, comportant suffisamment de groupes acides pour fournir les protons nécessaires pour la transformation en acides carboxyliques ramifiés de cette oléfine, ou d'un précurseur de cette dernière, et du monoxyde de carbone.
PCT/EP1998/001128 1997-02-25 1998-02-24 Procede pour la fabrication d'acides carboxyliques WO1998038149A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
KR10-1999-7007721A KR100497943B1 (ko) 1997-02-25 1998-02-24 카복실산 제조방법
CA002282350A CA2282350A1 (fr) 1997-02-25 1998-02-24 Procede pour la fabrication d'acides carboxyliques
JP53732398A JP4025373B2 (ja) 1997-02-25 1998-02-24 カルボン酸の製造方法
AU64001/98A AU726899B2 (en) 1997-02-25 1998-02-24 Process for the manufacture of carboxylic acids
AT98909484T ATE219043T1 (de) 1997-02-25 1998-02-24 Verfahren zur herstellung von carbonsäuren
NZ336802A NZ336802A (en) 1997-02-25 1998-02-24 Process for the manufacture of carboxylic acids
PCT/EP1998/001128 WO1998038149A1 (fr) 1997-02-25 1998-02-24 Procede pour la fabrication d'acides carboxyliques
EP98909484A EP0968166B1 (fr) 1997-02-25 1998-02-24 Procede pour la fabrication d'acides carboxyliques
DE69805980T DE69805980T2 (de) 1997-02-25 1998-02-24 Verfahren zur herstellung von carbonsäuren

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP97200537.5 1997-02-25
PCT/EP1998/001128 WO1998038149A1 (fr) 1997-02-25 1998-02-24 Procede pour la fabrication d'acides carboxyliques

Publications (1)

Publication Number Publication Date
WO1998038149A1 true WO1998038149A1 (fr) 1998-09-03

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Application Number Title Priority Date Filing Date
PCT/EP1998/001128 WO1998038149A1 (fr) 1997-02-25 1998-02-24 Procede pour la fabrication d'acides carboxyliques

Country Status (1)

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WO (1) WO1998038149A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000017146A1 (fr) * 1998-09-21 2000-03-30 Resolution Research Nederland B.V. Procede servant a preparer des acides carboxyliques quaternaires
WO2000024700A1 (fr) * 1998-10-22 2000-05-04 Resolution Research Nederland B.V. PROCEDE DE PRODUCTION D'ACIDES α,α CARBOXYLIQUES RAMIFIES

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0249976A1 (fr) * 1986-06-19 1987-12-23 BASF Aktiengesellschaft Procédé de production d'acides carboxyliques
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 (fr) * 1994-12-28 1996-07-04 Exxon Chemical Patents Inc. Production d'acides trialkylacetiques au moyen d'un catalyseur solide de resine cationique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0249976A1 (fr) * 1986-06-19 1987-12-23 BASF Aktiengesellschaft Procédé de production d'acides carboxyliques
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 (fr) * 1994-12-28 1996-07-04 Exxon Chemical Patents Inc. Production d'acides trialkylacetiques au moyen d'un catalyseur solide de resine cationique

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000017146A1 (fr) * 1998-09-21 2000-03-30 Resolution Research Nederland B.V. Procede servant a preparer des acides carboxyliques quaternaires
JP2002526464A (ja) * 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 第四カルボン酸の製造方法
WO2000024700A1 (fr) * 1998-10-22 2000-05-04 Resolution Research Nederland B.V. PROCEDE DE PRODUCTION D'ACIDES α,α CARBOXYLIQUES RAMIFIES
US6211406B1 (en) 1998-10-22 2001-04-03 Shell Oil Company Process for the manufacture of α, α-branched carboxylic acids
JP2002528428A (ja) * 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 α，α−分岐状カルボン酸の製造方法
KR100633971B1 (ko) * 1998-10-22 2006-10-16 레졸루션 레사아치 네덜란드 비.브이. 알파,알파-측쇄 카복실산의 제조방법

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