[go: up one dir, main page]

WO1999036385A1 - Production d'alkyl-esters - Google Patents

Production d'alkyl-esters Download PDF

Info

Publication number
WO1999036385A1
WO1999036385A1 PCT/GB1999/000146 GB9900146W WO9936385A1 WO 1999036385 A1 WO1999036385 A1 WO 1999036385A1 GB 9900146 W GB9900146 W GB 9900146W WO 9936385 A1 WO9936385 A1 WO 9936385A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
group
reactor
phosphorous
carbonylation
Prior art date
Application number
PCT/GB1999/000146
Other languages
English (en)
Inventor
Philip John Davies
Original Assignee
Ineos Acrylics Uk Limited
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 Ineos Acrylics Uk Limited filed Critical Ineos Acrylics Uk Limited
Priority to AU20684/99A priority Critical patent/AU2068499A/en
Publication of WO1999036385A1 publication Critical patent/WO1999036385A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond

Definitions

  • the present invention concerns a process for the production of alkyl esters of aliphatic carboxylic acids, in particular methyl propionate, from alkene, carbon monoxide and alkanoi.
  • alkanoic esters and acids by carbonylation of alkenes in the presence of an alkanoi or water, as appropriate, is well known.
  • EP-A-0411721 discloses a continuous process for the preparation of an alkyl propionate, which comprises reacting an alkanoi in a liquid phase with ethylene and carbon monoxide in a reaction vessel in the presence of a carbonylation catalyst and passing a gas through the reaction vessel, thereby forming a stream of vapour comprising alkyl propionate, gas and unreacted alkanoi.
  • the vapour stream is then condensed and the resulting liquid comprises alkyl propionate, alkanoi and impurities.
  • the alkanoi or alkanol/alkyl propionate azeotropic mixture is distilled from the alkyl propionate product stream and recycled to the reaction vessel .
  • WO/96/19434 describes the use of a catalyst comprising a bidentate phosphine ligand, a palladium compound and a source of anions in the carbonylation of olefins, especially ethylene, to form alkyl esters, e.g. methyl propionate.
  • a catalyst comprising a bidentate phosphine ligand, a palladium compound and a source of anions in the carbonylation of olefins, especially ethylene, to form alkyl esters, e.g. methyl propionate.
  • Such catalysts may be expensive to produce and therefore it is advantageous to the economics of such processes to increase the effectiveness and/or life of the catalyst to reduce the requirement for recycling treatment of the catalyst and hence reduce the overall catalyst cost.
  • a process for the carbonylation of an unsaturated compound comprises the steps of: a) supplying a first feed stream comprising carbon monoxide and an unsaturated compound to the reactor; b) supplying a second feed stream comprising an alkyl alcohol of formula R-OH, where R is an alkyl group, to the reactor; c) reacting together said first and second feed streams in the reactor in the presence of a metal-containing carbonylation catalyst, which catalyses the carbonylation reaction between carbon monoxide and the alkene, to form a product comprising an alkyl ester; characterised in that the carbonylation reaction is carried out in the presence of a further metal species.
  • the unsaturated compound is preferably a lower alkene, e.g. C 1 - C 6 , more preferably C, - C 4 , especially ethylene.
  • the carbonylation of ethylene in the presence of an alcohol R-OH leads to the formation of an alkyl propionate, CH 3 CH 2 COOR.
  • alkyl esters have a variety of uses, e.g. as solvents or as intermediates of other industrially useful compounds.
  • the alcohol R-OH is preferably a lower alkyl alcohol, e.g. C, - C 8 alcohol.
  • a particularly preferred alcohol is methanol.
  • the carbonylation catalyst preferably comprises a combination of palladium or a compound thereof and phosphorous-containing compound.
  • Various phosphine compounds are suitable catalysts and have been described in prior publications, e.g. tertiary phosphines of general formula R 1 R 2 R 3 P wherein R ⁇ R 2 and R 3 are each an optionally substituted alkyl or aryl group, e.g. triphenylphosphine.
  • a particularly preferred phosphorous-containing compound is a bidentate phosphine ligand of general formula (R 3 -C) 2 P-L 1 -X-L 2 -P-(C-R 3 ) 2 , in which each R is independently a pendant, optionally substituted, organic group through which the group is linked to tertiary carbon atom C; L 1 , L 2 are independently a linking group selected from an optionally substituted lower alkylene chain connecting the respective phosphorous atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorous atoms are linked on available adjacent carbon atoms.
  • a catalyst is described in WO/96/19434.
  • the pendant optionally substituted organic groups, R may be independently selected from a wide range of components.
  • the pendant groups are optionally substituted lower alkyl, e.g. C 1 . horr, and which may be branched or linear.
  • Particularly preferred is when the organic groups, R, when associated with their respective carbon atom form composite groups which are at least as sterically hindering as t-butyl. Steric hindrance in this context is as discussed at page 14 et seq of "Homogeneous Transition Metal Catalysis - A Gentle Art", by C Masters, published by Chapman and Hall, 1981.
  • the linking groups, L 1 and L 2 are independently selected from an optionally substituted, particularly lower alkyl, e.g. C to C 4 , substituted, lower alkylene, e.g. C- to C 4 chain. Especially preferred is when both L 1 and L 2 are methylene.
  • aryl moiety may be by other organic groups, e.g. alkyl, particularly , aryl, alkoxy, carbalkoxy, halo, nitro, trihalomethyl and cyano.
  • the aryl moiety may be a fused polycyclic group, e.g. naphthalene, biphenylene or indene.
  • bidentate ligands examples include ⁇ 'bis(di-t-butyl phosphino) - o - xylene (also known as 1 ,2 bis (di-t-butylphosphinomethyl) benzene), ⁇ 'bis (di-t-neopentyl phosphino) - o - xylene and bis 2,3(di-t-butyl phosphino) naphthalene.
  • the bidentate phosphine may be bonded to a suitable polymeric or inorganic substrate via at least one of the bridging group X, the linking group L 1 or the linking group L 2 , e.g. bis (di-t-butyl phosphino) - o - xylene may be bonded via the xylene group to polystyrene to give an immobile heterogeneous catalyst.
  • the amount of bidentate ligand used can vary within wide limits.
  • the bidentate ligand is present in an amount such that the ratio of the number of moles of the bidentate ligand present to the number of moles of palladium present is from 1 to 50, e.g. 1 to 10 and particularly from 1 to 5 mol per mol.
  • Suitable compounds of palladium include salts of palladium with, or compounds comprising weakly co-ordinated anions derived from nitric acid; sulphuric acid; lower alkanoic (up to C 12 ) acids such as acetic acid and propionic acid including halogenated carboxylic acids such as trifluoroacetic acid and trichloroacetic acid; sulphonic acids such as methanesulphonic acid, chlorosulphonic acid, fluorosulphonic acid, trifluoro methanesulphonic acid, benzenesulphonic acid, naphthalenesulphonic acid, toluenesulphonic acids, e.g.
  • p-toluenesulphonic acid t-butylsulphonic acid, and 2-hydroxypropanesulphonic acid
  • sulphonated ion exchange resins perhalic acids such as perchloric acid; halogenated carboxylic acids such as trichloroacetic acid and trifluoroacetic acid; orthophosphoric acid; phosphonic acids such as benzenephosphonic acid; and acids derived from interactions between Lewis acids and Broensted acids.
  • Other sources which may provide suitable anions include the optionally halogenated tetraphenylborate derivatives, e.g. perfluorotetraphenyl borate.
  • zero-valent palladium complexes particularly those with labile ligands e.g. alkenes such as dibenzylideneacetone or styrene or triphenyl phosphine may be used.
  • the catalyst system may be used homogeneously or heterogeneously. Preferably the catalyst system is used homogeneously.
  • the catalyst system is preferably constituted in the liquid phase which may be formed by one or more of the reactants or by the use of a suitable solvent.
  • an additional compound comprising an anion which is essentially non-coordinating to palladium ions is also present in the reaction mixture.
  • the anion may be introduced as one or more of an acid having a pKa measured in aqueous solution of less than 4, a salt with a cation that does not interfere with the reaction, e.g. metal salts or largely organic salts such as alkyl ammonium, and a precursor, such as an ester, that can break down under reaction conditions to generate the anion in situ and acids derived from interactions between Lewis acids and Broensted acids such as SbCI 4 " , FeCI 4 " and other similar compounds.
  • Suitable acids and salts include the acids and salts, other than unsubstituted carboxylates, listed supra.
  • a preferred source of an anion is methanesulphonic acid.
  • the molar ratio of anion to palladium may be from 1 :1 to 500:1 , preferably from 2:1 to 100:1 and particularly from 3:1 to 30:1.
  • the anion may be provided by a combination of acid and salt.
  • Suitable solvents that may be used in conjunction with the catalyst system include one or more aprotic solvents such as ethers, e.g. diethyl ether, dimethyl ether of diethylene glycol, anisole and diphenyl ether; aromatic compounds, including halo variants of such compounds, e.g. benzene, toluene, ethyl benzene, o-xyiene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; alkanes, including halo variants of such compounds, e.g.
  • aprotic solvents such as ethers, e.g. diethyl ether, dimethyl ether of diethylene glycol, anisole and diphenyl ether
  • aromatic compounds including halo variants of such compounds, e.g. benzene, tolu
  • nitriles e.g. benzonitrile and acetonitrile
  • esters e.g. methyl benzoate, methyl acetate, methyl propionate and dimethyl phthalate
  • sulphones e.g. diethyl sulphone and tetrahydrothiophene 1 , 1- dioxide
  • carboxyiic acids e.g. propionic acid.
  • Particularly suitable solvents are the reactants and products of the reaction. Therefore in the carbonylation of ethylene with carbon monoxide in the presence of methanol to form methyl propionate, preferred solvents are methyl propionate and methanol.
  • the process of the present invention is preferably carried out at a temperature from 20 to 250°C, in particular from 40 to 150°C and especially from 70 to 120°C.
  • the process may be conducted under a total pressure of from 1 x 10 5 to 100 x 10 5 N.m “2 and in particular from 5 x 10 5 to 50 x 10 5 N.m “2 .
  • the further metal species is preferably a cobalt compound.
  • a preferred cobalt compound is cobalt carbonyl (Co 2 (CO) 8 ) although other compounds of cobalt may also be expected to be effective.
  • the cobalt (Co) compound is preferably present in an amount to give a mole ratio Co:Pd of at least 0.01 :1 , more preferably at least 0.5:1 , especially at least 1 :1.
  • a process for the production of methyl propionate comprising the steps of a) supplying a first feed stream comprising carbon monoxide and ethylene in the gas phase to a reactor; b) supplying a second feed stream comprising methanol to the reactor; c) reacting together said first and second feed streams in the reactor in the presence of a carbonylation catalyst, comprising a combination of palladium (or a compound thereof) and a phosphorous-containing compound, which catalyses the carbonylation reaction between carbon monoxide and ethylene, to form a product stream containing methyl propionate; characterised in that a cobalt compound is present in the reaction mixture such that the ratio of Co:Pd is at least 0.01 :1.
  • a solid catalyst, palladium (di-t butylphosphino o-xylene) dibenzylidene acetone (37mg, 5.0 x 10 5 moles), cobalt carbonyl (9mg, 2.6 x 10 s moles) and methanesulphonic acid (68 ⁇ l, 1.0 x 10 "3 moles) were dissolved in methanol (219ml, 5.41 moles) and methyl propionate (81 mis, 0.841 moles) under an atmosphere of nitrogen.
  • the ratio of Co:Pd was approximately 1 :1.
  • Example 1 was repeated except that the amount of cobalt carbonyl added was 26 mg, 5.8 x 10 5 moles, giving a mole ratio Co:Pd of 3:1. the TON after four hours was found to be 21227.
  • Example 1 was repeated except that no cobalt carbonyl was added to the reaction mixture.
  • the TON was found to be 14000 after four hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de carbonylation d'un composé insaturé comprenant les opérations suivantes: a) on introduit dans un réacteur un premier flux d'alimentation comprenant du monoxyde de carbone et un composé insaturé; b) on introduit dans le réacteur un second flux d'alimentation comprenant un alkyle alcool de formule R-OH, dans laquelle R est un groupe alkyle; c) on fait réagir ensemble les premier et second flux d'alimentation dans le réacteur en présence d'un catalyseur de carbonylation contenant un métal, qui catalyse la réaction de carbonylation entre le monoxyde de carbone et l'alcène pour former un produit comprenant un alkyl-ester. Ce procédé est caractérisé en ce que la réaction de carbonylation est conduite en présence d'un espèce métallique additionnelle. Cette espèce métallique additionnelle est de préférence le cobalt.
PCT/GB1999/000146 1998-01-17 1999-01-15 Production d'alkyl-esters WO1999036385A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU20684/99A AU2068499A (en) 1998-01-17 1999-01-15 Production of alkyl esters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9800915.2 1998-01-17
GBGB9800915.2A GB9800915D0 (en) 1998-01-17 1998-01-17 Production of alkyl esters

Publications (1)

Publication Number Publication Date
WO1999036385A1 true WO1999036385A1 (fr) 1999-07-22

Family

ID=10825399

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/000146 WO1999036385A1 (fr) 1998-01-17 1999-01-15 Production d'alkyl-esters

Country Status (4)

Country Link
AU (1) AU2068499A (fr)
GB (1) GB9800915D0 (fr)
WO (1) WO1999036385A1 (fr)
ZA (1) ZA99293B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104529765A (zh) * 2014-12-18 2015-04-22 西南化工研究设计院有限公司 一种生产丙酸甲酯的反应装置及方法
US9908839B2 (en) 2014-06-24 2018-03-06 Dow Global Technologies Llc Process for producing low VOC coalescing aids
US9938226B2 (en) 2013-09-30 2018-04-10 Dow Global Technologies Llc Gas phase production of alkyl alkanoate
CN112830877A (zh) * 2019-11-22 2021-05-25 中国科学院大连化学物理研究所 一种负载型单原子贵金属催化剂在不饱和烃羧甲酯化反应中的应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3168553A (en) * 1961-08-25 1965-02-02 Shell Oil Co Reactions of olefins with carbon monoxide
FR2078713A5 (fr) * 1970-02-20 1971-11-05 Mobil Oil Corp
EP0055875A1 (fr) * 1981-01-06 1982-07-14 Shell Internationale Researchmaatschappij B.V. Procédé de carbonylation d'oléfines
US5315028A (en) * 1993-05-12 1994-05-24 Ethyl Corporation Olefinic process for preparing aryl-substituted aliphatic carboxylic esters
WO1996019434A1 (fr) * 1994-12-22 1996-06-27 Imperial Chemical Industries Plc Procede de carbonylation de l'ethylene et systeme de catalyse utilisable pour ce procede

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3168553A (en) * 1961-08-25 1965-02-02 Shell Oil Co Reactions of olefins with carbon monoxide
FR2078713A5 (fr) * 1970-02-20 1971-11-05 Mobil Oil Corp
EP0055875A1 (fr) * 1981-01-06 1982-07-14 Shell Internationale Researchmaatschappij B.V. Procédé de carbonylation d'oléfines
US5315028A (en) * 1993-05-12 1994-05-24 Ethyl Corporation Olefinic process for preparing aryl-substituted aliphatic carboxylic esters
WO1996019434A1 (fr) * 1994-12-22 1996-06-27 Imperial Chemical Industries Plc Procede de carbonylation de l'ethylene et systeme de catalyse utilisable pour ce procede

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9938226B2 (en) 2013-09-30 2018-04-10 Dow Global Technologies Llc Gas phase production of alkyl alkanoate
US9908839B2 (en) 2014-06-24 2018-03-06 Dow Global Technologies Llc Process for producing low VOC coalescing aids
CN104529765A (zh) * 2014-12-18 2015-04-22 西南化工研究设计院有限公司 一种生产丙酸甲酯的反应装置及方法
CN112830877A (zh) * 2019-11-22 2021-05-25 中国科学院大连化学物理研究所 一种负载型单原子贵金属催化剂在不饱和烃羧甲酯化反应中的应用
CN112830877B (zh) * 2019-11-22 2022-03-29 中国科学院大连化学物理研究所 一种负载型单原子贵金属催化剂在不饱和烃羧甲酯化反应中的应用

Also Published As

Publication number Publication date
GB9800915D0 (en) 1998-03-11
ZA99293B (en) 1999-07-19
AU2068499A (en) 1999-08-02

Similar Documents

Publication Publication Date Title
JP3949716B2 (ja) エチレンのカルボニル化法およびそれに使用するための触媒系
EP1027321B1 (fr) Production d'esters
AU737772B2 (en) Process for the carbonylation of ethylene
EP1263713B2 (fr) Procede de carbonylation de pentenenitrile
US6489506B2 (en) Process for the palladium and phosphine ligand catalyzed carbonylation of ethylene
KR100785978B1 (ko) 펜텐산 및 그의 유도체의 카르보닐화 방법
WO2002048094A1 (fr) Procede de fabrication de l'acide 5-cyanovalerique, l'acide adipique ou dimethyle adipate
WO1999036385A1 (fr) Production d'alkyl-esters
GB2261662A (en) Carbonylation of aryl halides
MXPA99008376A (en) Process for the carbonylation of ethylene
EP1023257A1 (fr) Procede de preparation d'un anhydride de l'acide pentenoique

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
NENP Non-entry into the national phase

Ref country code: KR

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase