WO1997025144A1 - Catalyseur d'esterification et procede pour sa preparation - Google Patents

Catalyseur d'esterification et procede pour sa preparation Download PDF

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Publication number
WO1997025144A1
WO1997025144A1 PCT/CN1996/000068 CN9600068W WO9725144A1 WO 1997025144 A1 WO1997025144 A1 WO 1997025144A1 CN 9600068 W CN9600068 W CN 9600068W WO 9725144 A1 WO9725144 A1 WO 9725144A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
metal
copper
cobalt
catalyst according
Prior art date
Application number
PCT/CN1996/000068
Other languages
English (en)
Chinese (zh)
Inventor
Peiyu Jiao
Changli Zhang
Original Assignee
Peiyu Jiao
Changli Zhang
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 Peiyu Jiao, Changli Zhang filed Critical Peiyu Jiao
Priority to AU67313/96A priority Critical patent/AU6731396A/en
Publication of WO1997025144A1 publication Critical patent/WO1997025144A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification

Definitions

  • the present invention relates to a catalyst for a tritiation reaction and a preparation method thereof.
  • esterification catalysts can be divided into two categories: acidic catalysts and non-acidic catalysts.
  • acidic catalysts are currently the most widely used catalysts, such as sulfuric acid, etc., USPat. 2, 787, 636; USPat. 2, 644, 839, etc.
  • Patent literature introduces sulfuric acid catalyst, which has the advantages of high catalytic activity, good compatibility with reactants, cheap and easy to obtain, etc. At the same time, it has strong corrosiveness, and has the effect of oxidative dehydration, especially when heated Poor stability, easy to affect product color, significant increase in by-products, reducing product quality performance.
  • higher temperature acetation reaction generally uses other non-acid catalysts, such as titanate, stannous oxide and sodium aluminate, etc., Ger.2, 042, 402; Patent Zhao 46-6971; Patent Zhao 47-3806 and other patent documents introduce titanate-based catalysts, but these catalysts also have low-temperature acetic acid reactions with low catalytic activity and cannot be used continuously. It is expensive and can only be used for the production of plasticizers. At present, most acetic acid reactions in the industry are still catalyzed by sparse acid liquid phase. Pollution. Thus, as environmental regulations continue to improve the environmental and safety requirements, questions.
  • non-acid catalysts such as titanate, stannous oxide and sodium aluminate, etc., Ger.2, 042, 402; Patent Zhao 46-6971; Patent Zhao 47-3806 and other patent documents introduce titanate-based catalysts, but these catalysts also have low-temperature acetic acid reactions with low catalytic activity and cannot be used continuously. It is expensive and can only be used
  • the purpose of the present invention is to provide a catalyst for esterification reaction and a preparation method thereof, which can prepare a catalyst with high catalytic activity, good selectivity, no side reaction, and can react in equal moles with stable reaction performance.
  • R is a harmless ethylene-diethylene harmless copolymer or a resin
  • Y is a sulfur atom or a phosphorus atom
  • M is a metal ion such as copper, iron, cobalt, nickel, zinc, aluminum, or a metal mixture thereof. Ions.
  • the resin is a cation exchange resin, and metal ions can be obtained from metal salts or metal oxides or metal elements.
  • a method for preparing a catalyst for esterification reaction characterized in that it comprises: immersing a cation exchange resin with 10% sulfuric acid, soaking for 6 hours to two days, then filtering, washing with distilled water to neutrality, and The metal ions are mixed uniformly and dried at 70-100.
  • the method provided by the present invention has simple process flow and convenient operation, and does not need to invest a large amount of capital equipment.
  • the prepared catalyst does not corrode the equipment during use and evaporates the residual liquid. No carbonization, smooth water separation, the amount of water can reach the theoretical value.
  • the esterification reaction can be carried out continuously or intermittently. No intermittent tailing is required for batch finishing, no environmental pollution, good heating stability, no side reactions, and can wait for molecules to react.
  • the quality and performance of the product are significantly improved, and the price is low. It can be used for low temperature and higher temperature esters.
  • the catalyst can continuously perform multiple esterification reactions, and the catalytic activity and selectivity are significantly higher.
  • the catalyst for the tritiation reaction provided by the present invention is composed of a cation exchange resin and a metal ion.
  • the metal ions described above are selected from metal salts or selected from metal oxides such as copper oxide, iron oxide; cobalt oxide, nickel oxide, oxide, alumina, and mixtures thereof or selected from metal elements.
  • the preferred metal ion is ⁇
  • the metal ions in the acid salt may be copper sulfate, iron sulfate, cobalt sulfate, nickel sulfate, zinc sulfate, or aluminum sulfate, or a mixture of copper sulfate and cobalt sulfate.
  • a particularly preferred metal ion is a metal copper ion.
  • the method provided by the present invention is: take cation exchange resin soaked with 10% sulphuric acid, soak for 6 hours to two days, then filter, wash with distilled water until neutral, and then mix with the above metal ions at 70-100 " Reserve after drying.
  • a 500 liter reactor was equipped with a fractionation column and a water separator of a reflux device. 220 kg (2500 mol) of isoamyl alcohol and 150 kg (2500 mol) of acetic acid were added, and then the catalyst dosing agent prepared in Example 3 was added. 2 kg, reflux reaction at 140 ⁇ , 45 kg of water was separated, 325 kg of isoamyl acetate was obtained, the content was 97%, and the product yield was 100%. Continuous addition of acid and yeast can continuously react for more than 6 batches.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

Cette invention se rapporte à un catalyseur d'estérification représenté par la formule: RYO3M, où R représente un copolymère styrène-divinylbenzène ou une résine de phénol-formaldéhyde; Y représente un atome de phosphore ou de soufre; M représente des ions de cuivre, fer, cobalt, nickel, zinc, aluminium ou un mélange de ceux-ci. Cette invention se rapporte également à un procédé de préparation d'un tel catalyseur. Un tel catalyseur peut être utilisé dans des réactions d'estérification à basse température et à température relativement élevée.
PCT/CN1996/000068 1996-01-08 1996-08-15 Catalyseur d'esterification et procede pour sa preparation WO1997025144A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU67313/96A AU6731396A (en) 1996-01-08 1996-08-15 An esterification catalyst and a process for its preparation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN 96118004 CN1136470A (zh) 1996-01-08 1996-01-08 一种酯化反应催化剂及其制备方法
CN96118004.8 1996-01-08

Publications (1)

Publication Number Publication Date
WO1997025144A1 true WO1997025144A1 (fr) 1997-07-17

Family

ID=5124706

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN1996/000068 WO1997025144A1 (fr) 1996-01-08 1996-08-15 Catalyseur d'esterification et procede pour sa preparation

Country Status (3)

Country Link
CN (1) CN1136470A (fr)
AU (1) AU6731396A (fr)
WO (1) WO1997025144A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6463120B1 (en) * 2001-02-01 2002-10-08 Forintek Canada Corp. X-ray measurement of resin distribution in a cellulosic material
CN111807957A (zh) * 2020-07-02 2020-10-23 深圳飞扬兴业科技有限公司 一种乙酸香叶酯的合成方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1061901C (zh) * 1997-03-12 2001-02-14 厦门大学 一种生产乙酸正丁酯的负载型固体酸催化剂
CN102962098B (zh) * 2012-11-16 2018-04-27 北京石油化工学院 用于合成醋酸仲丁酯的催化剂及其制备方法
CN104230708B (zh) * 2014-10-10 2015-12-09 徐震霖 一种甲酸甲酯的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179402A (en) * 1978-05-15 1979-12-18 Shell Oil Company Resin-metal-ligand composition
US4414410A (en) * 1982-01-13 1983-11-08 Texaco Inc. Process for preparing alkyl esters by homologation of the next lower alkyl ester
US4939292A (en) * 1985-08-01 1990-07-03 Phillips Petroleum Company Synthesis of esters from alcohols containing carbon monoxide as an impurity
US5241106A (en) * 1991-10-22 1993-08-31 Mitsui Toatsu Chemicals, Inc. Process for producing ethyl acetate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179402A (en) * 1978-05-15 1979-12-18 Shell Oil Company Resin-metal-ligand composition
US4414410A (en) * 1982-01-13 1983-11-08 Texaco Inc. Process for preparing alkyl esters by homologation of the next lower alkyl ester
US4939292A (en) * 1985-08-01 1990-07-03 Phillips Petroleum Company Synthesis of esters from alcohols containing carbon monoxide as an impurity
US5241106A (en) * 1991-10-22 1993-08-31 Mitsui Toatsu Chemicals, Inc. Process for producing ethyl acetate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6463120B1 (en) * 2001-02-01 2002-10-08 Forintek Canada Corp. X-ray measurement of resin distribution in a cellulosic material
CN111807957A (zh) * 2020-07-02 2020-10-23 深圳飞扬兴业科技有限公司 一种乙酸香叶酯的合成方法

Also Published As

Publication number Publication date
CN1136470A (zh) 1996-11-27
AU6731396A (en) 1997-08-01

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