WO1997025144A1 - Catalyseur d'esterification et procede pour sa preparation - Google Patents
Catalyseur d'esterification et procede pour sa preparation Download PDFInfo
- 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
Links
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
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 |
---|---|---|---|
CN96118004.8 | 1996-01-08 | ||
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 |
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)
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)
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 |
CN105013539B (zh) * | 2014-10-10 | 2017-04-19 | 徐震霖 | 一种制备甲酸甲酯的固相催化剂及其制备方法和应用 |
Citations (4)
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 |
-
1996
- 1996-01-08 CN CN 96118004 patent/CN1136470A/zh active Pending
- 1996-08-15 WO PCT/CN1996/000068 patent/WO1997025144A1/fr active Application Filing
- 1996-08-15 AU AU67313/96A patent/AU6731396A/en not_active Abandoned
Patent Citations (4)
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)
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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