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WO1997025144A1 - An esterification catalyst and a process for its preparation - Google Patents

An esterification catalyst and a process for its 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
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Prior art keywords
catalyst
metal
copper
cobalt
catalyst according
Prior art date
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PCT/CN1996/000068
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French (fr)
Chinese (zh)
Inventor
Peiyu Jiao
Changli Zhang
Original Assignee
Peiyu Jiao
Changli Zhang
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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/en

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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.

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

Abstract

The present invention relates to an esterification catalyst represented by the following formula: RYO3M wherein R indicates styrene-divinylbenzene copolymer or phenol-formaldehycle resin; Y indicates a phosphorus or sulfur atom; M indicates ions of copper, iron, cobalt, nickel, zinc, aluminium or a mixture thereof. The prsent invention also relates to a process for preparation of said catalyst. Said catalyst can be used in the esterifying reaction at a low and relatively high temperature.

Description

用于酯化反应的催化剂及其制备方法 本发明涉及一种用于醏化反应的催化剂及其制备方法，  The present invention relates to a catalyst for a tritiation reaction and a preparation method thereof.
已知酯化反应催化剂可分为酸性催化剂和非酸性催化剂两大类， 其 中酸性催化剂是目前使用最广泛的催化剂， 如硫酸等， U.S.Pat.2 , 787 , 636； U.S.Pat.2 , 644 , 839等专利文献介绍了硫酸催化剂， 它 具有催化活性高， 与反应物相溶性好， 价格便宜易得等优点. 但同时， 它又有较强的腐蚀性， 并具有氧化脱水的作用， 特别是加热时稳定性差， 容易影响产品色泽， 副产物明显增加， 降低了产品的质量性能. 因而温 度较高的醋化反应一般都采用其他非酸性催化剂， 如钛酸醋、 氧化亚锡 和铝酸钠等， Ger.2， 042 , 402； 特许昭 46 - 6971； 特许昭 47 - 3806等专利文献介绍了钛酸醋类催化剂， 但这些催化剂也存在低温醋化 反应催化活性低， 不能连续使用， 价^"昂贵， 只能用于增塑剂醏类的生 产。 目前工业上大部分醋化反应还是采用疏酸液相催化， 但由于废酸对 环境会造成污染. 因而， 随着环保法规对环境和安全要求的不断提高， 题。
Figure imgf000003_0001
索性研究， 大都致力于固 酸 催化剂的开发， 主要集中在分子筛和超强酸上， 然而这些氧化物固体酸 的低温活性较差， 在较高温度下不仅有副产物生成， 且易失活， 使用寿 命甚短。 而单独用强酸性阳离子交换树脂只能用于 100 以下的酯化反 应。 近年来国内外对杂多酸和固栽杂多酸进行了大量的研究， 虽表现出 优异的催化性能， 但在催化剂回收方面还存在一些问题， 能耗较高， 杂 多酸损失也较大. 固栽杂多酸也存在固栽牢度不稳定和溶脱量大， 反应 溫度较高时有副产物鲢和烯生成， 使醋化反应的选择性降低. It is known that esterification catalysts can be divided into two categories: acidic catalysts and non-acidic catalysts. Among them, 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. Therefore, 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.
Figure imgf000003_0001
Most of the researches are devoted to the development of solid acid catalysts, mainly focusing on molecular sieves and superacids. However, these oxide solid acids have poor low-temperature activity, and not only by-products are formed at higher temperatures, but also easily deactivated. Life is short. The strong acidic cation exchange resin alone can only be used for the esterification reaction below 100. In recent years, a large amount of research has been conducted on heteropoly acids and solid heteropoly acids at home and abroad. Although they show excellent catalytic performance, there are still some problems in catalyst recovery, high energy consumption, and large losses of heteropoly acids. Heteropolyacids also have unstable fastness to solids and a large amount of dissolution. By-products of amidine and ene are formed at higher reaction temperatures, which reduces the selectivity of the vinegarization reaction.
本发明的目的在于提供一种用于酯化反应的催化剂及其制备方法， 它能制取一种催化活性高， 选择性好， 无副反应产生， 可以等克分子进 行反应， 反应性能稳定， 可连续进行多次醋化反应， 既能用于低温醋化， 亦能用于较高温度酯化的新型酯化反应催化剂.  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. Can be used for continuous vinegarization, which can be used for low-temperature vinegarization and higher temperature esterification.
本发明的技术方案为：  The technical solution of the present invention is:
可用于酯化反应的催化 Μ， 其持征 ^伥化剂 ^有下述通式的金 属盐类化合物： -It can be used for the catalysis of esterification reaction. Its characteristics are as follows: Salt compounds:-
RY03M RY0 3 M
式中： R表示笨乙烯-二乙烯笨共聚体或朌^树脂； Y表示一硫原 子或一磷原子； M表示一金属离子如铜， 铁， 钴， 镍， 锌， 铝， 或者其 金属混合离子. 树脂为阳离子交换树脂， 金属离子可从金属盐或金属氧 化物或金属单质获得.  In the formula: R is a stupid ethylene-diethylene stupid 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.
一种用于酯化反应的催化剂的制备方法， 其特征在于它包括： 将阳 离子交换树脂用 10 %硫酸浸泡， 浸泡 6小时至两天， 然后过滤， 用蒸馏 水洗至中性， 再与上述的金属离子混匀， 在 70 - 100 下烘干后备用. 本发明提供的方法工艺流程简单， 操作方便， 无需投入大量的资金 设备， 所制备的催化剂在使用过程中对设备无腐蚀， 蒸残液无碳化现象， 分水顺畅， 分水量可达理论值. 酯化反应可连续或间断进行。 间歇精饰 时无需每釜排尾， 无环境污染， 加热稳定性好， 无副反应产生， 可以等 分子进行反应， 产品的质量性能明显提高， 并且价格低廉， 可用于低 温和较高温度的酯化反应. 在乙酸乙醋、 丁^、 异戊醋和邻笨二甲酸二 乙醋、 二辛酯等酯化反应中， 本催化剂可连续进行多次酯化反应， 催化 活性和选择性明显高于现今使用和研究中的各种酯化反应催化剂 .  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. In the esterification reaction of ethyl acetate, butyl acetate, isoamyl acetate, diethyl acetophenate, dioctyl ester, etc., the catalyst can continuously perform multiple esterification reactions, and the catalytic activity and selectivity are significantly higher. Various esterification catalysts in use and research today.
下面对本发明作详细的说明：  The present invention is described in detail below:
本发明所提供的用于醏化反应的催化剂由阳离子交换树脂和金属 离子组成.  The catalyst for the tritiation reaction provided by the present invention is composed of a cation exchange resin and a metal ion.
以上所述的金属离子选自金属盐类或选自金属氧化物如氧化铜、 氧 化铁； 氧化钴、 氧化镍、 氧化辞、 氧化铝及其混合物或选自金属单质. 优选的金属离子是硤酸盐中的金属离子， 分别可以为硫酸铜、 硫酸 铁、 硫酸钴、 硫酸镍、 硫酸锌、 酸铝， 也可以是硫酸铜与硫酸钴的混 合。  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 硖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.
特别优选的金属离子是金属铜离子.  A particularly preferred metal ion is a metal copper ion.
本发明所提供的方法为： 取阳离子交换树脂用 10 %琉酸浸泡， 浸泡 6小时至两天， 然后过滤， 用蒸馏水洗至中性， 再与上述的金属离子混 ， 在 70 - 100 " 下烘干后备用.  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.
^ 例 1：  ^ Example 1:
取 4公斤强 έ'ί性;^乙烯阳离子交换树脂（由上海树脂厂出售， 商标 732型树脂） 用 6升 10 %硫酸浸泡， 浸泡 24小时， 然后过滤， 用蒸馏 水洗至中性， 再与 400克硫酸铜混匀， 在 70 - 100 下烘干可得到深绿 色的催化剂 2.6公斤. Take 4kg strong; ^ ethylene cation exchange resin (sold by Shanghai Resin Factory, trademark Type 732 resin) Soaked in 6 liters of 10% sulfuric acid, soaked for 24 hours, then filtered, washed with distilled water to neutrality, mixed with 400 g of copper sulfate, and dried at 70-100 to obtain a dark green catalyst 2.6 kg .
实施例 1：  Example 1:
在配置分馏柱和分水器的烧瓶中， 投入乙醇 460克 （ 10克分子）和 乙酸 600克（ 10克分子 ） ， 再加入实施例 1制备的催化剂 10克， 在 80 'C回流反应 1小时， 分水 178克， 制得乙酸乙醋 881.6克， 含量为 96 % , 产品收率为 99.7 %。 继续补加酸和醇可连续反应达 10批以上.  In a flask equipped with a fractionation column and a water separator, 460 g (10 mol) of ethanol and 600 g (10 mol) of acetic acid were added, and then 10 g of the catalyst prepared in Example 1 was added, and the reaction was carried out at 80 ° C under reflux for 1 hour. 178 g of water was separated to obtain 881.6 g of ethyl acetate with a content of 96% and a product yield of 99.7%. Continuous addition of acid and alcohol can continuously react for more than 10 batches.
实施例 3：  Example 3:
取 4公斤强酸性笨乙浠阳离子交换树脂（由上海树脂厂出售， 商标 735型树脂） 用 6升 10 % i¾酸浸泡， 浸泡 24小时， 然后过滤， 用蒸馏 水洗至中性， 再与 400克硫酸铜和 40克硫酸钴混匀， 在 70 - 100 下 烘干可得到深棕绿色的催化剂 2.8公斤.  Take 4 kg of strongly acidic benzamidine cation exchange resin (sold by Shanghai Resin Factory, trademark 735 resin), soak with 6 liters of 10% i¾ acid, soak for 24 hours, then filter, wash with distilled water to neutrality, and then with 400 g Copper sulfate and 40 g of cobalt sulfate are mixed and dried at 70-100 to obtain a dark brown green catalyst of 2.8 kg.
实施例 4：  Example 4:
在 500立升反应器上， 配置回流装置的分馏柱和分水器， 投入异戊 醇 220公斤 （ 2500克分子） 和乙酸 150公斤 （ 2500克分子） , 再加入 实施例 3制备的催化剂量剂 2公斤， 在 140匸回流反应， 分水 45公斤， 制得乙酸异戊醋 325公斤， 含量为 97 % , 产品收率为 100 % . 继续补加 酸和酵可连续反应达 6批以上.  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 匸, 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.
实施例 5：  Example 5:
取 2公斤强酸性笨乙烯阳离子交换树脂（由天津南开大学化工厂出 售， 商标 D001型树脂） 用 3升 10 %硫酸浸泡， 浸泡 24小时， 然后过 滤， 用蒸馏水洗至中性， 再与 40克氧化铜混匀， 在 70 - 100 下烘干 可得到深绿色的催化剂 1.14公斤.  Take 2 kg of strong acid stupid ethylene cation exchange resin (sold by Tianjin Nankai University Chemical Factory, brand D001 resin), soak it with 3 liters of 10% sulfuric acid, soak it for 24 hours, then filter, wash with distilled water to neutrality, and then mix with 40 g Copper oxide is mixed well and dried at 70-100 to obtain 1.14 kg of dark green catalyst.

Claims

权 利 要 求 Rights request
1.可用于酯化反应的催化剂， 其特征是该催化剂为具有下述通式的 金属盐类化合物： 1. A catalyst that can be used in an esterification reaction, characterized in that the catalyst is a metal salt compound having the following general formula:
RY03M RY0 3 M
式中： R表示苯乙晞-二乙烯苯共聚体或酚醛树脂； Y表示一硫原 子或一磷原子； M表示一金属离子， 铜， 铁， 钴， 镍， 锌， 铝， 或者其 金属混合离子.  In the formula: R represents phenethylfluorene-divinylbenzene copolymer or phenol resin; Y represents a sulfur atom or a phosphorus atom; M represents a metal ion, copper, iron, cobalt, nickel, zinc, aluminum, or a mixture of metals thereof Ion.
2.根据权利要求 1所述的催化剂， 其特征在于所述的树脂为阳离子 交换树脂.  The catalyst according to claim 1, characterized in that said resin is a cation exchange resin.
3.根据权利要求 1所述的催化剂， 其特征在于所述的金属离子选自 金属盆或金属氧化物或金属单质.  3. The catalyst according to claim 1, characterized in that the metal ion is selected from a metal basin or a metal oxide or a metal element.
4.根据权利要求 3所述的催化剂， 其特征在于所述的金属盐为砥酸 盐或硝酸盐.  The catalyst according to claim 3, characterized in that said metal salt is a gallate or a nitrate.
5.根据权利要求 4所述的催化剂， 其特征在于所述的琉酸盐为铜， 铁， 钴， 镍， 锌， 铝的硫酸盐及它们的混合物.  5. The catalyst according to claim 4, characterized in that the sulphate is copper, iron, cobalt, nickel, zinc, aluminum sulfate and mixtures thereof.
6.根据权利要求 4所述的催化剂， 其特征在于所述的硝酸盐为铜， 铁， 钴， 镍， 锌， 铝的硝酸盐及它们的混合物.  6. The catalyst according to claim 4, characterized in that said nitrate is a nitrate of copper, iron, cobalt, nickel, zinc, aluminum and mixtures thereof.
7.根据权利要求 3所述的催化剂， 其特征在于所述的金属氧化物为 铜， 铁， 钴， 镍， 锌， 铝的氧化物及它们的混合物.  7. The catalyst according to claim 3, wherein the metal oxide is an oxide of copper, iron, cobalt, nickel, zinc, aluminum and a mixture thereof.
8.根据权利要求 3所述的催化剂， 其特征在于所述的金属单质为 铜， 铁， 钴， 镍， 锌， 铝的单质及它们的混合体.  The catalyst according to claim 3, characterized in that the elemental substance of metal is elemental substance of copper, iron, cobalt, nickel, zinc, aluminum and a mixture thereof.
9.可用于醋化反应的催化剂的制备方法， 其特征在于它包括： 将阳 离子交换树脂用 10 %硫酸浸泡， 然后过滤， 用蒸馏水洗至中性， 再与上 述的金属离子混匀， 在 70 - 100 下烘干后备用.  9. A method for preparing a catalyst that can be used in an acetation reaction, characterized in that it comprises: immersing a cation exchange resin with 10% sulfuric acid, then filtering, washing with distilled water to neutrality, and mixing with the above-mentioned metal ions at 70 -100 spares after drying.
PCT/CN1996/000068 1996-01-08 1996-08-15 An esterification catalyst and a process for its preparation WO1997025144A1 (en)

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CN102962098B (en) * 2012-11-16 2018-04-27 北京石油化工学院 Catalyst for synthesizing sec-Butyl Acetate and preparation method thereof
CN105013539B (en) * 2014-10-10 2017-04-19 徐震霖 Solid phase catalyst for preparing methyl formate, preparation method therefor and application thereof

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