WO2017012244A1 - 一种低级脂肪羧酸烷基酯的生产方法 - Google Patents

一种低级脂肪羧酸烷基酯的生产方法 Download PDF

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WO2017012244A1
WO2017012244A1 PCT/CN2015/096646 CN2015096646W WO2017012244A1 WO 2017012244 A1 WO2017012244 A1 WO 2017012244A1 CN 2015096646 W CN2015096646 W CN 2015096646W WO 2017012244 A1 WO2017012244 A1 WO 2017012244A1
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catalyst
molecular sieve
carbon monoxide
dimethyl ether
reaction
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English (en)
French (fr)
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刘红超
朱文良
倪友明
刘勇
刘中民
王林英
田鹏
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中国科学院大连化学物理研究所
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Priority to US15/743,904 priority Critical patent/US10087135B2/en
Priority to EP15898800.6A priority patent/EP3326994B1/en
Priority to JP2018502127A priority patent/JP6523550B2/ja
Priority to AU2015403142A priority patent/AU2015403142B2/en
Priority to CA2993146A priority patent/CA2993146C/en
Priority to PL15898800T priority patent/PL3326994T3/pl
Priority to BR112018001168-1A priority patent/BR112018001168B1/pt
Priority to EA201890299A priority patent/EA035233B1/ru
Publication of WO2017012244A1 publication Critical patent/WO2017012244A1/zh
Priority to ZA2018/00636A priority patent/ZA201800636B/en

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    • 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
    • C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds

Definitions

  • the present invention relates to a process for the carbonylation of lower alkyl ethers to produce lower carboxylic acid esters and derivatives thereof, and more particularly to a process for the carbonylation of dimethyl ether to produce methyl acetate and its derivatives acetic acid.
  • ethanol has good mutual solubility. It can be blended into gasoline as a blending component, partially replaces gasoline, and increases the octane number and oxygen content of gasoline, effectively promoting the full combustion of gasoline. Reduce carbon monoxide and hydrocarbon emissions from vehicle exhaust. As a partial substitute for vehicle fuel, ethanol can make China's vehicle fuels have diverse structural characteristics. At present, China mainly develops fuel ethanol from grain, especially corn. It has become the third largest producer and consumer of fuel ethanol in Brazil and the United States. However, according to China's national conditions, there are many disadvantages in using ethanol as raw material for ethanol production. Factors, the future development of China's fuel ethanol is more non-food routes.
  • the process route of coal-to-ethanol is mainly divided into two types: one is that the synthesis gas directly produces ethanol, but the noble metal ruthenium catalyst is required, the cost of the catalyst is high and the yield of ruthenium is limited; the second is that the synthesis gas is hydrogenated by acetic acid to produce ethanol.
  • the synthesis gas is first subjected to liquid phase carbonylation of methanol to acetic acid, and then hydrogenated to synthesize ethanol. This route is mature, but the equipment needs special alloys that are resistant to corrosion and the cost is high.
  • Wegman J Chem Soc Chem Comm 1994, (8), 947-948 carried out dimethyl ether carbonylation with heteropoly acid RhW 12 P0 4 /SiO 2 as a catalyst.
  • the yield of methyl acetate was 16 %, almost no other by-products are generated.
  • 2002 Russia's Volkova et al. (Catalysis Letters 2002, 80(3-4), 175-179) used Rh-modified rhodium-phosphorus heteropolyacid salt for the carbonylation of dimethyl ether.
  • the reaction rate of this catalyst is higher than that of Wegman.
  • the RhW 12 P0 4 /Si0 2 reaction rate is an order of magnitude higher.
  • U.S. Patent No. 2007,238,897 discloses molecular sieves having an eight-membered ring structure, such as MOR, FER and OFF, as ether carbonylation catalysts, and the size of the eight-membered ring channel is greater than 0.25 x 0.36 nm, with mordenite as a catalyst, 165
  • the space-time yield of 0.163-MeOAc(g-Cat.h) -1 was obtained under the conditions of °C and 1 MPa.
  • Patent WO2008132450A1 (2008) reports that copper and silver modified MOR catalysts have better performance than unmodified MOR catalysts in a hydrogen atmosphere at 250-350 °C.
  • Patent WO2009081099A1 discloses that the MOR carbonylation properties of small grains are superior to the carbonylation properties of large particle size MOR catalysts.
  • Patent WO2010130972A2 discloses a desiliconization, dealumination-treated MOR catalyst which can significantly improve the activity and reaction stability of the MOR catalyst by optimizing the combination of acid treatment and alkali treatment of MOR.
  • CN 103896769 A discloses a process for the carbonylation of dimethyl ether to produce methyl acetate, wherein mordenite and/or ferrierite molecular sieves are used as catalysts;
  • CN101903325A discloses a carbonylation of acetic acid and/or methyl acetate.
  • CN101687759 A discloses a methyl ether carbonylation process using a zeolite having a MOR, FER, OFF, GME framework structure, such as mordenite, ferrierite, and zeolitic zeolite ,Sodium chabazite;Wang Donghui ("Application of a Co-crystallized Molecular Sieve Catalyst in Carbonylation of Dimethyl Ether to Methyl Acetate", Chemical Production and Technology, Vol. 20, No. 3, 2013, pp.
  • a co-crystallized molecular sieve catalyst for the carbonylation of dimethyl ether to methyl acetate.
  • the catalyst is a BEA/MOR 2-phase co-crystal molecular sieve catalyst, and in the first paragraph, EMT/FAU 2-phase co-crystallization is mentioned.
  • Molecular sieves but not for the carbonylation of dimethyl ether to methyl acetate.
  • CN102950018A discloses data on the carbonylation of dimethyl ether on a rare earth ZSM-35/MOR eutectic molecular sieve.
  • CN101613274A utilizes a pyridine-based organic amine modified mordenite molecular sieve catalyst, and it is found that the modification of the molecular sieve can greatly improve the stability of the catalyst.
  • the conversion of dimethyl ether was 10-60%, the selectivity of methyl acetate was greater than 99%, and the activity of the catalyst remained stable after 48 hours of reaction.
  • Shen Wenjie et al. (Catal. Lett. 2010, 139: 33-37) compared the reactivity of methyl carbonyl carbonylation of dimethyl and ZSM-35 catalysts and found that ZSM-35 molecular sieve has better reaction stability.
  • the inventors have found that the lower alkyl ether carbonylation reaction is a typical acid catalyzed reaction, and the acidity and pore structure of the catalyst have a decisive influence on the catalytic performance of the catalyst.
  • EMT As a zeolite superior to the FAU topology, it has strong acidity and a large amount of acid. At the same time, EMT has two sets of mutually intersecting cavities connected by 2-dimensional cross-channels, and its superior pore connectivity is more conducive to the adsorption of reactants and the diffusion of product molecules.
  • the present invention provides a process for producing a fatty acid alkyl ester of the formula R 1 -COO-R 2 , which comprises reacting an alkyl ether of the formula R 1 -OR 2 with a carbon monoxide-containing feed gas as a catalyst The carbonylation reaction is carried out in the presence of an acidic EMT zeolite molecular sieve, wherein R 1 and R 2 each independently represent a C 1 - C 4 alkyl group.
  • R 1 and R 2 are each independently CH 3 -, CH 3 CH 2 -, CH 3 (CH 2 ) 2 -, (CH 3 ) 2 CH-, CH 3 (CH 2 ) 3 - or (CH) 3 ) 3 CH-; more preferably, both R 1 and R 2 are CH 3 -.
  • the acidic EMT zeolite molecular sieve has a silicon to aluminum atomic molar ratio of from 1.5 to 30, preferably from 2 to 15.
  • the acidic EMT zeolite molecular sieve further comprises one or more of gallium, iron, copper and silver as a cocatalyst; preferably, the cocatalyst is synthesized by in situ, metal ion exchange or impregnation
  • the support is introduced into the acidic EMT zeolite molecular sieve; more preferably, the promoter is contained in an amount of from 0.01 to 10.0% by weight based on the total mass of the catalyst.
  • the acidic EMT zeolite molecular sieve further comprises one or more selected from the group consisting of alumina, silica, and magnesia as a binder; preferably, based on the total weight of the catalyst, The content of the binder is 0 to 50% by weight.
  • the fatty acid alkyl ester is further hydrolyzed to produce the corresponding carboxylic acid, preferably the corresponding carboxylic acid is acetic acid.
  • the fatty acid alkyl ester is further hydrogenated to produce the corresponding alcohol, preferably the corresponding alcohol is ethanol.
  • the carbon monoxide-containing feed gas comprises carbon monoxide, hydrogen, and an inert gas selected from any one or more of nitrogen, helium, argon, carbon dioxide, methane, and ethane; preferably, Based on the total volume of the carbon monoxide-containing feed gas, the volume content of carbon monoxide is 50 to 100%, the volume content of hydrogen is 0 to 50%, and the volume of inert gas is 0 to 50%.
  • the carbonylation reaction is carried out at a temperature of from 170 ° C to 240 ° C and a pressure of from 1 to 15 MPa.
  • the carbonylation reaction is carried out in a fixed bed reactor, a fluidized bed reactor or a moving bed reactor.
  • the invention provides a novel method for producing lower fatty acid alkyl esters, in particular a new method for producing methyl acetate.
  • the method is carried out in the presence of acidic EMT zeolite molecular sieve as a catalyst, and has high reactivity and stability, and the stability is remarkably improved. Can meet the needs of industrial production.
  • the present invention provides an alkyl ether (R 1 -OR 2 ) and a carbon monoxide (CO)-containing raw material on a catalyst of an acidic EMT topology zeolite molecular sieve, preferably under anhydrous or trace water conditions, for carbonylation reaction a method for synthesizing a fatty acid alkyl ester (R 1 -COO-R 2 ) wherein R 1 and R 2 each independently represent a C 1 -C 4 alkyl group, for example, independently CH 3 -, CH 3 CH 2 -, CH 3 (CH 2 ) 2 -, (CH 3 ) 2 CH-, CH 3 (CH 2 ) 3 - or CH 3 ) 3 CH-.
  • lower fatty acid alkyl ester refers to a fatty acid alkyl ester represented by the formula R 1 -COO-R 2 wherein R 1 and R 2 each independently represent a C 1 -C 4 alkyl group.
  • the present invention provides a process for the production of methyl acetate by carbonylation of dimethyl ether and carbon monoxide over a catalyst of an acidic EMT topology zeolite molecular sieve.
  • the acidic EMT zeolite molecular sieve used in the present invention has a silicon to aluminum atomic molar ratio of from 1.5 to 30, more preferably from 2 to 15.
  • the acidic EMT molecular sieve used in the present invention comprises one or more of gallium, iron, copper, and silver as a cocatalyst (which may be in the form of a metal element or a compound thereof such as a metal oxide), for example, the auxiliary
  • a cocatalyst which may be in the form of a metal element or a compound thereof such as a metal oxide
  • the introduction method of the catalyst can be carried out in situ synthesis, metal ion exchange or impregnation loading.
  • the cocatalyst is present in an amount of from 0.01 to 10.0% by weight, based on the total weight of the catalyst.
  • the acidic EMT topology zeolite molecular sieve used in the present invention contains a binder, preferably one or more of alumina, silica and magnesia.
  • the binder is present in an amount of from 0 to 50% by weight based on the total weight of the catalyst.
  • the carbon monoxide-containing feed gas used in the present invention comprises carbon monoxide, hydrogen, and an inert gas selected from any one or more of nitrogen, helium, argon, carbon dioxide, methane, and ethane; preferably, based on The total volume of the carbon monoxide-containing feed gas, the volume content of carbon monoxide is 50 to 100%, the volume content of hydrogen is 0 to 50%, and the volume content of the inert gas is 0 to 50%.
  • the alkyl ether used in the present invention is dimethyl ether, and the fatty acid alkyl ester obtained after the carbonylation reaction is methyl acetate.
  • the fatty acid alkyl ester synthesized by the method of the present invention can be further hydrolyzed to produce the corresponding carboxylic acid, for example, by hydrolyzing the methyl acetate obtained above to produce acetic acid.
  • the carbon monoxide-containing feed gas used in the present invention may further comprise any one or any of hydrogen and an inert gas, wherein the inert gas may be nitrogen, helium, argon, carbon dioxide, methane and ethane. Any one or any of several.
  • the inert gas may be nitrogen, helium, argon, carbon dioxide, methane and ethane. Any one or any of several.
  • the carbonylation reaction temperature in the present invention is from 170 ° C to 240 ° C; and the pressure is from 1 to 15 MPa.
  • the carbonylation reaction in the present invention is carried out in a fixed bed reactor, a fluidized bed reactor or a moving bed reactor.
  • the molar ratio of dimethyl ether to carbon monoxide in the carbonylation reaction is in the range of 1:20 to 1:0.5.
  • the conversion of the alkyl ether (represented by dimethyl ether) and the selectivity of the lower fatty acid alkyl ester (represented by methyl acetate) are calculated based on the moles of carbon of dimethyl ether:
  • Methyl acetate selectivity (2/3) ⁇ (methyl moles of methyl acetate in the product) ⁇ [(mole of dimethyl ether carbon in the feed gas) - (moles of dimethyl ether carbon in the product) ] ⁇ (100%)
  • the four Na-EMTs with a silicon-aluminum atomic molar ratio of 2, 4, 15 and 25, respectively, and the Na-EMT with a molar ratio of silicon to silicon of 4, both Ga and Fe, are produced and supplied by the Dalian Institute of Chemical Physics.
  • a supported M/EMT catalyst was prepared by an equal volume impregnation method. 4.32 g of Fe(NO 3 ) 3 , 4.32 g of Cu(NO 3 ) 2 .3H 2 O and 3.04 g of AgNO 3 .3H 2 O were respectively dissolved in 18 ml of deionized water to prepare a corresponding aqueous nitrate solution. 20 g of 2#H-EMT zeolite molecular sieve catalyst was separately added to the above aqueous nitrate solution, allowed to stand for 24 hours, then separated, washed with deionized water, and the obtained sample was dried in an oven at 120 ° C for 12 hours, and the dried sample was placed in a horse. In the furnace, the temperature was raised to 550 ° C at a heating rate of 2 ° C / min, and calcined for 4 h to prepare 7 #, 8 #, 9 # catalyst, respectively.
  • 10 g of this catalyst was placed in a fixed-bed reactor with a tube inner diameter of 28 mm, and the temperature was raised to 550 ° C at 5 ° C/min under a nitrogen atmosphere. After maintaining for 4 hours, it was then lowered to the reaction temperature in a nitrogen atmosphere, and the pressure of the reaction system was raised to 5 MPa with CO at a reaction temperature of 190 °C.
  • the dimethyl ether feed has a space velocity of 0.10 h -1 , a molar ratio of dimethyl ether to carbon monoxide of 1:6, and a catalytic reaction run time under a molar ratio of carbon monoxide to hydrogen in a raw material gas of carbon monoxide of 2:1.
  • the results of (TOS) of 1, 50 and 100 hours are shown in Table 1.
  • reaction temperature was 230 ° C
  • reactors were a fluidized bed reactor and a moving bed reactor, respectively, and the other conditions were the same as in Example 1.
  • the reaction results are shown in Table 8.
  • R1 and R2 groups are the same and non-methyl. Other conditions are the same as in Example 1, and the results are shown in Table 9.
  • the carbonylation product methyl acetate was hydrolyzed to form acetic acid in the presence of a hydrolysis catalyst, the water-ester ratio was 4, the methyl acetate space velocity was 0.4 h -1 , and the catalyst loading was 10 g.
  • the reaction results are shown in Table 10.
  • the methylation product methyl acetate is hydrogenated to form ethanol in the presence of a hydrogenation catalyst at a pressure of 5.5 MPa, the molar ratio of hydrogen to methyl acetate in the feed gas is 20:1, and the molar ratio of hydrogen to carbon monoxide is 20:1.
  • the space velocity of methyl acetate was 3 h -1 and the catalyst loading was 10 g.
  • the reaction results are shown in Table 11.

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Abstract

本发明提供一种低级脂肪羧酸烷基酯的生产方法，所述方法包括将一种烷基醚(R1-O-R2)与含有一氧化碳(CO)的原料气在酸性EMT沸石分子筛的催化剂上进行羰基化反应，得到脂肪酸烷基酯(R1-COO-R2)，其中R1和R2分别独立地表示C1-C4烷基基团。本发明提供了一种生产低级脂肪酸烷基酯的新方法，该方法在作为催化剂的酸性EMT沸石分子筛存在下进行，反应活性高，稳定性得以显著提高，能够满足工业生产的需求。

Description

一种低级脂肪羧酸烷基酯的生产方法 技术领域
本发明涉及一种低级烷基醚羰基化生产低级羧酸酯及其衍生物的方法，特别涉及二甲醚羰基化生产乙酸甲酯及其衍生物乙酸的方法。
背景技术
随着现代工业的迅速发展，能源供需矛盾日趋突出。我国作为能源消费大国，同时又是能源短缺大国，迫切需要寻找可替代能源。乙醇作为一种清洁能源，具有很好的互溶性，可以作为调合组分掺混到汽油中，部分地替代汽油，并提高汽油的辛烷值及含氧量，有效促进汽油的充分燃烧，减少汽车尾气中一氧化碳、烃类的排放量。乙醇作为车用燃料的部分替代品，可使我国的车用燃料呈现多元化的结构特征。目前我国主要以粮食，尤其是玉米为原料发展燃料乙醇，已成为仅次于巴西、美国的第三大燃料乙醇生产和消费国，但根据我国国情，以粮食为原料进行乙醇生产存在诸多的不利因素，未来我国燃料乙醇发展更多的是非粮食路线。
从煤炭资源出发，经合成气生产乙醇是我国新型煤化工产业发展的一个重要方向，具有广阔的市场前景。这对煤炭资源清洁利用，缓解石油资源紧缺的矛盾，提高我国能源安全，具有重要的战略意义和深远影响。目前，煤制乙醇的工艺路线主要分为两种：一是合成气直接制乙醇，但需贵金属铑催化剂，催化剂的成本较高并且铑的产量有限；二是合成气经醋酸加氢制乙醇，合成气先经甲醇液相羰基化制乙酸，进而加氢合成乙醇。此路线工艺成熟，但设备需要抗腐蚀的特种合金，成本较高。
以二甲醚为原料，通过羰基化直接合成乙酸甲酯，再加氢制乙醇的路线尚处于研究阶段，但却是很有应用前景的全新路线。1983年Fujimoto(Appl Catal 1983,7(3),361-368)以Ni/AC为催化剂进行二甲醚羰基化气固相反应，在CO/DME摩尔比2.4-4范围内，发现二甲醚能与CO反应生成醋酸甲酯，选择性在80-92％之间，最高收率为20％。在1994年，Wegman(J Chem Soc Chem Comm 1994,(8),947-948)以杂多酸RhW12P04/Si02为催化剂进行二甲醚羰基化反应，乙酸甲酯的收率为16％，几乎没有其他副 产物生成。2002俄罗斯的Volkova等人(Catalysis Letters 2002,80(3-4),175-179)利用Rh修饰铯的磷钨杂多酸盐进行二甲醚的羰基化反应，该催化剂的反应速率比起Wegman的RhW12P04/Si02反应速率高了一个数量级。
2006年Berkeley的Enrique Iglesia研究小组(Angew.Chem,Int.Ed.45(2006)10,1617-1620,J.Catal.245(2007)110,J.Am.Chem.Soc.129(2007)4919)在具有8元环和12元环或10元环的分子筛体系，如Mordenite(丝光沸石)和Ferrierite(镁碱沸石)进行二甲醚的羰基化反应，结果认为在8元环的B酸活性中心上进行了羰基化反应，乙酸甲酯的选择性非常好，达到99％，但二甲醚羰基化活性非常低。
美国专利US2007238897披露了以具有八元环孔道结构的分子筛，比如MOR、FER和OFF作为醚类羰基化催化剂，且八元环孔道的尺寸要大于0.25×0.36nm，在以丝光沸石为催化剂、165℃、1MPa的条件下，获得了0.163-MeOAc(g-Cat.h)-1的时空收率。专利WO2008132450A1(2008)报道了铜、银修饰MOR催化剂，在氢气气氛、250-350℃条件下，其性能明显优于未修饰的MOR催化剂。专利WO2009081099A1披露了小晶粒的MOR羰基化性能要优于大粒径的MOR催化剂的羰基化性能。专利WO2010130972A2披露了一种脱硅脱铝处理的MOR催化剂，通过对MOR进行酸处理和碱处理优化组合，可以显著提高MOR催化剂的活性和反应稳定性。此外，CN103896769 A公开了一种二甲醚羰基化制备乙酸甲酯的方法，其中使用丝光沸石和/或镁碱沸石分子筛作为催化剂；CN101903325A公开了一种生产乙酸和/或乙酸甲酯的羰基化方法，其中以MOR结构类型的分子筛作为催化剂；CN101687759 A公开了一种甲醚羰基化方法，采用具有MOR、FER、OFF、GME框架结构的沸石，具体如丝光沸石、镁碱沸石、菱钾沸石、钠菱沸石；王东辉(“1种共结晶分子筛催化剂在二甲醚羰化制醋酸甲酯中的应用”《化工生产与技术》，2013年第20卷第3期，第14-18页)公开了一种共结晶分子筛催化剂在二甲醚羰化制醋酸甲酯中的应用，所述催化剂为BEA/MOR 2相共结晶分子筛催化剂，在第一段提及了EMT/FAU 2相共结晶分子筛，但未用于二甲醚羰基化至乙酸甲酯。CN102950018A披露了二甲醚在稀土ZSM-35/MOR共晶分子筛上羰基化反应上的数据。其结果显示共晶分子筛在活性和稳定性方面明显优于单独 使用ZSM-35时的活性和稳定性，稳定性明显优于单独使用MOR催化剂时的稳定性。徐龙伢等(RSC Adv.2013，3:16549-16557)又报道了经碱处理ZSM-35的二甲醚羰基化的反应性能。其结果显示ZSM-35经碱处理后具有明显具有介孔结构，提高了反应物和产物在催化剂上的扩散效果，相应地改善了催化剂的稳定性和活性。
CN101613274A利用吡啶类有机胺改性丝光沸石分子筛催化剂，发现分子筛的改性可以大幅度提高催化剂的稳定性。二甲醚的转化率10-60％，乙酸甲酯选择性大于99％，并在反应48小时后催化剂活性保持稳定。申文杰等(Catal.Lett.2010,139:33-37)对比研究了MOR和ZSM-35催化剂上二甲醚羰基化之乙酸甲酯反应活性的差别，发现ZSM-35分子筛具有更佳的反应稳定性和产物选择性，在250℃、1MPa，DME/CO/N2/He＝5/50/2.5/42.5，12.5ml/min的反应条件，二甲醚转化率达11％，乙酸甲酯选择性达到96％。
上述文献公开了大量二甲醚羰基化研究结果，其催化剂主要集中在具有八元环结构的MOR、FER等。在公开报道的结果中催化剂稳定运行小于100小时，极易失活，并且相关结果不能够满足工业生产的需求。
发明内容
本发明的目的是提供一种新的生产低级脂肪酸烷基酯的方法。
本发明人发现，低级烷基醚羰基化反应是典型的酸催化反应，催化剂的酸性以及孔结构对催化剂的催化性能具有决定性的影响。EMT沸石属于六方晶系，空间群为P63/mmc，晶胞参数a＝b1.7374nm，c＝2.8365nm，骨架密度为12.9T/nm3。其骨架结构是由12元环、6元环和4元环组成，是八面沸石FAU的一个简单的六方类似物。作为一种优于FAU拓扑结构的沸石，具有较强的酸性和较多的酸量。同时，EMT具有两套相互交叉的孔腔，这些孔腔由2维交叉孔道相连，其优越的孔道连接性更有利于反应物的吸附和产物分子的扩散。
基于此，本发明提供一种生产式R1-COO-R2的脂肪酸烷基酯的方法，所述方法包括将式R1-O-R2的烷基醚与含一氧化碳的原料气在作为催化剂的酸性EMT沸石分子筛存在下进行羰基化反应，其中R1和R2分别独立 地表示C1～C4烷基基团。优选地，R1和R2分别独立地为CH3-、CH3CH2-、CH3(CH2)2-、(CH3)2CH-、CH3(CH2)3-或(CH3)3CH-；更优选地，R1和R2均为CH3-。
在一个优选实施方案中，所述酸性EMT沸石分子筛中的硅铝原子摩尔比为1.5～30，优选地为2-15。
在一个优选实施方案中，所述酸性EMT沸石分子筛还包含镓、铁、铜和银中的一种或几种作为助催化剂；优选地，所述助催化剂通过原位合成、金属离子交换或浸渍担载引入到所述酸性EMT沸石分子筛中；更优选地，基于催化剂的总重量，所述助催化剂以金属单质计的含量为0.01～10.0wt％。
在一个优选实施方案中，所述酸性EMT沸石分子筛还包含选自氧化铝、二氧化硅和氧化镁中的一种或多种作为粘结剂；优选地，基于所述催化剂的总重量，所述粘结剂的含量为0～50wt％。
在一个优选实施方案中，所述脂肪酸烷基酯被进一步水解以生产对应的羧酸，优选地所述对应的羧酸为乙酸。
在一个优选实施方案中，所述脂肪酸烷基酯被进一步加氢还原以生产对应的醇，优选地所述对应的醇为乙醇。
在一个优选实施方案中，所述含一氧化碳的原料气包含一氧化碳、氢气以及选自氮气、氦气、氩气、二氧化碳、甲烷和乙烷中的任意一种或几种的惰性气体；优选地，基于所述含一氧化碳的原料气的总体积，一氧化碳的体积含量为50～100％，氢气的体积含量为0～50％，惰性气体的体积含量为0～50％。
在一个优选实施方案中，所述羰基化反应在170℃-240℃的温度和1-15MPa的压力下进行。
在一个优选实施方案中，所述羰基化反应在固定床反应器、流化床反应器或移动床反应器中进行。
本发明提供了一种生产低级脂肪酸烷基酯的新方法，特别是生产乙酸甲酯的新方法，该方法在作为催化剂的酸性EMT沸石分子筛存在下进行，反应活性高，稳定性得以显著提高，能够满足工业生产的需求。
具体实施方式
本发明提供一种烷基醚(R1-O-R2)与含有一氧化碳(CO)的原料在酸性EMT拓扑结构沸石分子筛的催化剂上，优选在无水或含有微量水的条件下，进行羰基化反应，合成得到脂肪酸烷基酯(R1-COO-R2)的方法，其中R1和R2分别独立地表示C1-C4烷基基团，例如分别独立地为CH3-、CH3CH2-、CH3(CH2)2-、(CH3)2CH-、CH3(CH2)3-或CH3)3CH-。
在本文中，术语“低级脂肪酸烷基酯”是指式R1-COO-R2表示的脂肪酸烷基酯，其中R1和R2分别独立地表示C1-C4烷基基团。
在一个特定实施方式中，本发明提供一种通过二甲醚和一氧化碳在酸性EMT拓扑结构沸石分子筛的催化剂上进行羰基化反应而生产乙酸甲酯的方法。
优选地，本发明使用的酸性EMT沸石分子筛中的硅铝原子摩尔比为1.5-30，更优选为2-15。
优选地，本发明使用的酸性EMT分子筛包含镓、铁、铜、银中的一种或几种作为助催化剂(其可以为金属单质或其化合物如金属氧化物的形式)，例如，所述助催化剂的引入方法可以原位合成、金属离子交换或浸渍担载。优选地，基于催化剂的总重量，所述助催化剂的含量为0.01～10.0wt％。
优选地，本发明使用的酸性EMT拓扑结构沸石分子筛含有粘结剂，该粘结剂优选为氧化铝、二氧化硅和氧化镁中的一种或多种。优选地，所述粘结剂的含量为催化剂总重量的0～50wt％。
优选地，本发明使用的含一氧化碳的原料气包含一氧化碳、氢气以及选自氮气、氦气、氩气、二氧化碳、甲烷和乙烷中的任意一种或几种的惰性气体；优选地，基于所述含一氧化碳的原料气的总体积，一氧化碳的体积含量为50～100％，氢气的体积含量为0～50％，惰性气体的体积含量为0～50％。
优选地，本发明使用的烷基醚为二甲醚，并且羰基化反应后得到的脂肪酸烷基酯为乙酸甲酯。
优选地，通过本发明的方法合成的脂肪酸烷基酯可以进一步水解以生产对应的羧酸，例如，水解上述得到的乙酸甲酯而可以生产乙酸。
优选地，本发明使用的含一氧化碳的原料气还可以包含氢气和惰性气体中的任意一种或任意几种，其中的惰性气体可以是氮气、氦气、氩气、二氧化碳、甲烷和乙烷中的任意一种或任意几种。
优选地，本发明中的羰基化反应温度为170℃-240℃；压力为1-15MPa。
优选地，本发明中的羰基化反应在固定床反应器、流化床反应器或移动床反应器中进行。
此外，尽管无需特别限制，但优选羰基化反应中，二甲醚和一氧化碳的摩尔比在1:20～1:0.5的范围。
实施例
以下通过一些实施例对本发明做出详细表述，但本发明并不局限于这些实施例。
实施例中，烷基醚(以二甲醚为代表)的转化率和低级脂肪酸烷基酯(以乙酸甲酯为代表)的选择性都基于二甲醚的碳摩尔数进行计算:
二甲醚的转化率＝[(原料气中的二甲醚碳摩尔数)－(产物中的二甲醚碳摩尔数)]÷(原料气中的二甲醚碳摩尔数)×(100％)
乙酸甲酯的选择性＝(2/3)×(产物中的乙酸甲酯碳摩尔数)÷[(原料气中的二甲醚碳摩尔数)－(产物中的二甲醚碳摩尔数)]×(100％)
硅铝原子摩尔比分别为2、4、15和25的四种Na-EMT以及硅铝原子摩尔比为4的骨架含Ga、Fe的Na-EMT均由大连化学物理研究所生产和提供。
催化剂制备例
H-EMT催化剂
分别将100克焙烧好的硅铝原子摩尔比分别为2、4、15和25的Na-EMT沸石分子筛用0.5mol/L硝酸铵交换三次，每次2小时，用去离子水洗涤，干燥，在550℃焙烧4小时，经挤压分别制备得到20-40目的1#、2#、3#和4#催化剂。
Ga-EMT催化剂
将100克焙烧好的含镓的Na-EMT沸石分子筛(硅铝原子摩尔比为4)用0.5mol/L硝酸铵交换三次，每次2小时，用去离子水洗涤，干燥，在550℃焙烧4小时，经挤压制备得到20-40目的5#催化剂。
Fe-EMT催化剂
将100克焙烧好的含铁的Na-EMT沸石分子筛(硅铝原子摩尔比为4)用0.5mol/L硝酸铵交换三次，每次2小时，用去离子水洗涤，干燥，在550℃焙烧4小时，经挤压制备得到20-40目的6#催化剂。
负载型M/EMT催化剂
采用等体积浸渍法制备负载型M/EMT催化剂。分别将4.32g Fe(NO3)3、4.32g Cu(NO3)2·3H2O和3.04g AgNO3·3H2O溶于18ml去离子水中配成相应的硝酸盐水溶液。将20g 2#H-EMT沸石分子筛催化剂分别加入上述硝酸盐水溶液中，静置24小时，然后经分离，去离子水洗涤，所得样品在120℃烘箱中干燥12小时，干燥后的样品置于马弗炉中，以2℃/min的升温速率升温到550℃，焙烧4h，分别制备得到7#、8#、9#催化剂。
离子交换型M-EMT催化剂
将20g 2#H-EMT沸石分子筛催化剂和300ml 0.15mol硝酸铁水溶液置入烧瓶，在80℃，冷却回流的条件下下搅拌处理2小时，固液比1:15。过滤分离，去离子水洗涤，重复上述步骤2次，120℃干燥12小时，干燥后样品置于马弗炉中，以2℃/min的升温速率升温到550℃，焙烧4h，得到10#催化剂。
H-EMT催化剂成型
取80g硅铝原子摩尔比为4的Na-EMT、28g拟薄水铝石与10％稀硝酸混合均匀后挤条成型，在550℃焙烧4小时，用0.5mol/L硝酸铵交换三次(2小时/次)，用去离子水洗涤，干燥，在550℃焙烧4小时，制得11#催化剂。
取80g硅铝原子摩尔比为4的Na-EMT、20g氧化镁与10％稀硝酸混合均匀后挤条成型，在550℃焙烧4小时，用0.5mol/L硝酸铵交换三次，每次2小时，用去离子水洗涤，干燥，在550℃焙烧4小时，制得12#催化剂。
取80g硅铝原子摩尔比为4的Na-EMT、50g硅溶胶与10％稀硝酸混合均匀后挤条成型，在550℃焙烧4小时，用0.5mol/L硝酸铵交换三次，每次2小时，用去离子水洗涤，干燥，在550℃焙烧4小时，制得13#催化剂。
合成例
对比例
以H-MOR(硅铝原子摩尔比Si/Al＝6.7)为对比催化剂，将10g该催化剂装入列管内径为28毫米固定床反应器内，氮气气氛下以5℃/min升温到550℃，保持4小时，然后在氮气气氛下降至反应温度，用CO将反应系统的压力提升至5MPa，反应温度190℃。二甲醚进料空速为0.10h-1、二甲醚和一氧化碳的摩尔比为1:6，一氧化碳的原料气中的一氧化碳和氢气的摩尔比为2:1的条件下，催化反应运行时间(TOS)为1、50和100小时的结果见表1。
表1：对比催化剂的反应结果
反应时间(h) 1 50 100
二甲醚转化率(％) 35.7 23.8 9.8
乙酸甲酯选择性(％) 99.8 78.2 25.3
实施例1
根据表2所示，将10g相应催化剂装入列管内径为28毫米的固定床反应器内，氮气气氛下以5℃/min升温到550℃，保持4小时，然后在氮气氛下降至反应温度190℃，用CO将反应系统的压力提升至5MPa。二甲醚进料空速为0.10h-1；二甲醚和一氧化碳的摩尔比为1:6，一氧化碳的原料气中的一氧化碳和氢气的摩尔比为2:1的条件下，催化反应结果见表 2。
表2：二甲醚羰基化催化剂的评价结果
Figure PCTCN2015096646-appb-000001
TOS:反应运行时间。
实施例2
在不同反应温度下二甲醚羰基化反应结果
将10g 3#催化剂装入列管内径为28毫米固定床反应器内，氮气气氛下以5℃/min升温到550℃，保持4小时，然后在氮气气氛下降至反应温度，用CO将反应系统的压力提升至5MPa。将反应原料自上而下通过催化剂床层。二甲醚进料空速为0.10h-1；一氧化碳和二甲醚的摩尔比为6:1，一氧化碳的原料气中的一氧化碳和氢气的摩尔比为2:1的条件下，催化反应运行100小时的结果见表3。
表3：不同反应温度时二甲醚在H-EMT催化剂上的反应结果
反应温度(℃) 170 200 230 240
二甲醚转化率(％) 15.7 42.1 76.0 87.8
乙酸甲酯选择性(％) 97.8 99.7 94.5 90.4
实施例3
在不同反应压力下二甲醚羰基化反应结果
使用4#催化剂，反应压力分别为1、6、10、15MPa，其它条件同实施例1。在反应运行100小时时，反应结果见表4。
表4：不同反应压力时二甲醚在H-EMT催化剂上的反应结果
反应压力(MPa) 1 6 10 15
二甲醚转化率(％) 18.3 29.3 41.8 52.3
乙酸甲酯选择性(％) 98.7 99.1 99.4 99.8
实施例4
在不同二甲醚空速下二甲醚羰基化反应结果
使用6#催化剂，二甲醚进料空速分别为0.25h-1、1h-1和2h-1，其它条件同实施例1。在反应运行100小时时，反应结果见表5。
表5：不同二甲醚进料空速时二甲醚在H-EMT催化剂上的反应结果
二甲醚进料空速(h-1) 0.25 1 2
二甲醚转化率(％) 18.3 14.3 10.8
乙酸甲酯选择性(％) 99.7 99.1 97.9
实施例5
在不同二甲醚和一氧化碳摩尔比下二甲醚羰基化反应结果
使用6#催化剂，一氧化碳和二甲醚的摩尔比分别为12:1、8:1、4:1和2:1，其它条件同实施例1。在反应运行100小时时，反应结果见表6。
表6：在不同二甲醚和一氧化碳摩尔比率下二甲醚在H-EMT催化剂上的反应结果
一氧化碳/二甲醚摩尔比 1:12 1:8 1:4 1:2
二甲醚转化率(％) 43.6 36.7 18.8 12.3
乙酸甲酯选择性(％) 97.8 98.1 99.5 99.4
实施例6
在含一氧化碳的原料气含有惰性气体下二甲醚羰基化反应结果
使用9#催化剂，二甲醚进料空速为0.1h-1，二甲醚和一氧化碳原料气摩尔比率为1:9，反应温度为190℃时，其它条件同实施例1。在反应运行200小时时，反应结果见表7。
表7：在含一氧化碳的原料气含有惰性气体下二甲醚在H-EMT催化剂上的反应结果
Figure PCTCN2015096646-appb-000002
实施例7
不同反应器类型的反应结果
使用2#催化剂，反应温度为230℃，反应器分别为流化床反应器和移动床反应器，其它条件同实施例1。反应结果见表8。
表8：在不同反应器类型下在H-EMT催化剂上的反应结果
反应器类型 流化床 移动床
二甲醚转化率(％) 89.2 91.5
乙酸甲酯选择性(％) 98.7 98.5
实施例8
在不同于二甲醚的其他烷基醚类反应原料下的反应结果
R1和R2基团相同且非甲基，其它条件同实施例1，反应结果见表9。
表9：反应原料非二甲醚时在H-EMT催化剂上的反应结果
R1 R2 R1-O-R2转化率(％) R-COO-R选择性(％)
CH3CH2- CH3CH2- 30.6 98.2
CH3(CH2)2- CH3(CH2)2- 28.7 97.8
CH3)3CH- CH3)3CH- 26.8 98.8
实施例9
乙酸甲酯水解制备乙酸
羰基化产物乙酸甲酯在水解催化剂存在条件下水解生成乙酸，水酯比为4，乙酸甲酯空速为0.4h-1，催化剂装填量10g，反应结果见表10。
表10乙酸甲酯水解制乙酸反应结果
反应温度(℃) 50 60 70
乙酸甲酯转化率(％) 55.7 72.1 89.0
实施例10
乙酸甲酯加氢制备乙醇
羰基化产物乙酸甲酯在加氢催化剂存在条件下加氢生成乙醇反应，压力5.5MPa,原料气中氢气和乙酸甲酯的摩尔比例为20:1，氢气和一氧化碳的摩尔比为20:1，乙酸甲酯的空速为3h-1，催化剂装填量10g，反应结果见表11。
表11乙酸甲酯加氢制乙醇反应结果
Figure PCTCN2015096646-appb-000003
以上已对本发明进行了详细描述，但本发明并不局限于本文所描述具体实施方式。本领域技术人员理解，在不背离本发明范围的情况下，可以作出其他更改和变形。本发明的范围由所附权利要求限定。

Claims (10)

  1. 一种生产式R1-COO-R2的脂肪酸烷基酯的方法，所述方法包括将式R1-O-R2的烷基醚与含一氧化碳的原料气在载有作为催化剂的酸性EMT沸石分子筛的反应器中进行羰基化反应，其中R1和R2分别独立地表示C1～C4烷基基团。
  2. 如权利要求1所述的方法，其特征在于，所述酸性EMT沸石分子筛的硅铝原子摩尔比为1.5～30，优选地为2-15。
  3. 如权利要求1所述的方法，其特征在于，所述酸性EMT沸石分子筛还包含镓、铁、铜和银中的一种或几种作为助催化剂；优选地，所述助催化剂通过原位合成、金属离子交换或浸渍担载引入到所述酸性EMT沸石分子筛中；更优选地，基于催化剂的总重量，所述助催化剂以金属单质计的含量为0.01～10.0wt％。
  4. 如权利要求1-3中任一项所述的方法，其特征在于，所述酸性EMT沸石分子筛还包含选自氧化铝、二氧化硅和氧化镁中的一种或多种作为粘结剂；优选地，基于所述催化剂的总重量，所述粘结剂的含量为0～50wt％。
  5. 如权利要求1所述的方法，其特征在于，所述R1和R2分别独立地为CH3-、CH3CH2-、CH3(CH2)2-、(CH3)2CH-、CH3(CH2)3-或(CH3)3CH-；优选地，所述R1和R2均为CH3-。
  6. 如权利要求1所述的方法，其特征在于，所述脂肪酸烷基酯被进一步水解以生产对应的羧酸，优选地所述对应的羧酸为乙酸。
  7. 如权利要求1所述的方法，其特征在于，所述脂肪酸烷基酯被进一步加氢还原以生产对应的醇，优选地所述对应的醇为乙醇。
  8. 如权利要求1所述的方法，其特征在于，所述含一氧化碳的原料气包含一氧化碳、氢气以及选自氮气、氦气、氩气、二氧化碳、甲烷和乙烷中的任意一种或几种的惰性气体；优选地，基于所述含一氧化碳的原料气的总体积，一氧化碳的体积含量为50～100％，氢气的体积含量为0～50％，惰性气体的体积含量为0～50％。
  9. 如权利要求1所述的方法，其特征在于，所述羰基化反应在170℃-240℃的温度和1-15MPa的压力下进行。
  10. 如权利要求1所述的方法，其特征在于，所述羰基化反应在固定床反应器、流化床反应器或移动床反应器中进行。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11292761B2 (en) * 2017-09-29 2022-04-05 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for directly producing methyl acetate and/or acetic acid from syngas

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106365995B (zh) * 2015-07-20 2018-06-05 中国科学院大连化学物理研究所 一种乙酸甲酯的生产方法
CN109574798B (zh) * 2017-09-29 2023-10-31 中国科学院大连化学物理研究所 一种合成气直接生产乙醇的方法
WO2020155143A1 (zh) * 2019-02-02 2020-08-06 中国科学院大连化学物理研究所 一种二甲醚羰基化生产乙酸甲酯的方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070238897A1 (en) * 2005-05-05 2007-10-11 The Regents Of The University Of California Process for carbonylation of alkyl ethers
CN101600678A (zh) * 2006-12-15 2009-12-09 加州大学评议会 脂肪醇和/或其反应性衍生物羰基化的方法
CN101613274A (zh) * 2008-06-25 2009-12-30 中国科学院大连化学物理研究所 一种二甲醚羰基化制备乙酸甲酯的方法
CN101903325A (zh) * 2007-12-20 2010-12-01 英国石油化学品有限公司 生产乙酸和/或乙酸甲酯的羰基化方法
CN103896769A (zh) * 2012-12-25 2014-07-02 中国科学院大连化学物理研究所 一种二甲醚羰基化制备乙酸甲酯的方法
CN104725224A (zh) * 2013-12-23 2015-06-24 中国科学院大连化学物理研究所 制备聚甲氧基二甲醚羰化物及甲氧基乙酸甲酯的方法
CN104725229A (zh) * 2013-12-23 2015-06-24 中国科学院大连化学物理研究所 制备聚甲氧基二甲醚羰化物及甲氧基乙酸甲酯的方法
CN104725230A (zh) * 2013-12-23 2015-06-24 中国科学院大连化学物理研究所 制备聚甲氧基二甲醚羰化物及甲氧基乙酸甲酯的方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3606169A1 (de) * 1986-02-26 1987-08-27 Basf Ag Verfahren zur herstellung von essigsaeure, methylacetat und/oder dimethylether
US5218140A (en) * 1988-08-02 1993-06-08 Union Carbide Chemicals & Plastics Technology Corporation Carbonylation reaction and catalyst therefor
JP3965527B2 (ja) * 1995-06-21 2007-08-29 日産化学工業株式会社 ピラゾールのｎ−アルキル化方法
US20060252959A1 (en) * 2005-05-05 2006-11-09 The Regents Of The University Of California Process for carbonylation of alkyl ethers
EP1985606A1 (en) 2007-04-26 2008-10-29 BP Chemicals Limited Process for the carbonylation of dimethyl ether
EP1985607A1 (en) * 2007-04-26 2008-10-29 BP Chemicals Limited Process for the carbonylation of dimethyl ether
EP2251314A1 (en) 2009-05-14 2010-11-17 BP Chemicals Limited Carbonylation process
JP2012131721A (ja) * 2010-12-20 2012-07-12 Tosoh Corp ４，４’−メチレンジアニリンの製造方法
JP2012250971A (ja) * 2011-05-12 2012-12-20 Tosoh Corp 芳香族ポリアミンの製造方法
CN102950018B (zh) 2011-08-26 2014-12-24 中国科学院大连化学物理研究所 用于二甲醚羰基化合成乙酸甲酯的催化剂及其制备方法
CN105899459B (zh) * 2013-11-05 2018-11-09 巴斯夫欧洲公司 具有bea骨架结构的含锡沸石材料
CN106365995B (zh) * 2015-07-20 2018-06-05 中国科学院大连化学物理研究所 一种乙酸甲酯的生产方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070238897A1 (en) * 2005-05-05 2007-10-11 The Regents Of The University Of California Process for carbonylation of alkyl ethers
CN101600678A (zh) * 2006-12-15 2009-12-09 加州大学评议会 脂肪醇和/或其反应性衍生物羰基化的方法
CN101903325A (zh) * 2007-12-20 2010-12-01 英国石油化学品有限公司 生产乙酸和/或乙酸甲酯的羰基化方法
CN101613274A (zh) * 2008-06-25 2009-12-30 中国科学院大连化学物理研究所 一种二甲醚羰基化制备乙酸甲酯的方法
CN103896769A (zh) * 2012-12-25 2014-07-02 中国科学院大连化学物理研究所 一种二甲醚羰基化制备乙酸甲酯的方法
CN104725224A (zh) * 2013-12-23 2015-06-24 中国科学院大连化学物理研究所 制备聚甲氧基二甲醚羰化物及甲氧基乙酸甲酯的方法
CN104725229A (zh) * 2013-12-23 2015-06-24 中国科学院大连化学物理研究所 制备聚甲氧基二甲醚羰化物及甲氧基乙酸甲酯的方法
CN104725230A (zh) * 2013-12-23 2015-06-24 中国科学院大连化学物理研究所 制备聚甲氧基二甲醚羰化物及甲氧基乙酸甲酯的方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CELIK, F.E. ET AL.: "An Investigation into the Mechanism and Kinetics of Dimethoxymethane Carbonylation over FAU and MFI Zeolites", JOURNAL OF CATALYSIS, vol. 274, 2 August 2010 (2010-08-02), pages 150 - 162, XP055347944, ISSN: 0021-9517 *
GAO, DAOWEI ET AL.: "Research Advance on EMT Zeolite Synthesis and Application", CHEMICAL PRODUCTION AND TECHNOLOGY, vol. 19, no. 6, 31 December 2012 (2012-12-31), pages 46 - 50, XP009503663, ISSN: 1006-6829 *
WU, WENBING ET AL.: "Process of Synthesis and Application of Methyl Acetate", JIANGSU CHEMICAL INDUSTRY, vol. 32, no. 5, 31 October 2004 (2004-10-31), XP009503662, ISSN: 1002-1116 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11292761B2 (en) * 2017-09-29 2022-04-05 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for directly producing methyl acetate and/or acetic acid from syngas

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