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WO2015095998A1 - Procédé de préparation de composé carbonylé d'éther méthylique de polyoxyméthylène et d'ester méthylique d'acide méthoxyacétique - Google Patents

Procédé de préparation de composé carbonylé d'éther méthylique de polyoxyméthylène et d'ester méthylique d'acide méthoxyacétique Download PDF

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Publication number
WO2015095998A1
WO2015095998A1 PCT/CN2013/090215 CN2013090215W WO2015095998A1 WO 2015095998 A1 WO2015095998 A1 WO 2015095998A1 CN 2013090215 W CN2013090215 W CN 2013090215W WO 2015095998 A1 WO2015095998 A1 WO 2015095998A1
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reaction
molecular sieve
catalyst
dimethyl ether
raw material
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Chinese (zh)
Inventor
倪友明
朱文良
刘勇
刘红超
刘中民
孟霜鹤
李利娜
刘世平
周慧
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
    • 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
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for the preparation of polymethoxy dimethyl ether carbonyl and methyl methoxyacetate as intermediates for the production of ethylene glycol. Background technique
  • Ethylene glycol is an important chemical raw material and strategic material for the manufacture of polyester (which can be used to produce polyester, PET bottles, films), explosives, glyoxal, and as an antifreeze, plasticizer, hydraulic fluid and Solvents, etc.
  • China's ethylene glycol imports exceeded 5.8 million tons. It is estimated that China's ethylene glycol demand will reach 11.2 million tons in 2015, with a production capacity of about 5 million tons, and the supply and demand gap will still reach 6.2 million tons. Therefore, China's ethylene glycol production
  • Internationally, petroleum cracked ethylene is mainly oxidized to obtain epoxy acetamidine, and ethylene epoxide is hydrated to obtain ethylene glycol.
  • coal-based ethylene glycol new coal chemical technology can not only ensure the country's energy security, but also make full use of China's coal resources. It is the most realistic choice for the future coal chemical industry.
  • Polymethoxy dimethyl ether (or polymethoxy acetal, English name Polyoxymethylene dimethyl ethers) has the formula CH 3 0(C3 ⁇ 40) n CH 3 , where n 2 , generally referred to as DMM n (or PODE n :).
  • DMM n or PODE n :
  • DMM 3 ⁇ 4 can be used as a diesel additive.
  • the nature is low. Therefore, it is often necessary to repeatedly separate and react the by-products in the preparation process, so that the energy consumption is large and the economy is poor. Therefore, if the DMM 2 as a by-product can be directly processed into a product with higher economic value, the economics of the process will be improved.
  • An object of the present invention is to provide a process for producing polymethoxy dimethyl ether carbonyl and methyl methoxyacetate as an intermediate for producing ethylene glycol by carbonylation.
  • the present invention provides a process for preparing a polymethoxy dimethyl ether carbonylate as an intermediate for the production of ethylene glycol by carbonylation, characterized in that the starting material polymethoxy dimethyl ether CH 3 0 (CH 2 0) n CH 3 with the same oxidized carbon and hydrogen passing through a reactor carrying a desiliconized modified acidic molecular sieve catalyst at a reaction temperature of 60 to 140 ° C, a reaction pressure of 2 to 10 MPa, polymethoxy dimethyl ether Producing a product polymethoxy dimethyl ether carbonyl by reacting a mass space velocity of O jl O .O h without adding other solvent, wherein at least one of the raw material and the product is under the reaction conditions
  • the desiliconization-modified acidic molecular sieve catalyst is a solid phase, carbon monoxide and hydrogen are in a gas phase to make the reaction process a gas-liquid-solid three-phase reaction, and the molar ratio of carbon
  • the invention also provides a process for preparing methyl methoxyacetate and polymethoxy dimethyl ether carbonyl as an intermediate for producing ethylene glycol by carbonylation, characterized in that the raw material acetal CH 3 0-C3 ⁇ 4 is used.
  • a reactor carrying a desiliconized modified acidic molecular sieve catalyst carrying a desiliconized modified acidic molecular sieve catalyst, at a reaction temperature of 60 to 140 ° C, a reaction pressure of 2 to 10 MPa, and a mass space velocity of methylal of 0.2 to 10.0 h - 1
  • preparing the product methyl methoxyacetate and polymethoxy dimethyl ether carbonyl by reacting without adding other solvent wherein under the reaction conditions, the raw material and the At least one of the products is a liquid phase, the desiliconized modified acidic molecular sieve catalyst is a solid phase, carbon monoxide and hydrogen are in a gas phase such that the reaction process is a gas-liquid-solid three-phase reaction, and carbon monoxide and the raw material are moles.
  • the ratio is 2:1 to 20:1, and the molar ratio of hydrogen to the raw material is 1:1 to 5:1.
  • the product polymethoxy dimethyl ether carbonyl is -0-C3 ⁇ 4-0- in the molecular chain of polymethoxy dimethyl ether CH 3 0(CH 2 0;) n CH 3
  • the polymethoxy dimethyl ether is dipoly methoxy dimethyl ether CH 3 0(C 3 ⁇ 40) 2 CH 3 .
  • the polymethoxy dimethyl ether carbonyl is one or more of the following:
  • the desiliconization-modified acidic molecular sieve catalyst is prepared by adding an acidic molecular sieve to 0.05 to 6.0 mol/L, preferably 0.2 to 1.5 mol/L of sodium hydroxide, potassium hydroxide, lithium hydroxide or magnesium hydroxide.
  • the reaction is carried out at 15 to 95 ° C, preferably 50 to 85 ° C for 0.5 to 24 h, and the filter cake after filtration is 0.01 to 0.01 0.5 mol/L of an aqueous solution selected from hydrochloric acid, nitric acid, sulfuric acid or acetic acid is washed and neutralized to acidity, and then the neutralized salt solution is washed with deionized water, then subjected to ammonium ion exchange, filtration, drying and calcination to obtain The desiliconized modified acidic molecular sieve catalyst.
  • an aqueous solution selected from hydrochloric acid, nitric acid, sulfuric acid or acetic acid is washed and neutralized to acidity, and then the neutralized salt solution is washed with deionized water, then subjected to ammonium ion exchange, filtration, drying and calcination to obtain The desiliconized modified acidic molecular sieve catalyst.
  • the desiliconized modified acidic molecular sieve catalyst is of the structural type MWW, FER, MFI, MOR, FAU or BEA.
  • the desiliconized modified acidic molecular sieve catalyst is one or more of MCM-22 molecular sieve, ferrierite, ZSM-5 molecular sieve, mordenite, Y zeolite or Beta molecular sieve.
  • the reaction temperature is 60 to 120 ° C
  • the reaction pressure is 4 to 10 MPa
  • the mass space velocity of the raw material is 0.5 to 3.0 h - the molar ratio of carbon monoxide to the raw material is 2:1 ⁇ 15:1, the molar ratio of hydrogen to the raw material is 1:1 to 3:1.
  • the reaction temperature is 60 to 90 ° C
  • the reaction pressure is 5 to 10 MPa
  • the mass space velocity of the raw material is 0.5 to 1.5 h - the molar ratio of carbon monoxide to the raw material is 2:1 ⁇ 10:1, the molar ratio of hydrogen to the raw material is 1:1 to 2:1.
  • the reactor is a fixed bed reactor, a tank reactor, a moving bed reactor or a fluidized bed reactor that effects a continuous reaction.
  • the conversion rate of the raw material polymethoxy dimethyl ether or methylal is high, the selectivity of each product is high, the catalyst has a long service life, no external solvent is needed, the reaction condition is mild, and the product can be continuously produced, and has industrial application. potential.
  • the obtained product can be hydrolyzed by hydrogenation or hydrolyzed to produce ethylene glycol.
  • the present invention provides a process for preparing a polymethoxy dimethyl ether carbonyl compound, characterized in that a raw material containing polymethoxy dimethyl ether CH 3 O CH 2 C n CH 3 , carbon monoxide and optionally hydrogen is passed a reactor carrying a desiliconized modified acidic molecular sieve catalyst at a reaction temperature of 60 to 140 ° C, a reaction pressure of 2 to 10 MPa, a polymethoxy dimethyl ether mass space velocity of 0.2 to 10.0 h" 1 and not added
  • the reaction is carried out under the conditions of other solvents to prepare polymethoxy dimethyl ether carbonyl; under the reaction conditions, at least one of the raw material polymethoxy dimethyl ether and the product polymethoxy dimethyl ether carbonyl is in a liquid phase, and the catalyst is solid.
  • the raw materials carbon monoxide and hydrogen are in the gas phase, and the reaction process is a gas-liquid solid three-phase reaction; in the raw material, the molar ratio of carbon monoxide to polymethoxy dimethyl ether is 2:1 ⁇ 20:1, hydrogen and polymethoxy The molar ratio of methyl ether is from 1:1 to 5:1.
  • the reaction process is a gas-liquid-solid three-phase reaction
  • the reaction temperature is 60 ⁇ : 120 ° C
  • the reaction pressure is 4 ⁇ 10 MPa
  • the mass space velocity of polymethoxy dimethyl ether is 0.5 ⁇ 3.0 h
  • “1 molar ratio of carbon monoxide with polyoxymethylene dimethyl ether is 2: 1 ⁇ 15: 1 molar ratio of hydrogen to preferably polyoxymethylene dimethyl ether is 1: 1 ⁇ 3: 1 .
  • the reaction process is a gas-liquid-solid three-phase reaction
  • the reaction temperature is 60 to 90 ° C
  • the reaction pressure is 5 to: 10 MPa
  • the mass space velocity of the polymethoxy dimethyl ether is 0.5 to 1.5 h.
  • the molar ratio of carbon monoxide to polymethoxy dimethyl ether is 2:1 to 10:1
  • the preferred molar ratio of hydrogen to polymethoxy dimethyl ether is 1:1 to 2:1.
  • both the conversion of polymethoxy dimethyl ether and the selectivity of polymethoxy dimethyl ether carbonyl are calculated based on the moles of polymethoxy dimethyl ether carbon:
  • Polymethoxy dimethyl ether conversion [(polymethylene dimethyl ether carbon moles in the feed:) one (polymethoxy dimethyl ether carbon moles in the discharge:) ] ⁇ (in the feed Polymethoxy dimethyl ether carbon mole number) X (100%)
  • Polymethoxy dimethyl ether carbonyl selectivity (Molar number of carbon after removal of carbonyl by polymethoxy dimethyl ether carbonyl in the discharge:) ⁇ [(Polymethoxyl dimethyl ether carbon number in feed) ) 1 (polymethylene dimethyl ether carbon moles in the discharge)] X (100%)
  • the invention also provides a preparation method of methyl methoxyacetate and polymethoxy dimethyl ether carbonyl, which comprises raw materials containing methylal CH 3 0-CH 2 -OCH 3 , carbon monoxide and hydrogen.
  • the reaction temperature is 60 to 140 ° C
  • the reaction pressure is 2 to 10 MPa
  • the mass space velocity of the methylal is 0.2 to 10.0 h- 1, and no other solvent is added.
  • the reaction is carried out to prepare methyl methoxyacetate and polymethoxy dimethyl ether carbonyl; under the reaction conditions, at least one of the raw material methyl acetal and the product methyl methoxyacetate and polymethoxy dimethyl ether carbonyl is In the liquid phase, the catalyst is a solid phase, the raw materials carbon monoxide and hydrogen are in the gas phase, and the reaction process is a gas-liquid-solid three-phase reaction; in the raw material, the molar ratio of carbon monoxide to methylal is 2:1 to 20:1, hydrogen and methylal The molar ratio is 1:1 to 5:1.
  • the reaction process is a gas-liquid-solid three-phase reaction
  • the reaction temperature is 60 to: 120 ° C
  • the reaction pressure is 4 to: 10 MPa
  • the mass space velocity of the methylal is 0.5 to 3.0 h - carbon monoxide and
  • the molar ratio of methylal is 2: 1 to 15: 1
  • the preferred molar ratio of hydrogen to methylal is 1:1 to 3:1.
  • the reaction process is a gas-liquid-solid three-phase reaction
  • the reaction temperature is 60 to 90 ° C
  • the reaction pressure is 5 to: 10 MPa
  • the mass space velocity of the methylal is 0.5 to 1.5 h - carbon monoxide and carbon
  • the molar ratio of acetal is 2:1 to 10:1
  • the preferred molar ratio of hydrogen to methylal is 1:1 to 2:1.
  • the conversion of methylal and the selectivity of the product are calculated based on the methylal number of methylal:
  • the preparation method of the desiliconization modified acidic molecular sieve catalyst comprises placing the molecular sieve into an optional 0.05 ⁇ 6.0 mol/L, preferably 0.2 ⁇ 1.5 mol/L sodium hydroxide, potassium hydroxide, lithium hydroxide, and hydroxide.
  • the reaction is carried out at 15 to 95 ° C, preferably 50 to 85 ° C for 0.5 to 24 h, and the filter cake after filtration is 0.01 to 0.01 Wash with 0.5 mol/L hydrochloric acid, nitric acid, sulfuric acid or acetic acid solution, neutralize the acidity of the filter cake, wash the neutralized salt solution with deionized water, and then obtain the conventional ammonium ion exchange, filtration, drying and calcination procedures. Desiliconized modified acidic molecular sieve catalyst.
  • the structure of the acidic molecular sieve catalyst is MWW, FER, MFI, MOR, FAU or BEA.
  • the acidic molecular sieve catalyst is a mixture of any one or any one of MCM-22 molecular sieve, ferrierite, ZSM-5 molecular sieve, mordenite, Y zeolite or Beta molecular sieve, and the silicon to aluminum atomic ratio is 3. :1 ⁇ 150:1.
  • the standard operating procedure for converting a cationic molecular sieve into an acidic molecular sieve is: placing 50 g of the dried cationic molecular sieve into 400 ml of a 0.8 M N3 ⁇ 4N0 3 solution and stirring at 80 ° C for 12 h. After filtration, it was washed with 800 ml of distilled water. This ion exchange process was repeated three times to obtain a molecular sieve of the N3 ⁇ 4+ type. After sufficient drying, it was placed in a muffle furnace, raised to 550 °C at 2 °C/mm and kept calcined for 4 h to obtain an acidic molecular sieve.
  • the polymethoxy dimethyl ether carbonyl is in the molecular chain of polymethoxy dimethyl ether
  • the product of the -o-c3 ⁇ 4-(co)-o-structural unit, the polymethoxy dimethyl ether carbonyl compound contains one or more carbonyl groups.
  • the polymethoxy dimethyl ether carbonyl compound produced in the examples may be one or more of the following:
  • CH 3 -0-(CO) -CH 2 -0-CH 2 -0-CH 3 is abbreviated as C5-1,
  • CH 3 -0 -CH 2 -(CO)-0-CH 2 -0-CH 3 is abbreviated as C5-2,
  • CH 3 -0-(CO)-CH 2 -0-(CO)-CH 2 -0-CH 3 is abbreviated as C6-1,
  • CH 3 -0-(CO)-CH 2 -0-CH 2 -(CO)-0-CH 3 is abbreviated as C6-2.
  • the product of the present invention methyl methoxyacetate or polymethoxy dimethyl ether carbonyl
  • the hydrogen is hydrolyzed or hydrolyzed and hydrolyzed to obtain a double turn.
  • the product can also be used as a steam and diesel additive.
  • DDM 2 dimer methoxy diether
  • the reactor is a continuously flowing fixed bed reactor, a still reactor, a moving bed reactor or a fluidized bed reactor.
  • the invention is described in detail below by way of examples, but the invention is not limited to the examples.
  • Example 1
  • Catalyst A A 50 g sodium-to-aluminum ratio of 40:1 MCM-22 molecular sieve was converted to an acidic molecular sieve using standard operating procedures, designated as Catalyst A, see Table 1.
  • a 50 g sodium-alkaline zeolite having a sodium to silicon-aluminum ratio of 10:1 was converted to an acidic molecular sieve using standard operating procedures, designated as Catalyst C, as shown in Table 1.
  • Catalyst C an acidic molecular sieve using standard operating procedures, designated as Catalyst C, as shown in Table 1.
  • Catalyst E A 50 g sodium-to-aluminum ratio of 150:1 ZSM-5 molecular sieve was converted to an acidic molecular sieve using standard operating procedures, designated as Catalyst E, as shown in Table 1.
  • Catalyst G A 50 g sodium-magnesium-alumina ratio of 3:1 mordenite was converted to an acidic molecular sieve using standard operating procedures, designated as Catalyst G, as shown in Table 1.
  • Y molecular sieves with a 50 g sodium-to-aluminum ratio of 20:1 were converted to acidic molecular sieves using standard operating procedures and designated as Catalyst I, see Table 1.
  • a 50 g sodium/aluminum ratio of 15:1 Beta molecular sieve was converted to an acid molecular sieve using standard operating procedures, which was designated as Catalyst K, as shown in Table 1.
  • the product was analyzed by gas chromatography. After the reaction was substantially stabilized, the conversion of dimer methoxy dimethyl ether and the selectivity of polymethoxy dimethyl ether carbonyl were calculated. The results are shown in Table 2.
  • Example 13 The catalyst of Example 13 was changed to Catalyst B, and the remaining experimental procedures were identical to those of Example 13, and the results are shown in Table 2.
  • Example 15 The catalyst of Example 15 was changed to Catalyst D, and the remaining experimental procedures were identical to those of Example 15, and the results are shown in Table 2.
  • Example 17 The catalyst of Example 17 was changed to Catalyst F, and the rest of the experimental procedures were carried out in the same manner as in Example 17, and the results are shown in Table 2.
  • the experimental procedure was the same as in Example 13 and the reaction results are shown in Table 2.
  • Example 19 The catalyst of Example 19 was replaced with Catalyst H, and the remaining experimental procedures and Example 19 Consistent, the reaction results are shown in Table 2.
  • Example 21 The catalyst of Example 21 was changed to Catalyst J, and the remaining experimental procedures were carried out in the same manner as in Example 21, and the results are shown in Table 2.
  • Example 23 The catalyst of Example 23 was changed to Catalyst L, and the remaining experimental procedures were carried out in the same manner as in Example 23, and the results are shown in Table 2.
  • WHSV polymethoxy dimethyl ether mass space velocity
  • Example 25 The catalyst of Example 25 was changed to Catalyst F, and the other conditions were unchanged. The results of the reaction are shown in Table 2.
  • Example 27 The catalyst of Example 27 was changed to Catalyst J, and other conditions were unchanged. The reaction results are shown in Table 2.
  • Catalyst A sample was compressed and pulverized into 20 to 40 mesh for activity testing.
  • Example 29 The catalyst of Example 29 was changed to Catalyst B, and the remaining experimental procedures were identical to those of Example 29, and the results are shown in Table 3.
  • Example 31 The catalyst in Example 31 was changed to Catalyst D, and the remaining experimental procedures were identical to those in Example 31, and the results are shown in Table 3.
  • Example 33 The catalyst of Example 33 was changed to Catalyst F, and the rest of the experimental procedures were carried out in the same manner as in Example 33, and the results are shown in Table 3.
  • Example 35 The catalyst in Example 35 was replaced with Catalyst H, and the remaining experimental procedures and Example 35 Consistent, the reaction results are shown in Table 3.
  • Example 37 The catalyst of Example 37 was changed to Catalyst J, and the remaining experimental procedures were the same as those of Example 37, and the results are shown in Table 3.
  • Example 39 The catalyst of Example 39 was changed to Catalyst L, and the remaining experimental procedures were carried out in the same manner as in Example 39, and the results are shown in Table 3.
  • the catalyst used in the process of the present invention is a desiliconized modified acidic molecular sieve catalyst
  • the raw material is polymethoxy dimethyl ether or methylal with a mixture of the same carbon oxide and hydrogen.
  • the raw material can stably and efficiently produce the product polymethoxy dimethyl ether carbonyl or methyl methoxyacetate as an intermediate for producing ethylene glycol through a catalyst, and the reaction process is gas-liquid solid three-phase. reaction.
  • the carbonylation reaction of methoxy dimethyl ether or methylal is a strong exothermic reaction.
  • the reaction temperature is relatively low, and the liquid heat capacity and the latent heat of phase change are well, and the reaction temperature can be well controlled to prevent industrial production.
  • the gas-liquid-solid three-phase reaction adopted by the invention can be operated at a concentration of high polymethoxy dimethyl ether or methylal, which improves the single-pass reaction productivity in industrial production, and reduces energy consumption during compression, circulation and separation. , improve economic performance.
  • the conversion of the raw material polymethoxy dimethyl ether or methylal is high, and the product polymethoxy dimethyl ether carbonyl or methyl methoxyacetate has high selectivity, and the catalyst has a long single life.
  • the liquid phase raw material reactant or product itself is an excellent solvent, and no additional solvent is required.
  • the liquid phase reactant or product can dissolve the pre-carbon material in the catalytic reaction process, which is beneficial to improve the activity and stability of the catalyst, the reaction condition is mild, and can be continuously produced, and has potential for industrial application.
  • a carbonylation reaction uses a mixed gas of carbon monoxide and hydrogen as a gas phase, and a high-purity carbon monoxide is required in comparison with the existing coal chemical production ethylene glycol technology.
  • the present invention does not require high-purity carbon monoxide, and can greatly reduce the separation gas of synthesis gas. Consumption, improve the economics of the production process.
  • the addition of hydrogen to the reaction gas can also increase the conversion of polymethoxy dimethyl ether or methylal and the selectivity of polymethoxy dimethyl ether carbonyl or methyl methoxyacetate, thereby prolonging the single-pass life of the catalyst.
  • the molecular sieve desiliconization modification method of the invention is simple and easy to operate, and is suitable for industrial large-scale production.
  • the desiliconization modification can extend the single-pass life of the catalyst by 5 to 10 times, which is very effective in reducing the number of catalyst regenerations per year, which is beneficial to the process.
  • polymethoxy dimethyl ether carbonyl compound or methyl methoxyacetate produced in the present invention can be produced by hydrohydrolysis or post-hydrolysis to produce ethylene glycol.
  • the invention has been described in detail above, but the invention is not limited to the description herein. Body embodiment. Other variations and modifications can be made by those skilled in the art without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

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Abstract

La présente invention concerne un procédé de préparation d'éther diméthylique de polyoxyméthylène et/ou d'ester méthylique d'acide méthoxyacétique, un intermédiaire de l'éthylène glycol. Le procédé comprend les étapes suivantes : laisser passer des matières premières éther diméthylique de polyoxyméthylène ou méthylal, monoxyde de carbone et oxygène dans un réacteur chargé d'un catalyseur de tamis moléculaire acide sur lequel une modification par désilicification est effectuée ; et préparer les produits correspondants dans des conditions dans lesquelles aucun autre solvant n'est ajouté, le procédé de réaction étant une réaction en trois phases, gaz, liquide et solide. Dans la présente invention, le taux de transformation de la matière première éther diméthylique de polyoxyméthylène ou méthylal est élevée, la sélectivité des produits est élevée, la durée de vie du catalyseur est élevée, aucun solvant supplémentaire n'est requis, les conditions de réaction sont modérées, la production en continu est possible et le procédé présente un potentiel d'application industrielle. Les produits peuvent être hydrogénés et sont ensuite hydrolysés, ou ils peuvent être hydrolysés et sont ensuite hydrogénés, afin de produire de l'éthylène glycol.
PCT/CN2013/090215 2013-12-23 2013-12-23 Procédé de préparation de composé carbonylé d'éther méthylique de polyoxyméthylène et d'ester méthylique d'acide méthoxyacétique Ceased WO2015095998A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2010048300A1 (fr) * 2008-10-23 2010-04-29 The Regents Of The University Of California Production catalysée en phase gazeuse d’alcoxyacétates d’alkyle à partir de dialcoxyméthanes
CN102701977A (zh) * 2012-06-21 2012-10-03 东莞市同舟化工有限公司 一种甲氧基乙酸甲酯的连续合成方法
CN103172517A (zh) * 2011-12-20 2013-06-26 中国科学院大连化学物理研究所 一种生产甲氧基乙酸甲酯的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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