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WO2015095999A1 - Procédé pour préparer un composé de polyoxyméthylène-diméthyléther-carbonyle et du méthoxyacétate de méthyle - Google Patents

Procédé pour préparer un composé de polyoxyméthylène-diméthyléther-carbonyle et du méthoxyacétate de méthyle Download PDF

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WO2015095999A1
WO2015095999A1 PCT/CN2013/090217 CN2013090217W WO2015095999A1 WO 2015095999 A1 WO2015095999 A1 WO 2015095999A1 CN 2013090217 W CN2013090217 W CN 2013090217W WO 2015095999 A1 WO2015095999 A1 WO 2015095999A1
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reaction
catalyst
molecular sieve
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
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • 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
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • C07C41/48—Preparation of compounds having groups
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • 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 dealuminated 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 dealuminated 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 mon
  • the invention also provides a method 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 is used.
  • 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 dealuminated modified acidic molecular sieve catalyst is prepared by subjecting an acid molecular sieve catalyst to a dealumination modification comprising a steam treatment followed by an acid treatment.
  • the steam treatment temperature is 400 to 700 ° C, and the time is 1 to 8 h ; and the acid used in the acid treatment is 0.03 to 3.0 mol/L, which is selected from the group consisting of hydrochloric acid and sulfuric acid.
  • One or more acids of nitric acid, acetic acid, oxalic acid, citric acid, and the acid treatment temperature is 15 to 95 ° C, and the time is 1 to 24 ho
  • the dealuminized modified acidic molecular sieve catalyst has a structure type of MWW, FER, MFI, MOR, FAU or BEA.
  • the dealuminated 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 to 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 method 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 hydrogen is carried through
  • the reactor of the aluminum-modified acidic molecular sieve catalyst has a reaction temperature of 60 to 140 ° C, a reaction pressure of 2 to 10 MPa, a mass space velocity of polymethoxy dimethyl ether of 0.2 to 10.0 h- 1, and no other solvent is added.
  • the reaction is carried out under conditions 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 a solid phase. 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 dimethyl ether The molar ratio is 1:1 to 5:1, where n 2 is an integer.
  • 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.
  • Polymethoxy dimethyl ether carbonyl selectivity (Molar number of carbon after removal of carbonyl by polymethoxy dimethyl ether carbonyl in feed:) ⁇ [(Polyoxyl dimethyl ether carbon number in feed) :) one (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 without adding other solvent.
  • 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 5.0 to 10 MPa
  • the mass space velocity of the methylal is 0.5 to 1.5 h -1 , - oxidation
  • the molar ratio of carbon to methylal 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:
  • Methyl methoxyacetate selectivity (molar number of carbon after removal of carbonyl by methyl methoxyacetate in the discharge) ⁇ [(moles of methyl acetal in the feed) 1 (methyl acetal in the discharge) Number) ] ⁇ ( ⁇ %)
  • Polymethoxy dimethyl ether carbonyl selectivity (Molar number of carbon after removal of carbonyl by polymethoxy dimethyl ether carbonyl in the discharge:) ⁇ [(: moles of methyl acetal in the feed) Molecular weight of methylal in the discharge)) X (100%)
  • the method of dealumination modification includes steam treatment and acid treatment.
  • the steam treatment temperature is 400 to 700 ° C, preferably 550 to 650 ° C, and the steam treatment time is not limited, preferably 1 to 8 h ;
  • the acid used in the acid treatment is 0.03 to 3.0 mol/L, preferably 0.1. ⁇ 1.0 mol / L of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, citric acid, one or more mixed acid, acid treatment temperature of 15 ⁇ 95 ° C, preferably 60 ⁇ 80 ° C, acid treatment time is not limited , preferably 1 ⁇ 24 h.
  • 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 sodium-type molecular sieves into acidic molecular sieves is as follows: 50 g of dried Na+ molecular sieves are placed in 400 ml of 0.8 M N3 ⁇ 4N0 3 solution, stirred at 80 ° C for 12 h, filtered. Wash 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, can be hydrolyzed by hydrogenation or hydrolyzed to obtain ethylene glycol. Further, the product can also be used as a steam and diesel additive. For example, taking dimeric methoxy dimethyl ether (DMM 2 ) CH 3 0(C3 ⁇ 40) 2 C3 ⁇ 4 as an example
  • DDM 2 dimeric methoxy dimethyl ether
  • 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.
  • 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.
  • Example 5 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, which is designated as Catalyst D, as shown in Table 1.
  • Catalyst D An acidic molecular sieve using standard operating procedures, which is designated as Catalyst D, as shown in Table 1.
  • a 100 g sodium-alkaline zeolite having a sodium-to-silicon-aluminum ratio of 10:1 was subjected to steam treatment at 700 °C for 1 h, and then converted into an acidic molecular sieve by a standard operating procedure, which is referred to as catalyst E, as shown in Table 1.
  • Catalyst G 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 G, as shown in Table 1.
  • a 50 g sodium-magnesia-alumina ratio of 3:1 mordenite was converted to an acidic molecular sieve using standard operating procedures and designated as Catalyst J, see Table 1.
  • a 100 g sodium silicate having a ratio of sodium to silicon of 3:1 was subjected to steam treatment at 650 ° C for 3 h, and then converted into an acidic molecular sieve by a standard operating procedure, which was designated as catalyst K, as shown in 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 P, as shown in Table 1.
  • a 100 g sodium-aluminum-aluminum ratio 15:1 beta molecular sieve was passed through a water vapor treatment at 600 °C for 4 h, and then converted into an acidic molecular sieve by a standard operating procedure, which was recorded as a catalyst Q, as shown in Table 1.
  • Catalyst A samples were compressed and pulverized into 20 to 40 mesh for activity testing.
  • Example 19 The catalyst of Example 19 was changed to Catalyst B, and the remaining experimental procedures were identical to those of Example 19, and the results are shown in Table 2.
  • Example 19 The catalyst of Example 19 was changed to Catalyst C, and the remaining experimental procedures were identical to those of Example 19, and the results are shown in Table 2.
  • Example 22 The catalyst of Example 22 was replaced by Catalyst E, and the remaining experimental procedures were carried out in the same manner as in Example 22, and the results are shown in Table 2.
  • Example 22 The catalyst of Example 22 was replaced by Catalyst F, and the rest of the experimental procedures were carried out in the same manner as in Example 22, and the results are shown in Table 2.
  • Example 25 The catalyst in Example 25 was changed to Catalyst H, and the remaining experimental procedures were identical to those in Example 25. The results are shown in Table 2.
  • Example 25 The catalyst of Example 25 was changed to Catalyst I, and the remaining experimental procedures were carried out in the same manner as in Example 25, and the results are shown in Table 2.
  • the experimental procedure was identical to that of Example 19, and the results of the reaction are shown in Table 2.
  • Example 28 The catalyst of Example 28 was changed to Catalyst K, and the remaining experimental procedures were identical to those of Example 28, and the results are shown in Table 2.
  • Example 28 The catalyst of Example 28 was changed to Catalyst L, and the rest of the experimental procedures were carried out in the same manner as in Example 28, and the results are shown in Table 2.
  • Example 31 The catalyst in Example 31 was changed to Catalyst N, and the remaining experimental procedures were identical to those in Example 31, and the results are shown in Table 2.
  • Example 31 The catalyst in Example 31 was changed to Catalyst 0, and the remaining experimental procedures were identical to those in Example 31, and the results are shown in Table 2.
  • the procedure is the same as in Example 19, and the reaction results are shown in Table 2.
  • Example 34 The catalyst of Example 34 was changed to Catalyst Q, and the remaining experimental procedures were identical to those of Example 34, and the results are shown in Table 2.
  • Example 34 The catalyst of Example 34 was changed to Catalyst R, and the remaining experimental procedures were identical to those of Example 34, and the results are shown in Table 2.
  • Example 39 The catalyst of Example 37 was changed to Catalyst H, and other conditions were unchanged. The results of the reaction are shown in Table 2. Example 39
  • Example 37 The catalyst of Example 37 was changed to Catalyst I, and the other conditions were unchanged.
  • the reaction results are shown in Table 2.
  • Example 40 The catalyst of Example 40 was changed to Catalyst N, and the other conditions were unchanged.
  • the reaction results are shown in Table 2.
  • Example 40 The catalyst of Example 40 was changed to Catalyst 0, and other conditions were unchanged. The results of the reaction are shown in Table 2.
  • Catalyst A sample was compressed and pulverized into 20 to 40 mesh for activity testing.
  • Weigh 10 g of the catalyst A, put it into a stainless steel reaction tube with an inner diameter of 8.5 mm, activate with nitrogen at normal pressure, 550 ° C for 4 hours, then drop to the reaction temperature 0 90 ° C, pass carbon monoxide: contraction
  • Aldehyde: Hydrogen (CO: DMM: 3 ⁇ 4 ) 7:1 : 1
  • the reaction results are shown in Table 3.
  • Example 43 The catalyst of Example 43 was changed to Catalyst B, and the remaining experimental procedures were identical to those of Example 43 and the results are shown in Table 3.
  • Example 43 The catalyst in Example 43 was changed to Catalyst C, and the remaining experimental procedures were identical to those in Example 43 and the results are shown in Table 3.
  • the reaction results are shown in Table 3.
  • Example 46 The catalyst in Example 46 was changed to Catalyst E, and the remaining experimental procedures were carried out in the same manner as in Example 46, and the results are shown in Table 3.
  • Example 46 The catalyst of Example 46 was changed to Catalyst F, and the remaining experimental procedures were carried out in the same manner as in Example 46, and the results are shown in Table 3.
  • Example 51 The catalyst of Example 49 was changed to Catalyst H, and the remaining experimental procedures were identical to those of Example 49, and the results are shown in Table 3.
  • Example 51 The catalyst of Example 49 was changed to Catalyst H, and the remaining experimental procedures were identical to those of Example 49, and the results are shown in Table 3.
  • Example 49 The catalyst of Example 49 was changed to Catalyst I, and the rest of the experimental procedures were identical to those of Example 49, and the results are shown in Table 3.
  • Example 52 The catalyst in Example 52 was changed to Catalyst K, and the remaining experimental procedures were identical to those in Example 52, and the results are shown in Table 3.
  • Example 52 The catalyst of Example 52 was changed to Catalyst L, and the remaining experimental procedures were carried out in the same manner as in Example 52, and the results are shown in Table 3.
  • Example 55 The catalyst of Example 55 was changed to Catalyst N, and the remaining experimental procedures were identical to those of Example 55, and the results are shown in Table 3.
  • Example 55 The catalyst in Example 55 was changed to Catalyst 0, and the remaining experimental procedures were identical to those in Example 55, and the results are shown in Table 3.
  • Example 60 The catalyst in Example 58 was replaced with Catalyst Q, and the remaining experimental procedures were identical to those in Example 58 and the results are shown in Table 3.
  • Example 60 The catalyst in Example 58 was replaced with Catalyst Q, and the remaining experimental procedures were identical to those in Example 58 and the results are shown in Table 3.
  • Example 58 The catalyst of Example 58 was changed to Catalyst R, and the remaining experimental procedures were identical to those of the Examples, and the results are shown in Table 3.
  • the catalyst used in the process of the present invention is a dealuminated 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 high concentration of polymethoxy dimethyl ether or methylal, which improves the single-pass reaction productivity in industrial production, and reduces the energy during compression, circulation and separation. Consumption, 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 dealuminization modification method of the invention is simple and easy to operate, and is suitable for industrial large-scale production. After dealuminization modification, the single-pass life of the catalyst can be extended by 5 to 10 times, which effectively reduces the number of catalyst regeneration times per year, which is beneficial to the process. Improve annual production capacity, reduce raw material waste, reduce waste gas discharge, reduce catalyst loss due to pressure relief and carbon deposition, extend production equipment life cycle, and improve economic performance.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour préparer un composé de polyoxyméthylène-diméthyléther-carbonyle et/ou du méthoxyacétate de méthyle servant d'intermédiaire pour produire de l'éthylèneglycol, consistant à : faire passer une matière première de polyoxyméthylène-diméthyléther ou de diméthoxyméthane ensemble avec du monoxyde de carbone et de l'hydrogène gazeux au travers d'un réacteur portant un catalyseur zéolithique acide modifié par désalumination et préparer les produits correspondants par réaction, dans des conditions de réaction appropriées, sans addition d'un quelconque autre solvant, le procédé de réaction étant une réaction en trois phases gaz-liquide-solide. Dans le procédé de la présente invention, le taux de conversion de la matière première polyoxyméthylène-diméthyléther ou diméthoxyméthane est élevé, la sélectivité des produits est élevée, la durée de vie du catalyseur est allongée, le besoin d'un solvant supplémentaire est rendu inutile, les conditions de réaction sont relativement douces, une production continue est permise et le potentiel pour une application industrielle est fourni. De même, les produits acquis peuvent être, soit hydrogénés puis hydrolysés, soit hydrolysés puis hydrogénés pour produire de l'éthylèneglycol.
PCT/CN2013/090217 2013-12-23 2013-12-23 Procédé pour préparer un composé de polyoxyméthylène-diméthyléther-carbonyle et du méthoxyacétate de méthyle Ceased WO2015095999A1 (fr)

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CN107899609A (zh) * 2017-11-16 2018-04-13 山西大学 一种生产聚甲醛二甲醚的催化剂及其制备方法
CN111995521A (zh) * 2020-09-01 2020-11-27 山西大学 一种用于二甲氧基甲烷气相羰基化合成甲氧基乙酸甲酯的反应装置及其方法

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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
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EP2177499A1 (fr) * 2008-10-13 2010-04-21 BP Chemicals Limited Procédé de carbonylation
CN102245297A (zh) * 2008-10-13 2011-11-16 英国石油化学品有限公司 Mor型沸石的选择性脱铝
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CN107899609A (zh) * 2017-11-16 2018-04-13 山西大学 一种生产聚甲醛二甲醚的催化剂及其制备方法
CN107899609B (zh) * 2017-11-16 2020-07-10 山西大学 一种生产聚甲醛二甲醚的催化剂及其制备方法
CN111995521A (zh) * 2020-09-01 2020-11-27 山西大学 一种用于二甲氧基甲烷气相羰基化合成甲氧基乙酸甲酯的反应装置及其方法

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