WO2015095999A1 - Method for preparing polyoxymethylene dimethyl ether carbonyl compound and methyl methoxyacetate - Google Patents
Method for preparing polyoxymethylene dimethyl ether carbonyl compound and methyl methoxyacetate Download PDFInfo
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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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- WIPO (PCT)
- Prior art keywords
- reaction
- catalyst
- molecular sieve
- dimethyl ether
- raw material
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 35
- -1 polyoxymethylene dimethyl ether Polymers 0.000 title claims abstract description 31
- ICPWFHKNYYRBSZ-UHFFFAOYSA-M 2-methoxypropanoate Chemical compound COC(C)C([O-])=O ICPWFHKNYYRBSZ-UHFFFAOYSA-M 0.000 title claims abstract description 21
- 150000001728 carbonyl compounds Chemical class 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 135
- 238000006243 chemical reaction Methods 0.000 claims abstract description 123
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 41
- 230000002378 acidificating effect Effects 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims description 66
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 66
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 33
- 239000012071 phase Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010306 acid treatment Methods 0.000 claims description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 9
- 238000005810 carbonylation reaction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 239000000543 intermediate Substances 0.000 claims description 7
- 230000006315 carbonylation Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052680 mordenite Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 3
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 238000010924 continuous production Methods 0.000 abstract 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 97
- 238000002474 experimental method Methods 0.000 description 31
- 239000000047 product Substances 0.000 description 27
- 238000010561 standard procedure Methods 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003245 coal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QECJIGNJADOMIG-UHFFFAOYSA-N [C].COC Chemical compound [C].COC QECJIGNJADOMIG-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920002675 Polyoxyl Polymers 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- WGHCVSYNPVNMID-UHFFFAOYSA-N alumane;sodium Chemical compound [Na].[AlH3].[AlH3] WGHCVSYNPVNMID-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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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Abstract
Provided is a method for preparing a polyoxymethylene dimethyl ether carbonyl compound and/or methyl methoxyacetate serving as an intermediate for producing ethylene glycol, comprising: passing a raw material polyoxymethylene dimethyl ether or dimethoxymethane together with carbon monoxide and hydrogen gas through a reactor carrying a delumination-modified acidic zeolite catalyst, and preparing corresponding products by reacting in appropriate reaction conditions without adding any other solvent, where the reaction process is a gas-liquid-solid three-phase reaction. In the method of the present invention, the conversion rate of the raw material polyoxymethylene dimethyl ether or dimethoxymethane is high, the selectivity of the products is high, catalyst service life is extended, the need for additional solvent is obviated, the reaction conditions are relatively mild, continuous production is allowed, and the potential for industrial application is provided. Also, the products acquired can either be hydrogenated then hydrolyzed or be hydrolyzed then hydrogenated to produce ethylene glycol.
Description
制备聚甲氧基二甲醚羰化物及甲氧基乙酸甲酯的方法 技术领域 Process for preparing polymethoxy dimethyl ether carbonyl and methyl methoxy acetate
本发明涉及一种作为生产乙二醇的中间体的聚甲氧基二甲醚羰化物 及甲氧基乙酸甲酯的制备方法。 背景技术 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
乙二醇是国家重要的化工原料和战略物资，用于制造聚酯（可进一歩 生产涤纶、 PET瓶子、 薄膜）、 炸药、 乙二醛， 并可作为防冻剂、 增塑剂、 水力流体和溶剂等。 2009 年中国的乙二醇进口量超过 580 万吨， 预计 2015 年我国乙二醇需求将达到 1120 万吨， 生产能力约 500 万吨， 供需 缺口仍达 620 万吨， 因此， 我国乙二醇生产新技术的开发应用具有很好 的市场前景。国际上主要采用石油裂解的乙烯经氧化得到环氧乙垸，环氧 乙垸水合得到乙二醇。鉴于我国 "富煤缺油少气"的能源资源结构与原油 价格长期维持高位运行等现状，煤制乙二醇新型煤化工技术既能保障国家 的能源安全，又充分利用了我国的煤炭资源，是未来煤化工产业最现实的 选择。 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. In 2009, 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 The development and application of new technologies has a good market prospect. Internationally, petroleum cracked ethylene is mainly oxidized to obtain epoxy acetamidine, and ethylene epoxide is hydrated to obtain ethylene glycol. In view of the current situation of China's "rich coal, lack of oil and gas" energy resources structure and crude oil prices for a long time, 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.
目前， 国内比较成熟的技术是由中国科学院福建物构所开发的 "CO 气相催化合成草酸酯和草酸酯催化加氢合成乙二醇成套工艺技术。 " 2009 年 12月上旬， 备受业界瞩目的全球首套工业化示范装置一内蒙古通辽金 煤化工公司 "煤制乙二醇项目 "一期工程、 年产 20万吨煤制乙二醇项目 顺利打通全线工艺流程， 生产出合格乙二醇产品。然而工艺单元较多， 工 业气体纯度要求高，在氧化偶联过程中需要使用贵金属催化剂，需要利用 潜在环境污染的氮氧化合物等会制约该流程的经济性、环保性、节能性以 及进一歩工程放大。 At present, the more mature technology in China is developed by the Fujian Institute of Materials, Chinese Academy of Sciences, "CO gas phase catalytic synthesis of oxalate and oxalate catalytic hydrogenation synthesis of ethylene glycol complete process technology." In early December 2009, the industry The world's first industrial demonstration equipment, the first phase of the "coal ethylene glycol project" project of Inner Mongolia Tongliao Jinmei Chemical Co., Ltd., and the annual production of 200,000 tons of coal-to-glycol project successfully opened the entire process, producing qualified ethylene glycol. product. However, there are many process units, high purity requirements for industrial gases, precious metal catalysts are needed in the oxidative coupling process, and nitrogen oxides that require potential environmental pollution may limit the economics, environmental protection, energy conservation, and further engineering of the process. amplification.
聚甲氧基二甲醚（或叫聚甲氧基甲缩醛， 英文名为 Polyoxymethylene dimethyl ethers) 的分子式为 CH30(C¾0)nCH3， 其中 n 2， 一般简称为 DMMn (：或 PODEn：)。 在制备聚甲氧基二甲醚的过程中， 其生成的产物分布 不合理， 甲缩醛和 DMM2较高， 而可以用作柴油添加剂的 DMM3〜4选择
性却较低，因此，常常需要对其制备过程中的副产物进行反复分离再反应， 这样能耗较大， 经济性较差。 因此， 如果能将作为副产物的 DMM2直接 加工成经济价值更高的产品将会提高此过程的经济性。 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 :). In the process of preparing polymethoxy dimethyl ether, the product formed is unreasonable, and the methyl acetal and DMM 2 are higher, and 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.
近年来， 美国 UC， Berkeley的 Alexis T. Bell教授课题组提出利用甲 缩醛气相羰基化法制备甲氧基乙酸甲酯，然后加氢水解得到乙二醇的一条 新路线， 其中最关键的一歩是气羰基化反应。然而催化剂寿命短、原料气 中甲缩醛浓度低、 甲缩醛转化率与甲氧基乙酸甲酯选择性都不够理想，离 工业化还有相当长的距离 [Angew. Chem. Int. Ed., 2009, 48, 4813〜4815; J. Catal, 2010, 270, 185〜 195; J. Catal, 2010, 274, 150〜 162; WO 2010/048300 Al ]。 发明内容 In recent years, Prof. Alexis T. Bell of UC, Berkeley, USA, proposed a new route for the preparation of methyl methoxyacetate by vapor phase carbonylation of methylal, followed by hydrogenation to obtain ethylene glycol. The most critical one is It is a gas carbonylation reaction. However, the catalyst life is short, the methyl acetal concentration in the feed gas is low, the methyl acetal conversion rate and the methyl methoxyacetate selectivity are not ideal, and there is still a long distance from industrialization [Angew. Chem. Int. Ed., 2009, 48, 4813~4815; J. Catal, 2010, 270, 185~195; J. Catal, 2010, 274, 150~162; WO 2010/048300 Al]. Summary of the invention
本发明的目的在于提供一种通过羰基化制备作为生产乙二醇的中间 体的聚甲氧基二甲醚羰化物及甲氧基乙酸甲酯的方法。 SUMMARY OF THE INVENTION 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.
为此，本发明提供了一种通过羰基化制备作为生产乙二醇的中间体的 聚甲氧基二甲醚羰化物的方法， 其特征在于， 将原料聚甲氧基二甲醚 CH30(CH20)nCH3连同一氧化碳和氢气通过载有脱铝改性的酸性分子筛 催化剂的反应器， 在反应温度 60〜140°C、 反应压力 2〜10 MPa、 聚甲氧 基二甲醚质量空速为 O j l O .O h 且不添加其他溶剂的条件下反应制备产 物聚甲氧基二甲醚羰化物，其中在所述反应条件下，所述原料与所述产物 中的至少一种为液相，所述脱铝改性的酸性分子筛催化剂为固相，一氧化 碳和氢气为气相以使反应过程为气液固三相反应，并且一氧化碳与所述原 料的摩尔比为 2:1〜20:1， 氢气与所述原料的摩尔比为 1 :1〜5:1， 其中 n ^2且为整数。 To this end, 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 In the liquid phase, 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 monoxide to the raw material is 2:1~ 20:1, the molar ratio of hydrogen to the starting material is 1:1 to 5:1, wherein n^2 is an integer.
本发明还提供了一种通过羰基化制备作为生产乙二醇的中间体甲氧 基乙酸甲酯及聚甲氧基二甲醚羰化物的方法，其特征在于，将原料甲缩醛 CH30-C¾-OC¾连同一氧化碳和氢气通过载有脱铝改性的酸性分子筛催 化剂的反应器， 在反应温度 60〜140°C、 反应压力 2〜10 MPa、 甲缩醛质 量空速为 0.2〜10.0 h—1且不添加其他溶剂的条件下反应制备产物甲氧基乙 酸甲酯及聚甲氧基二甲醚羰化物，其中在所述反应条件下，所述原料与所
述产物中的至少一种为液相， 所述脱铝改性的酸性分子筛催化剂为固相， 一氧化碳和氢气为气相以使反应过程为气液固三相反应，并且一氧化碳与 所述原料的摩尔比为 2:1〜20:1， 氢气与所述原料的摩尔比为 1 :1〜5:1。 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. -C3⁄4-OC3⁄4 with the same oxidized carbon and hydrogen passing through a reactor carrying dealuminized 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 and reacting without the addition of other solvents to produce the product methyl methoxyacetate and polymethoxy dimethyl ether carbonyl, wherein under the reaction conditions, the raw materials and At least one of the products is a liquid phase, the dealuminated 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.
在一个优选实施方案中，所述产物聚甲氧基二甲醚羰化物是在聚甲氧 基二甲醚 CH30(CH20;)nCH3分子链的 -0-C¾-0-结构单元上插入一个或多 个羰基 -CO-后形成的具有 -C CO)-C¾-0-或 -0-CH2-(CO)-0-结构单元的 产物， 其中 n 2。 In a preferred embodiment, 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 A product having a -C CO)-C3⁄4-0- or -0-CH 2 -(CO)-0- structural unit formed after insertion of one or more carbonyl-CO- groups on a structural unit, wherein n 2 .
在一个优选实施方案中， 所述聚甲氧基二甲醚为二聚甲氧基二甲醚 CH30(C¾0)2CH3。 In a preferred embodiment, the polymethoxy dimethyl ether is dipoly methoxy dimethyl ether CH 3 0(C 3⁄40) 2 CH 3 .
在一个优选实施方案中，所述聚甲氧基二甲醚羰化物为以下中的一种 或多种： In a preferred embodiment, the polymethoxy dimethyl ether carbonyl is one or more of the following:
CH3-0-(CO)-CH2-0-CH2-0-CH3， CH 3 -0-(CO)-CH 2 -0-CH 2 -0-CH 3 ,
CH3-0 -C¾-(C0)-0-C¾-0-CH3， CH 3 -0 -C3⁄4-(C0)-0-C3⁄4-0-CH 3 ,
CH3-0-(CO)-CH2-0-(CO)-CH2-0-CH3， 禾口 CH 3 -0-(CO)-CH 2 -0-(CO)-CH 2 -0-CH 3 , and
CH3-0-(CO)-CH2-0-CH2-(CO)-0-CH3。 CH 3 -0-(CO)-CH 2 -0-CH 2 -(CO)-0-CH 3 .
在一个优选实施方案中，所述脱铝改性的酸性分子筛催化剂通过使酸 性分子筛催化剂经过包括水蒸气处理与酸处理的脱铝改性制备。 In a preferred embodiment, 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.
在一个优选实施方案中， 所述水蒸气处理的温度为 400〜700°C， 时 间为 1〜8 h; 所述酸处理中使用的酸为 0.03〜3.0 mol/L的选自盐酸、 硫 酸、 硝酸、 醋酸、 草酸、 柠檬酸中的一种或者多种酸， 并且所述酸处理的 温度为 15〜95 °C， 时间为 1〜24 h o In a preferred embodiment, 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
在一个优选实施方案中，所述脱铝改性的酸性分子筛催化剂的结构类 型为 MWW、 FER、 MFI、 M0R、 FAU或 BEA。 In a preferred embodiment, the dealuminized modified acidic molecular sieve catalyst has a structure type of MWW, FER, MFI, MOR, FAU or BEA.
在一个优选实施方案中， 所述脱铝改性的酸性分子筛催化剂为 MCM-22分子筛、 镁碱沸石、 ZSM-5分子筛、 丝光沸石、 Y沸石或 Beta 分子筛中的一种或几种。 In a preferred embodiment, 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.
在一个优选实施方案中， 反应温度为 60〜120°C， 反应压力为 4〜10 MPa,所述原料的质量空速为 0.5〜3.0 h— 一氧化碳与所述原料的摩尔比 为 2:1〜15:1， 氢气与所述原料的摩尔比为 1:1〜3:1。 In a preferred embodiment, the reaction temperature is 60 to 120 ° C, the reaction pressure is 4 to 10 MPa, and 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.
在一个优选实施方案中， 反应温度为 60〜90°C， 反应压力为 5〜10
MPa,所述原料的质量空速为 0.5〜1.5 h— 一氧化碳与所述原料的摩尔比 为 2:1〜10:1， 氢气与所述原料的摩尔比为 1:1〜2:1。 In a preferred embodiment, the reaction temperature is 60 to 90 ° C, and 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, and the molar ratio of hydrogen to the raw material is 1:1 to 2:1.
在一个优选实施方案中， 所述反应器是实现连续反应的固定床反应 器、 釜式反应器、 移动床反应器或流化床反应器。 In a preferred embodiment, the reactor is a fixed bed reactor, a tank reactor, a moving bed reactor or a fluidized bed reactor that effects a continuous reaction.
本发明方法中原料聚甲氧基二甲醚或甲缩醛的转化率高，各产物的选 择性高， 催化剂寿命长， 不需要使用外加溶剂， 反应条件比较温和， 能够 连续生产， 具备工业化应用潜力。而且， 所获的产物能够通过加氢后水解 或者水解后加氢生产乙二醇。 具体实施方式 In the method of the invention, 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. Moreover, the obtained product can be hydrolyzed by hydrogenation or hydrolyzed to produce ethylene glycol. detailed description
本发明提供一种制备聚甲氧基二甲醚羰化物的方法，其特征在于，将 含有聚甲氧基二甲醚 CH3O CH2C nCH3、一氧化碳和氢气的原料通过载有 脱铝改性的酸性分子筛催化剂的反应器， 在反应温度 60〜140°C、 反应压 力 2〜10 MPa、 聚甲氧基二甲醚质量空速为 0.2〜10.0 h— 1且不添加其他溶 剂的条件下反应，制备聚甲氧基二甲醚羰化物；反应条件下原料聚甲氧基 二甲醚与产物聚甲氧基二甲醚羰化物至少一种为液相，催化剂为固相，原 料一氧化碳和氢气为气相， 反应过程为气液固三相反应； 原料中， 一氧化 碳与聚甲氧基二甲醚的摩尔比为 2:1〜20:1， 氢气与聚甲氧基二甲醚的摩 尔比为 1 :1〜5:1， 其中 n 2且为整数。 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.
所述的聚甲氧基二甲醚为单一组分或混合物， 分子式为 CH30(CH20)nCH3,其中 n 2且为整数，优选 n=2， B CH30(CH20)2CH30 在一个优选实施方式中， 反应过程为气液固三相反应， 反应温度为 60〜： 120°C，反应压力为 4〜10 MPa，聚甲氧基二甲醚质量空速为 0.5〜3.0 h"1 , 一氧化碳与聚甲氧基二甲醚的摩尔比为 2:1〜15:1优选的氢气与聚甲 氧基二甲醚的摩尔比为 1 :1〜3:1。 The polymethoxy dimethyl ether is a single component or a mixture having the formula CH 3 0(CH 2 0) n CH 3 , wherein n 2 is an integer, preferably n=2, B CH 3 0 (CH 2 0) 2 CH 30 In a preferred embodiment, 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, and 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 .
在一个优选实施方式中， 反应过程为气液固三相反应， 反应温度为 60〜90°C， 反应压力为 5〜： 10 MPa, 聚甲氧基二甲醚质量空速为 0.5〜1.5 h"1 , 一氧化碳与聚甲氧基二甲醚的摩尔比为 2:1〜10:1， 优选的氢气与聚 甲氧基二甲醚的摩尔比为 1 :1〜2:1。 In a preferred embodiment, 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, and the mass space velocity of the polymethoxy dimethyl ether is 0.5 to 1.5 h. " 1. The molar ratio of carbon monoxide to polymethoxy dimethyl ether is 2:1 to 10:1, and the preferred molar ratio of hydrogen to polymethoxy dimethyl ether is 1:1 to 2:1.
在本发明一些实施例中，聚甲氧基二甲醚的转化率和聚甲氧基二甲醚
羰化物的选择性都基于聚甲氧基二甲醚碳摩尔数进行计算： 聚甲氧基二甲醚转化率 = [(进料中聚甲氧基二甲醚碳摩尔数：)一（出 料聚甲氧基二甲醚碳摩尔数 )] ÷ (：进料中聚甲氧基二甲醚碳摩尔数：) X (100%) In some embodiments of the invention, the conversion of polymethoxy dimethyl ether and polymethoxy dimethyl ether The selectivity of the carbonyl compound is calculated based on the number of moles of polymethoxy dimethyl ether carbon: Polymethoxy dimethyl ether conversion = [(polymethylene dimethyl ether carbon number in the feed:) one (out The amount of carbon in the polymethoxy dimethyl ether is ) (: the number of moles of polymethoxy dimethyl ether in the feed: X) (100%)
聚甲氧基二甲醚羰化物选择性 = (进料中聚甲氧基二甲醚羰化物除 去羰基后的碳摩尔数：) ÷ [(进料中聚甲氧基二甲醚碳摩尔数：)一 (出料中聚 甲氧基二甲醚碳摩尔数） ] X (100%) 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%)
本发明还提供一种甲氧基乙酸甲酯及聚甲氧基二甲醚羰化物的制备 方法， 其特征在于， 将含有甲缩醛 CH30-CH2-OCH3、 一氧化碳和氢气的 原料通过载有脱铝改性的酸性分子筛催化剂的反应器， 在反应温度 60〜 140°C、 反应压力 2〜10 MPa甲缩醛质量空速为 0.2〜10.0 h— 1且不添加其 他溶剂的条件下反应，制备甲氧基乙酸甲酯及聚甲氧基二甲醚羰化物；反 应条件下原料甲缩醛与产物甲氧基乙酸甲酯及聚甲氧基二甲醚羰化物至 少一种为液相， 催化剂为固相， 原料一氧化碳和氢气为气相， 反应过程为 气液固三相反应； 原料中， 一氧化碳与甲缩醛的摩尔比为 2:1〜20:1， 氢 气与甲缩醛的摩尔比为 1 :1〜5:1。 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. By the reactor carrying the dealuminated modified acidic molecular sieve catalyst, the reaction temperature is 60 to 140 ° C, the reaction pressure is 2 to 10 MPa, and 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.
在一个优选实施方式中， 反应过程为气液固三相反应， 反应温度为 60〜： 120°C， 反应压力为 4〜： 10 MPa, 甲缩醛质量空速为 0.5〜3.0 h— 一 氧化碳与甲缩醛的摩尔比为 2: 1〜15: 1 优选的氢气与甲缩醛的摩尔比为 1 : 1〜3:1。 In a preferred embodiment, 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, and 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.
在一个优选实施方式中， 反应过程为气液固三相反应， 反应温度为 60〜90°C， 反应压力为 5.0〜10 MPa， 甲缩醛质量空速为 0.5〜1.5 h—1 , — 氧化碳与甲缩醛的摩尔比为 2: 1〜10: 1， 优选的氢气与甲缩醛的摩尔比为 1 : 1〜2:1。 In a preferred embodiment, 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, and 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, and the preferred molar ratio of hydrogen to methylal is 1: 1 to 2:1.
在一些实施例中，甲缩醛的转化率和产物的选择性都基于甲缩醛碳摩 尔数进行计算： In some embodiments, the conversion of methylal and the selectivity of the product are calculated based on the methylal number of methylal:
甲缩醛转化率 = [(进料中甲缩醛碳摩尔数：)一（出料中甲缩醛碳摩尔 数)] ÷ (进料中甲缩醛碳摩尔数：） X (100%) Conversion of methylal = [(mole of methyl acetal in feed:) 1 (molar of carbon in the output)] ÷ (molar of methyl acetal in feed:) X (100%)
甲氧基乙酸甲酯选择性 = (出料中甲氧基乙酸甲酯除去羰基后的碳 摩尔数) ÷ [(进料中甲缩醛碳摩尔数)一（出料中甲缩醛碳摩尔数) ] χ(ιοο%)
聚甲氧基二甲醚羰化物选择性 = (出料中聚甲氧基二甲醚羰化物除 去羰基后的碳摩尔数：) ÷ [(：进料中甲缩醛碳摩尔数） 一 (出料中甲缩醛碳摩 尔数）] X (100%) 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) ] χ(ιοο%) 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%)
所述的脱铝改性的方法包括水蒸气处理与酸处理。 The method of dealumination modification includes steam treatment and acid treatment.
所述的水蒸气处理温度为 400〜700°C， 优选 550〜650°C， 水蒸气处 理时间不限， 优选 1〜8 h; 酸处理中使用的酸为 0.03〜3.0 mol/L, 优选 0.1〜1.0 mol/L的盐酸、 硫酸、 硝酸、 醋酸、 草酸、 柠檬酸中的一种或者 多种混合酸，酸处理温度为 15〜95 °C，优选 60〜80 °C，酸处理时间不限， 优选 l〜24 h。 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.
所述的酸性分子筛催化剂的结构类型为 MWW、 FER、 MFI、 MOR、 FAU或 BEA。 优选地， 所述的酸性分子筛催化剂为 MCM-22分子筛、 镁 碱沸石、 ZSM-5分子筛、 丝光沸石、 Y沸石或 Beta分子筛中的任意一种 或任意几种的混合， 硅铝原子比为 3:1〜150:1。 The structure of the acidic molecular sieve catalyst is MWW, FER, MFI, MOR, FAU or BEA. Preferably, 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.
在实施例中， 钠型分子筛转换成酸性分子筛的标准操作程序为： 将 50 g干燥后的 Na+型分子筛放入 400 ml的 0.8 M N¾N03溶液中，在 80 °C 下搅拌 12 h， 过滤后用 800 ml的蒸馏水洗涤。 此离子交换过程重复三次 得到 N¾+型的分子筛。 经过充分干燥后， 置于马弗炉中， 以 2 °C/mm 升 高到 550 °C并保持煅烧 4 h得到酸性分子筛。 In the examples, 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.
所述的聚甲氧基二甲醚羰化物是在聚甲氧基二甲醚分子链的 The polymethoxy dimethyl ether carbonyl is in the molecular chain of polymethoxy dimethyl ether
-0-CH2-0-结构单元上插入羰基 -co-后形成的具有 -C CO C¾-O-或-0-CH2-0- formed on the structural unit after the insertion of a carbonyl group -co- has -C CO C3⁄4-O- or
-o-c¾-(co)-o-结构单元的产物，聚甲氧基二甲醚羰化物含有一个或多个 羰基。 The product of the -o-c3⁄4-(co)-o-structural unit, the polymethoxy dimethyl ether carbonyl compound contains one or more carbonyl groups.
实施例中产生的聚甲氧基二甲醚羰化物可以为以下中的一种或多种： The polymethoxy dimethyl ether carbonyl compound produced in the examples may be one or more of the following:
CH3-0-(CO) -CH2-0-CH2-0-CH3 简称为 C5-1, CH 3 -0-(CO) -CH 2 -0-CH 2 -0-CH 3 is abbreviated as C5-1,
CH3-0 -CH2-(CO)-0-CH2-0-CH3简称为 C5-2, CH 3 -0 -CH 2 -(CO)-0-CH 2 -0-CH 3 is abbreviated as C5-2,
CH3-0-(CO)-CH2-0-(CO)-CH2-0-CH3简称为 C6-1, CH 3 -0-(CO)-CH 2 -0-(CO)-CH 2 -0-CH 3 is abbreviated as C6-1,
CH3-0-(CO)-CH2-0-CH2-(CO)-0-CH3简称为 C6-2。 CH 3 -0-(CO)-CH 2 -0-CH 2 -(CO)-0-CH 3 is abbreviated as C6-2.
本发明的产物甲氧基乙酸甲酯或聚甲氧基二甲醚羰化物可以通过加 氢后水解或水解后加氢得到乙二醇， 此外， 所述产物还可以用作汽、柴油 添加剂。 例如， 以二聚甲氧基二甲醚 （DMM2) CH30(C¾0)2C¾为例简
要表达生成乙二醇的反应过程为: 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 The reaction process to express ethylene glycol is:
CO r CH30(CO) CH2OCH2OCH3 + CO r CH 3 0(CO) CH 2 OCH 2 OCH 3 +
CH30(CH20)2CH3 ► CH3OCH2(CO)OCH2OCH3+ CH 3 0(CH 2 0) 2 CH 3 ► CH 3 OCH 2 (CO)OCH 2 OCH 3 +
CH30(CO) CH20(CO)CH2OCH3+CH 3 0(CO) CH 2 0(CO)CH 2 OCH 3 +
、 CH30(CO) CH2OCH2(CO)OCH3 , CH 3 0(CO) CH 2 OCH 2 (CO)OCH 3
H20 H 2 0
HOCH2CH2OH HOCH 2 CH 2 OH
在一个优选实施方式中，所述反应器是连续流动的固定床反应器、釜 ；反应器、 移动床反应器或流化床反应器。 下面通过实施例详述本发明， 但本发明并不局限于这些实施例。 In a preferred embodiment, 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.
实施例 1 Example 1
将 50 g钠型硅铝比为 40:1的 MCM-22分子筛利用标准操作程序转换 成酸性分子筛， 记为催化剂 A， 见表 1。 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.
实施例 2 Example 2
将 100 g钠型硅铝比为 40:1的 MCM-22分子筛在 550 °C条件下通入 水蒸气处理 4 h， 然后利用标准操作程序转化成酸性分子筛， 记为催化剂 B, 见表 1。 100 g of MCM-22 molecular sieve with a ratio of 100 g of sodium-silica-aluminum to 40:1 was subjected to steam treatment at 550 °C for 4 h, and then converted into an acidic molecular sieve by a standard operating procedure, which was designated as Catalyst B, as shown in Table 1.
实施例 3 Example 3
将 100 g钠型硅铝比为 40:1的 MCM-22分子筛在 60 °C条件下 500 ml 的 0.1 mol/L盐酸溶液中处理 1 h， 然后利用标准操作程序转化成酸性分 子筛， 记为催化剂 C， 见表 1。 100 g of 40:1 MCM-22 molecular sieve was treated in 500 ml of 0.1 mol/L hydrochloric acid solution at 60 °C for 1 h, and then converted into acidic molecular sieve by standard operating procedure, which was recorded as catalyst. C, see Table 1.
实施例 4 Example 4
将 50 g钠型硅铝比为 10:1的镁碱沸石利用标准操作程序转换成酸性 分子筛， 记为催化剂 D， 见表 1。
实施例 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. Example 5
将 100 g钠型硅铝比为 10:1的镁碱沸石在 700 °C条件下通入水蒸气 处理 l h， 然后利用标准操作程序转化成酸性分子筛， 记为催化剂 E, 见 表 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.
实施例 6 Example 6
将 100 g钠型硅铝比为 10:1的镁碱沸石在 80 °C条件下 500 ml的 0.4 mol/L硫酸溶液中处理 4 h， 然后利用标准操作程序转化成酸性分子筛， 记为催化剂 F, 见表 1。 100 g of magnesium-alkaline zeolite with a sodium-to-silicon-aluminum ratio of 10:1 was treated in 500 ml of 0.4 mol/L sulfuric acid solution at 80 °C for 4 h, and then converted into acidic molecular sieve by standard operating procedure, which was recorded as catalyst F. See Table 1.
实施例 7 Example 7
将 50 g钠型硅铝比为 150:1的 ZSM-5分子筛利用标准操作程序转换 成酸性分子筛， 记为催化剂 G， 见表 1。 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.
实施例 8 Example 8
将 100 g钠型硅铝比为 150:1的 ZSM-5分子筛在 400 °C条件下通入 水蒸气处理 8 h， 然后利用标准操作程序转化成酸性分子筛， 记为催化剂 H, 见表 1。 100 g of ZSM-5 molecular sieve with a ratio of sodium chloride to aluminum of 150:1 was subjected to steam treatment at 400 °C for 8 h, and then converted into an acidic molecular sieve by a standard operating procedure, which was designated as catalyst H, as shown in Table 1.
实施例 9 Example 9
将 100 g钠型硅铝比为 150:1的 ZSM-5分子筛在 75 °C条件下 500 ml 的 1.0 mol/L醋酸溶液中处理 8 h， 然后利用标准操作程序转化成酸性分 子筛， 记为催化剂 I， 见表 1。 100 g of ZSM-5 molecular sieve with a sodium-to-silicon ratio of 150:1 was treated in 500 ml of 1.0 mol/L acetic acid solution at 75 °C for 8 h, and then converted into acidic molecular sieve by standard operating procedure, which was recorded as a catalyst. I, see Table 1.
实施例 10 Example 10
将 50 g钠型硅铝比为 3:1的丝光沸石利用标准操作程序转换成酸性 分子筛， 记为催化剂 J, 见表 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.
实施例 11 Example 11
将 100 g钠型硅铝比为 3:1的丝光沸石在 650 °C条件下通入水蒸气处 理 3 h， 然后利用标准操作程序转化成酸性分子筛， 记为催化剂 K， 见表 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.
实施例 12 Example 12
将 100 g钠型硅铝比为 3:1的丝光沸石在 60 °C条件下 500 ml的 3.0 mol/L柠檬酸溶液中处理 12 h， 然后利用标准操作程序转化成酸性分子 筛， 记为催化剂 L, 见表 1。
实施例 13 100 g of sodium silicate with a ratio of sodium to silicon and aluminum of 3:1 was treated in 500 ml of 3.0 mol/L citric acid solution at 60 °C for 12 h, and then converted into acidic molecular sieve by standard operating procedure, which was recorded as catalyst L. See Table 1. Example 13
将 50 g钠型硅铝比为 20:1的 Y分子筛利用标准操作程序转换成酸性 分子筛， 记为催化剂 M， 见表 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 recorded as Catalyst M, see Table 1.
实施例 14 Example 14
将 100 g钠型硅铝比为 20:1的 Y分子筛在 500 °C条件下通入水蒸气 处理 2 h， 然后利用标准操作程序转化成酸性分子筛， 记为催化剂 N， 见 表 1。 100 g of a 20:1 Y molecular sieve having a ratio of sodium to silicon and aluminum was subjected to steam treatment at 500 °C for 2 h, and then converted into an acidic molecular sieve by a standard operating procedure, which was designated as catalyst N, as shown in Table 1.
实施例 15 Example 15
将 100 g钠型硅铝比为 20:1的 Y分子筛在 95 °C条件下 500 ml的 1.5 mol/L草酸溶液中处理 5 h， 然后利用标准操作程序转化成酸性分子筛， 记为催化剂 0， 见表 1。 100 g of a 20:1 Y molecular sieve was treated in a 500 ml 1.5 mol/L oxalic acid solution at 95 °C for 5 h, and then converted into an acidic molecular sieve by a standard operating procedure, which was recorded as a catalyst 0. See Table 1.
实施例 16 Example 16
将 50 g钠型硅铝比为 15:1的 Beta分子筛利用标准操作程序转换成酸 性分子筛， 记为催化剂 P, 见表 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.
实施例 17 Example 17
将 100 g钠型硅铝比为 15:1的 Beta分子筛在 600 °C条件下通入水蒸 气处理 4 h， 然后利用标准操作程序转化成酸性分子筛， 记为催化剂 Q， 见表 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.
实施例 18 Example 18
将 100 g钠型硅铝比为 15:1的 Beta分子筛在 15 °C条件下 500 ml的 0.03 mol/L硝酸溶液中处理 24 h，然后利用标准操作程序转化成酸性分子 筛， 记为催化剂 R， 见表 1。
100 g of a 15:1 Beta molecular sieve was treated in 500 ml of 0.03 mol/L nitric acid solution at 15 °C for 24 h, and then converted into an acidic molecular sieve by a standard operating procedure, which was recorded as catalyst R. See Table 1.
表 1 实施例 1〜18中催化剂制备方法 Table 1 Example 1 to 18 catalyst preparation method
催化剂 A样品压片、 粉碎成 20〜40目， 用于活性测试。 称取该催化 剂 A 10 g， 装入内径为 8.5 mm的不锈钢反应管内， 在常压、 550°C下用氮 气活化 4小时， 然后降到反应温度 （T) =90 °C， 通入一氧化碳：二聚甲氧 基二甲醚： 氢气 (CO: DMM2: ¾)= 7:1 : 1， 缓慢升压到反应压力 (P) =10 MPa, 二聚甲氧基二甲醚质量空速WHSV;>=0.2 h—1,用气相色谱分析产物， 反应基本稳定后，计算二聚甲氧基二甲醚的转化率和聚甲氧基二甲醚羰化 物的选择性， 反应结果见表 2。 Catalyst A samples were compressed and pulverized into 20 to 40 mesh for activity testing. The catalyst A 10 g was weighed into a stainless steel reaction tube having an inner diameter of 8.5 mm, activated with nitrogen at normal pressure, 550 ° C for 4 hours, and then lowered to a reaction temperature (T) = 90 ° C, and carbon monoxide was introduced: Dimer methoxy dimethyl ether: Hydrogen (CO: DMM 2 : 3⁄4) = 7:1 : 1, Slowly boost to reaction pressure (P) = 10 MPa, Dimer methoxy dimethyl ether mass space velocity WHSV ;>=0.2 h- 1 , the product was analyzed by gas chromatography. After the reaction was basically stable, the conversion of dimer methoxy dimethyl ether and the selectivity of polymethoxy dimethyl ether carbonyl were calculated. The reaction results are shown in Table 2. .
实施例 20 Example 20
将实施例 19 中的催化剂换成催化剂 B， 其余实验歩骤与实施例 19 一致， 反应结果见表 2。 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.
实施例 21 Example 21
将实施例 19 中的催化剂换成催化剂 C， 其余实验歩骤与实施例 19 一致， 反应结果见表 2。 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.
实施例 22 Example 22
将实施例 19中的催化剂换成催化剂 D， 反应条件换为： T = 60 °C，
CO: DMM2: H2 = 13:1 :3 , P = 4MPa, WHSV^^ h—1 , 其余实验歩骤与实施 例 19一致， 反应结果见表 2。 The catalyst in Example 19 was changed to Catalyst D, and the reaction conditions were changed to: T = 60 °C, CO: DMM 2 : H 2 = 13:1 : 3 , P = 4 MPa, WHSV^^ h - 1 , and the remaining experimental steps were identical to those in Example 19, and the results are shown in Table 2.
实施例 23 Example 23
将实施例 22中的催化剂换成催化剂 E,其余实验歩骤与实施例 22— 致， 反应结果见表 2。 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.
实施例 24 Example 24
将实施例 22中的催化剂换成催化剂 F,其余实验歩骤与实施例 22— 致， 反应结果见表 2。 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.
实施例 25 Example 25
将实施例 19中的催化剂换成催化剂 G, 反应条件换为： T = 140 °C， CO: DMM2: H2 = 2:1 :5 , P = 6.5 MPa, WHSV =3.0 h"1 , , 其余实验歩骤与 实施例 19一致， 反应结果见表 2。 The catalyst of Example 19 was changed to Catalyst G, and the reaction conditions were changed to: T = 140 °C, CO: DMM 2 : H 2 = 2:1 : 5 , P = 6.5 MPa, WHSV = 3.0 h" 1 , , The remaining experimental procedures were identical to those of Example 19, and the results are shown in Table 2.
实施例 26 Example 26
将实施例 25 中的催化剂换成催化剂 H， 其余实验歩骤与实施例 25 一致， 反应结果见表 2。 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.
实施例 27 Example 27
将实施例 25中的催化剂换成催化剂 I， 其余实验歩骤与实施例 25— 致， 反应结果见表 2。 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.
实施例 28 Example 28
将实施例 19中的催化剂换成催化剂 J, 反应条件换为： T = 105 °C， CO: DMM2: H2 = 20:1 :1 , P =5.0MPa, WHSV =1.0 h—1,其余实验歩骤与实施 例 19一致， 反应结果见表 2。 The catalyst of Example 19 was changed to Catalyst J, and the reaction conditions were changed to: T = 105 ° C, CO: DMM 2 : H 2 = 20:1 :1 , P = 5.0 MPa, WHSV = 1.0 h - 1 , and the rest The experimental procedure was identical to that of Example 19, and the results of the reaction are shown in Table 2.
实施例 29 Example 29
将实施例 28 中的催化剂换成催化剂 K， 其余实验歩骤与实施例 28 一致， 反应结果见表 2。 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.
实施例 30 Example 30
将实施例 28中的催化剂换成催化剂 L,其余实验歩骤与实施例 28— 致， 反应结果见表 2。 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.
实施例 31 Example 31
将实施例 19中的催化剂换成催化剂 Μ, 反应条件换为： Τ = 73 °C，
CO: DMM2: H2 = 10:1:2, P = 2MPa, WHSV =10.0 h"1, 其余实验歩骤与实 施例 19一致， 反应结果见表 2。 The catalyst of Example 19 was replaced with a catalyst crucible, and the reaction conditions were changed to: Τ = 73 °C, CO: DMM 2 : H 2 = 10:1:2, P = 2 MPa, WHSV = 10.0 h" 1 , the remaining experimental steps were identical to those in Example 19, and the results are shown in Table 2.
实施例 32 Example 32
将实施例 31 中的催化剂换成催化剂 N， 其余实验歩骤与实施例 31 一致， 反应结果见表 2。 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.
实施例 33 Example 33
将实施例 31 中的催化剂换成催化剂 0， 其余实验歩骤与实施例 31 一致， 反应结果见表 2。 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.
实施例 34 Example 34
将实施例 19中的催化剂换成催化剂 P, 反应条件换为： T = 120 °C， CO: DMM2: ¾ = 15:1:4， P = 4.7MPa, WHSV =0.5 h"1 ， 其余实验歩骤与 实施例 19一致， 反应结果见表 2. The catalyst of Example 19 was changed to Catalyst P, and the reaction conditions were changed to: T = 120 °C, CO: DMM 2 : 3⁄4 = 15:1:4, P = 4.7 MPa, WHSV = 0.5 h" 1 , the remaining experiments The procedure is the same as in Example 19, and the reaction results are shown in Table 2.
实施例 35 Example 35
将实施例 34 中的催化剂换成催化剂 Q， 其余实验歩骤与实施例 34 一致， 反应结果见表 2。 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.
实施例 36 Example 36
将实施例 34 中的催化剂换成催化剂 R， 其余实验歩骤与实施例 34 一致， 反应结果见表 2。 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.
实施例 37 Example 37
催化剂 G样品压片、 粉碎成 20〜40目， 用于活性测试。 称取催化剂 样品 10 g， 装入内径为 8.5 mm的不锈钢反应管内， 在常压、 550°C下用 氮气活化 4 小时， 然后降到反应温度 （T) =88 °C， 通入原料一氧化碳: 聚甲氧基二甲醚： 氢气(^0: 0 11:¾：)=8:1:1， 其中 DMMn各组分的质 量比为： DMM2:DMM3:DMM4:DMM5 :DMM6 = 51.2 :26.6 : 12.8： 6.5： 2.9， 缓慢升压到反应压力 P) = 8 MPa, 聚甲氧基二甲醚质量空速 WHSV;>=1.5h— 用气相色谱分析产物， 反应基本稳定后， 反应结果见表 2。 The catalyst G sample was tableted and pulverized into 20 to 40 mesh for use in an activity test. 10 g of the catalyst sample was weighed, placed in a stainless steel reaction tube with an inner diameter of 8.5 mm, activated with nitrogen at normal pressure, 550 ° C for 4 hours, and then lowered to a reaction temperature (T) = 88 ° C, and passed through a raw material of carbon monoxide: Polymethoxy dimethyl ether: Hydrogen (^0: 0 11 : 3⁄4:) = 8:1:1, wherein the mass ratio of each component of DMM n is: DMM 2 : DMM 3 : DMM4: DMM 5 : DMM 6 = 51.2 : 26.6 : 12.8: 6.5: 2.9, Slowly boost to reaction pressure P) = 8 MPa, polymethoxy dimethyl ether mass space velocity WHSV; >= 1.5h - product analysis by gas chromatography, the reaction is basically stable The reaction results are shown in Table 2.
实施例 38 Example 38
将实施例 37中的催化剂换成催化剂 H， 其它条件不变， 反应结果见 表 2。
实施例 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
将实施例 37 中的催化剂换成催化剂 I， 其它条件不变， 反应结果见 表 2。 The catalyst of Example 37 was changed to Catalyst I, and the other conditions were unchanged. The reaction results are shown in Table 2.
实施例 40 Example 40
催化剂 M样品压片、粉碎成 20〜40目， 用于活性测试。称取催化剂 样品 10 g， 装入内径为 8.5 mm的不锈钢反应管内， 在常压、 550°C下用 氮气活化 4 小时， 然后降到反应温度 （T) =95 °C， 通入原料一氧化碳: 聚甲氧基二甲醚： 氢气CO: DMMn: ¾ ;)= 10:1 :1， 其中 DMMn各组分的质 量比为： DMM2： DMM3： DMM4： DMM5： DMM6 = 47.7： 26.9： 14.0： 7.8： 3.6， 缓慢升压到反应压力 P) =7 MPa , 聚甲氧基二甲醚质量空速 (WHSV)=2.0 h— 用气相色谱分析产物，反应基本稳定后，反应结果见表 2。 The catalyst M sample was tableted and pulverized into 20 to 40 mesh for use in an activity test. 10 g of the catalyst sample was weighed, placed in a stainless steel reaction tube with an inner diameter of 8.5 mm, activated with nitrogen at normal pressure, 550 ° C for 4 hours, and then lowered to the reaction temperature (T) = 95 ° C, and passed through the raw material carbon monoxide: Polymethoxy dimethyl ether: Hydrogen CO: DMM n : 3⁄4 ;) = 10:1 :1, wherein the mass ratio of each component of DMM n is: DMM 2 : DMM 3 : DMM4: DMM 5 : DMM 6 = 47.7 : 26.9: 14.0: 7.8: 3.6, Slowly boosted to reaction pressure P) = 7 MPa, polymethoxy dimethyl ether mass space velocity (WHSV) = 2.0 h - product analyzed by gas chromatography, reaction is basically stable, reaction The results are shown in Table 2.
实施例 41 Example 41
将实施例 40中的催化剂换成催化剂 N， 其它条件不变， 反应结果见 表 2。 The catalyst of Example 40 was changed to Catalyst N, and the other conditions were unchanged. The reaction results are shown in Table 2.
实施例 42 Example 42
将实施例 40中的催化剂换成催化剂 0， 其它条件不变， 反应结果见 表 2。 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.
对比例 1 Comparative example 1
将实施例 30中的气体比例换成 CO: DMM2: ¾ = 20:1 :0， 其余实验歩 骤与实施例 30—致， 反应结果见表 2。 The gas ratio in Example 30 was changed to CO: DMM 2 : 3⁄4 = 20:1:0, and the rest of the experimental procedures were the same as in Example 30, and the results are shown in Table 2.
对比例 2 Comparative example 2
将实施例 32中的气体比例换成 CO: DMM2: ¾ = 10:1 :0， 其余实验歩 骤与实施例 32—致， 反应结果见表 2。
The gas ratio in Example 32 was changed to CO: DMM 2 : 3⁄4 = 10:1:0, and the rest of the experimental procedures were the same as in Example 32, and the results are shown in Table 2.
买施例 19〜42与对比例 1~2的催化反应结果 Buying Examples 19~42 and Comparative Example 1~2 Catalytic Reaction Results
实施例 43 Example 43
催化剂 A样品压片、 粉碎成 20〜40目， 用于活性测试。 称取该催化 剂 A 10 g， 装入内径为 8.5 mm的不锈钢反应管内， 在常压、 550°C下用氮 气活化 4小时， 然后降到反应温度 0 = 90 °C， 通入一氧化碳:甲缩醛：氢 气 （CO: DMM: ¾ )= 7:1 : 1， 缓慢升压到反应压力 (P) = lO MPa, 控制甲缩 醛质量空速 (WHSV;)=0.2 h— 用气相色谱分析产物， 反应基本稳定后，计算 甲缩醛的转化率和产物的选择性， 反应结果见表 3。 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, Slowly pressurize to reaction pressure (P) = lO MPa, control methylal mass space velocity (WHSV;) = 0.2 h - product analyzed by gas chromatography After the reaction was substantially stable, the conversion of methylal and the selectivity of the product were calculated. The reaction results are shown in Table 3.
实施例 44 Example 44
将实施例 43 中的催化剂换成催化剂 B， 其余实验歩骤与实施例 43 一致， 反应结果见表 3。 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.
实施例 45 Example 45
将实施例 43 中的催化剂换成催化剂 C， 其余实验歩骤与实施例 43 一致， 反应结果见表 3。 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.
实施例 46 Example 46
将实施例 43中的催化剂换成催化剂 D， T = 60 °C， CO: DMM: ¾ = 13:1 :3， P = 4MPa, WHSV=1.5 h— 其余实验歩骤与实施例 43—致， 反应 结果见表 3。 The catalyst of Example 43 was replaced by Catalyst D, T = 60 °C, CO: DMM: 3⁄4 = 13:1:3, P = 4 MPa, WHSV = 1.5 h - the remaining experimental steps were consistent with Example 43. The reaction results are shown in Table 3.
实施例 47 Example 47
将实施例 46中的催化剂换成催化剂 E,其余实验歩骤与实施例 46— 致， 反应结果见表 3。 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.
实施例 48 Example 48
将实施例 46中的催化剂换成催化剂 F,其余实验歩骤与实施例 46— 致， 反应结果见表 3。 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.
实施例 49 Example 49
将实施例 43中的催化剂换成催化剂 G， 反应条件换为： T = 140 °C , CO: DMM: ¾ = 2:1 :5, P= 6.5 MPa, WHSV=3.0 h"1 ,其余实验歩骤与实施例The catalyst in Example 43 was changed to Catalyst G, and the reaction conditions were changed to: T = 140 °C, CO: DMM: 3⁄4 = 2:1:5, P = 6.5 MPa, WHSV = 3.0 h" 1 , the remaining experiments歩And examples
43—致， 反应结果见表 3。 43—The reaction results are shown in Table 3.
实施例 50 Example 50
将实施例 49 中的催化剂换成催化剂 H， 其余实验歩骤与实施例 49 一致， 反应结果见表 3。
实施例 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
将实施例 49中的催化剂换成催化剂 I， 其余实验歩骤与实施例 49一 致， 反应结果见表 3。 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.
实施例 52 Example 52
将实施例 43中的催化剂换成催化剂 J，反应条件换为： T = 105 °C , CO: DMM: ¾ = 20:1 : 1, P= 5.0 MPa, WHSV=1.0 h"1 ,其余实验歩骤与实施例 43 一致， 反应结果见表 3。 The catalyst in Example 43 was changed to Catalyst J, and the reaction conditions were changed to: T = 105 °C, CO: DMM: 3⁄4 = 20:1: 1, P = 5.0 MPa, WHSV = 1.0 h" 1 , the remaining experiments歩The results are in agreement with Example 43 and the results are shown in Table 3.
实施例 53 Example 53
将实施例 52 中的催化剂换成催化剂 K， 其余实验歩骤与实施例 52 一致， 反应结果见表 3。 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.
实施例 54 Example 54
将实施例 52中的催化剂换成催化剂 L,其余实验歩骤与实施例 52— 致， 反应结果见表 3。 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.
实施例 55 Example 55
将实施例 43中的催化剂换成催化剂 Μ,反应条件换为： Τ = 73 °C , CO: DMM: ¾ = 10:1 :2, P= 2 MPa, WHSV=10.0 h"1 , 其余实验歩骤与实施例 43 一致， 反应结果见表 3。 The catalyst in Example 43 was replaced with a catalyst crucible, and the reaction conditions were changed to: Τ = 73 °C, CO: DMM: 3⁄4 = 10:1:2, P = 2 MPa, WHSV = 10.0 h" 1 , the remaining experiments歩The results are in agreement with Example 43 and the results are shown in Table 3.
实施例 56 Example 56
将实施例 55 中的催化剂换成催化剂 N， 其余实验歩骤与实施例 55 一致， 反应结果见表 3。 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.
实施例 57 Example 57
将实施例 55 中的催化剂换成催化剂 0， 其余实验歩骤与实施例 55 一致， 反应结果见表 3。 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.
实施例 58 Example 58
将实施例 43中的催化剂换成催化剂 P,反应条件换为：T = 120 °C , CO: DMM: ¾ = 15:1 :4, P= 4.7 MPa, WHSV=0.5 h"1 ,其余实验歩骤与实施例 43 一致， 反应结果见表 3。 The catalyst in Example 43 was changed to Catalyst P, and the reaction conditions were changed to: T = 120 °C, CO: DMM: 3⁄4 = 15:1:4, P = 4.7 MPa, WHSV = 0.5 h" 1 , the remaining experiments歩The results are in agreement with Example 43 and the results are shown in Table 3.
实施例 59 Example 59
将实施例 58 中的催化剂换成催化剂 Q， 其余实验歩骤与实施例 58 一致， 反应结果见表 3。
实施例 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
将实施例 58 中的催化剂换成催化剂 R， 其余实验歩骤与实施例 一致， 反应结果见表 3。 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.
对比例 3 Comparative example 3
将实施例 54中的气体比例换为 CO: DMM: ¾ = 20:1:0， 其余实验 骤与实施例 54—致， 反应结果见表 3。 The gas ratio in Example 54 was changed to CO: DMM: 3⁄4 = 20:1:0, and the remaining experiments were carried out in the same manner as in Example 54 and the results are shown in Table 3.
对比例 4 Comparative example 4
将实施例 56中的气体比例换为 CO: DMM: ¾ = 10:1:0， 其余实验 骤与实施例 56—致， 反应结果见表 3。
The gas ratio in Example 56 was changed to CO: DMM: 3⁄4 = 10:1:0, and the remaining experiments were carried out in the same manner as in Example 56, and the results are shown in Table 3.
买施例 43〜60与对比例 3-4的催化反应结果 Buying Examples 43~60 and Comparative Example 3-4 Catalytic Reaction Results
本发明的有益效果包括但不限于：本发明的方法所采用的催化剂为脱 铝改性的酸性分子筛催化剂，原料为聚甲氧基二甲醚或甲缩醛连同一氧化 碳和氢气的混合气。在本发明的反应条件下， 原料通过催化剂能够稳定高 效生产作为生产乙二醇的中间体的产物聚甲氧基二甲醚羰化物或甲氧基 乙酸甲酯， 反应过程为气液固三相反应。 甲氧基二甲醚或甲缩醛羰基化反 应为强放热反应， 本发明中反应温度比较低， 再加上液相热容大与相变潜 热， 能够很好控制反应温度， 防止工业生产过程中飞温的问题。 同时本发 明采用的气液固三相反应能够在高的聚甲氧基二甲醚或甲缩醛浓度下操 作， 提高了工业生产中单程反应产能， 减少了压缩、循环以及分离过程中 的能耗， 提高经济性能。 Advantageous effects of the present invention include, but are not limited to, the catalyst used in the process of the present invention is a dealuminated modified acidic molecular sieve catalyst, and the raw material is polymethoxy dimethyl ether or methylal with a mixture of the same carbon oxide and hydrogen. Under the reaction conditions of the present invention, 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. In the present invention, 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 problem of flying temperature in the process. At the same time, 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.
本发明中原料聚甲氧基二甲醚或甲缩醛的转化率高，产物聚甲氧基二 甲醚羰化物或甲氧基乙酸甲酯选择性高， 催化剂单程寿命长。此外， 在本 发明方法中， 液相原料反应物或产物本身就是优良溶剂， 不需要使用外加 溶剂。另外液相反应物或产物能够溶解催化反应过程中的预积碳物质， 有 利于提高催化剂的活性和稳定性， 反应条件比较温和， 能够连续生产， 具 备工业化应用潜力。 In the present invention, 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. Further, in the process of the present invention, the liquid phase raw material reactant or product itself is an excellent solvent, and no additional solvent is required. In addition, 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.
而且， 本发明中羰基化反应采用一氧化碳和氢气的混合气作为气相， 相对于现有煤化工生产乙二醇技术需要高纯度一氧化碳，本发明不需要高 纯度一氧化碳， 可以大幅度降低合成气分离能耗， 提高生产过程中的经济 性。另外反应气中加入氢气还能够提高聚甲氧基二甲醚或甲缩醛转化率和 聚甲氧基二甲醚羰化物或甲氧基乙酸甲酯选择性， 延长催化剂单程寿命。 Moreover, in the present invention, 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. In addition, 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.
本发明中的分子筛脱铝改性方法简单易操作， 适合工业大规模生产， 经过脱铝改性能够将催化剂的单程寿命延长 5〜10倍，非常有效地减少了 每年催化剂重生的次数， 有利于提高年产能力， 减少原料浪费， 减少废气 废水排放， 减少催化剂因泄压和烧积碳而造成的损耗， 延长生产设备使用 周期， 提高经济性能。 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.
此外，本发明中生产的聚甲氧基二甲醚羰化物或甲氧基乙酸甲酯能够 通过加氢水解或者水解后加氢生产乙二醇。
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。
Further, the 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 specific embodiments described herein. 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.
Claims
1、 一种通过羰基化制备作为生产乙二醇的中间体的聚甲氧基二甲醚 羰化物的方法， 其特征在于， 将原料聚甲氧基二甲醚 CH30(CH20)nCH3 连同一氧化碳和氢气通过载有脱铝改性的酸性分子筛催化剂的反应器，在 反应温度 60〜140°C、 反应压力 2〜10 MPa、 聚甲氧基二甲醚质量空速为 0.2〜10.0 且不添加其他溶剂的条件下反应制备产物聚甲氧基二甲醚羰 化物，其中在所述反应条件下，所述原料与所述产物中的至少一种为液相， 所述脱铝改性的酸性分子筛催化剂为固相，一氧化碳和氢气为气相以使反 应过程为气液固三相反应， 并且一氧化碳与所述原料的摩尔比为 2:1〜 20:1 , 氢气与所述原料的摩尔比为 1 :1〜5:1， 其中 n 2且为整数。 1. A method for preparing polymethoxydimethylether carbonyl as an intermediate for the production of ethylene glycol through carbonylation, which is characterized in that the raw material polymethoxydimethylether CH 3 0 (CH 2 0) n CH 3 together with carbon monoxide and hydrogen pass through a reactor carrying a dealumination-modified acidic molecular sieve catalyst, at a reaction temperature of 60~140°C, a reaction pressure of 2~10 MPa, and a polymethoxydimethylether mass space velocity of 0.2 ~10.0 and the product polymethoxydimethyl ether carbonyl is prepared by reaction without adding other solvents, wherein under the reaction conditions, at least one of the raw material and the product is in liquid phase, and the dehydration The aluminum-modified acidic molecular sieve catalyst is in the solid phase, and carbon monoxide and hydrogen are in the gas phase so that the reaction process is a gas-liquid-solid three-phase reaction, and the molar ratio of carbon monoxide to the raw material is 2:1~20:1, and the molar ratio of hydrogen and the The molar ratio of raw materials is 1:1~5:1, where n is 2 and is an integer.
2、 一种通过羰基化制备作为生产乙二醇的中间体甲氧基乙酸甲酯及 聚甲氧基二甲醚羰化物的方法， 其特征在于， 将原料甲缩醛 CH30-CH2-OCH3连同一氧化碳和氢气通过载有脱铝改性的酸性分子筛催 化剂的反应器， 在反应温度 60〜140°C、 反应压力 2〜10 MPa、 甲缩醛质 量空速为 0.2〜10.0 h"1且不添加其他溶剂的条件下反应制备产物甲氧基乙 酸甲酯及聚甲氧基二甲醚羰化物， 其中在所述反应条件下， 所述原料与所 述产物中的至少一种为液相， 所述脱铝改性的酸性分子筛催化剂为固相， 一氧化碳和氢气为气相以使反应过程为气液固三相反应，并且一氧化碳与 所述原料的摩尔比为 2:1〜20:1， 氢气与所述原料的摩尔比为 1 :1〜5:1。 2. A method for preparing methyl methoxyacetate and polymethoxydimethyl ether carbonyl as intermediates for the production of ethylene glycol through carbonylation, characterized in that the raw material methylal CH 3 0-CH 2 -OCH 3 together with carbon monoxide and hydrogen pass through a reactor carrying a dealumination-modified acidic molecular sieve catalyst, at a reaction temperature of 60~140°C, a reaction pressure of 2~10 MPa, and a methylal mass space velocity of 0.2~10.0 h." 1. Preparation of products methyl methoxyacetate and polymethoxydimethylether carbonyl by reaction without adding other solvents, wherein under the reaction conditions, at least one of the raw materials and the products is Liquid phase, the dealumination-modified acidic molecular sieve catalyst is in the solid phase, carbon monoxide and hydrogen are in the gas phase so that the reaction process is a gas-liquid-solid three-phase reaction, and the molar ratio of carbon monoxide to the raw material is 2:1~20: 1. The molar ratio of hydrogen to the raw material is 1:1~5:1.
3、 根据权利要求 1或 2所述的方法， 其特征在于， 所述产物聚甲氧 基二甲醚羰化物是在聚甲氧基二甲醚 CH3O CH20;)nCH3 分子链的 -0-CH2-0-结构单元中插入一个或多个羰基 -CO-后形成的具有 -0-(CO)-C¾-0-或 -0-C¾-(CO)-0-结构单元的产物， 其中 n 2。 3. The method according to claim 1 or 2, characterized in that the product polymethoxydimethylether carbonyl is polymethoxydimethylether CH 3 O CH 2 0;) n CH 3 molecules The -0-(CO)-C¾-0- or -0-C¾-(CO)-0- structural unit formed by inserting one or more carbonyl groups -CO- into the -0-CH2-0- structural unit of the chain The product of , where n 2.
4、 根据权利要求 1所述的方法， 其特征在于， 所述聚甲氧基二甲醚 为二聚甲氧基二甲醚 CH30(C¾0)2CH3。 4. The method according to claim 1, characterized in that the polymethoxydimethylether is dimethoxydimethylether CH 3 0 (C¾0) 2 CH 3 .
5、 根据权利要求 1或 2所述的方法， 其特征在于， 所述聚甲氧基二 甲醚羰化物为以下中的一种或多种： 5. The method according to claim 1 or 2, characterized in that the polymethoxydimethyl ether carbonyl compound is one or more of the following:
CH3-0-(CO)-CH2-0-CH2-0-CH3， CH 3 -0-(CO)-CH 2 -0-CH 2 -0-CH 3 ,
CH3-0 -C¾-(CO)-0-C¾-0-CH3，
CH3-0-(CO)-CH2-0-(CO)-CH2-0-CH3， 禾口 CH 3 -0 -C¾-(CO)-0-C¾-0-CH 3 , CH 3 -0-(CO)-CH 2 -0-(CO)-CH 2 -0-CH 3 , Hekou
CH3-0-(CO)-CH2-0-CH2-(CO)-0-CH3。 CH 3 -0-(CO)-CH 2 -0-CH 2 -(CO)-0-CH 3 .
6、 根据权利要求 1或 2所述的方法， 其特征在于， 所述脱铝改性的 酸性分子筛催化剂通过使酸性分子筛催化剂经过包括水蒸气处理与酸处 理的脱铝改性制备。 6. The method according to claim 1 or 2, characterized in that the dealumination-modified acidic molecular sieve catalyst is prepared by subjecting the acidic molecular sieve catalyst to dealumination modification including steam treatment and acid treatment.
7、 根据权利要求 6所述的方法， 其特征在于， 所述水蒸气处理的温 度为 400〜700°C， 时间为 1〜8 h; 所述酸处理中使用的酸为 0.03〜3.0 mol/L的选自盐酸、 硫酸、 硝酸、 醋酸、 草酸、 柠檬酸中的一种或者多种 酸， 并且所述酸处理的温度为 15〜95 °C， 时间为 l〜24 h。 7. The method according to claim 6, characterized in that the temperature of the steam treatment is 400~700°C and the time is 1~8 h ; the acid used in the acid treatment is 0.03~3.0 mol/ L is selected from one or more acids selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, and citric acid, and the acid treatment temperature is 15 to 95 ° C, and the time is 1 to 24 h.
8、 根据权利要求 1或 2所述的方法， 其特征在于， 所述脱铝改性的 酸性分子筛催化剂的结构类型为 MWW、 FER、 MFI、 MOR、 FAU或 BEA。 8. The method according to claim 1 or 2, characterized in that the structural type of the dealumination-modified acidic molecular sieve catalyst is MWW, FER, MFI, MOR, FAU or BEA.
9、 根据权利要求 8所述的方法， 其特征在于， 所述脱铝改性的酸性 分子筛催化剂为 MCM-22分子筛、 镁碱沸石、 ZSM-5分子筛、 丝光沸石、 Y沸石或 Beta分子筛中的一种或几种。 9. The method according to claim 8, characterized in that the dealumination-modified acidic molecular sieve catalyst is MCM-22 molecular sieve, ferrierite, ZSM-5 molecular sieve, mordenite, Y zeolite or Beta molecular sieve. One or several.
10、根据权利要求 1或 2所述的方法， 其特征在于， 反应温度为 60〜 120 °C , 反应压力为 4〜： 10 MPa， 所述原料的质量空速为 0.5〜3.0 h— 一 氧化碳与所述原料的摩尔比为 2:1〜15:1， 氢气与所述原料的摩尔比为 1:1〜3:1。 10. The method according to claim 1 or 2, characterized in that the reaction temperature is 60~120°C, the reaction pressure is 4~10 MPa, and the mass space velocity of the raw material is 0.5~3.0 h - carbon monoxide and The molar ratio of the raw materials is 2:1~15:1, and the molar ratio of hydrogen to the raw materials is 1:1~3:1.
11、根据权利要求 1或 2所述的方法， 其特征在于， 反应温度为 60〜 90°C， 反应压力为 5〜： lO MPa, 所述原料的质量空速为 0.5〜1.5 h— 一氧 化碳与所述原料的摩尔比为 2:1〜10:1， 氢气与所述原料的摩尔比为 1 :1〜 2:1。 11. The method according to claim 1 or 2, characterized in that the reaction temperature is 60~90°C, the reaction pressure is 5~10 MPa, and the mass space velocity of the raw material is 0.5~1.5 h - carbon monoxide and The molar ratio of the raw materials is 2:1~10:1, and the molar ratio of hydrogen to the raw materials is 1:1~2:1.
12、 根据权利要求 1或 2所述的方法， 其特征在于， 所述反应器是实 现连续反应的固定床反应器、釜式反应器、移动床反应器或流化床反应器。
12. The method according to claim 1 or 2, characterized in that the reactor is a fixed bed reactor, a kettle reactor, a moving bed reactor or a fluidized bed reactor that realizes continuous reaction.
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| CN107899609A (en) * | 2017-11-16 | 2018-04-13 | 山西大学 | A kind of catalyst for producing polyoxymethylene dimethyl ether and preparation method thereof |
| CN111995521A (en) * | 2020-09-01 | 2020-11-27 | 山西大学 | Reaction device and method for synthesizing methyl methoxyacetate by virtue of gas-phase carbonylation of dimethoxymethane |
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| CN107899609A (en) * | 2017-11-16 | 2018-04-13 | 山西大学 | A kind of catalyst for producing polyoxymethylene dimethyl ether and preparation method thereof |
| CN107899609B (en) * | 2017-11-16 | 2020-07-10 | 山西大学 | Catalyst for producing polyformaldehyde dimethyl ether and preparation method thereof |
| CN111995521A (en) * | 2020-09-01 | 2020-11-27 | 山西大学 | Reaction device and method for synthesizing methyl methoxyacetate by virtue of gas-phase carbonylation of dimethoxymethane |
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