CN114054024A - Dimethyl oxalate hydrogenation catalyst and preparation method and application thereof - Google Patents
Dimethyl oxalate hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN114054024A CN114054024A CN202111150411.5A CN202111150411A CN114054024A CN 114054024 A CN114054024 A CN 114054024A CN 202111150411 A CN202111150411 A CN 202111150411A CN 114054024 A CN114054024 A CN 114054024A
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- China
- Prior art keywords
- catalyst
- active component
- dimethyl oxalate
- oxalate hydrogenation
- hydrogenation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 153
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 92
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 27
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 24
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 150000001879 copper Chemical class 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000011863 silicon-based powder Substances 0.000 claims description 4
- 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 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims 8
- 238000001704 evaporation Methods 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 31
- 230000001276 controlling effect Effects 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 229910052681 coesite Inorganic materials 0.000 description 16
- 229910052906 cristobalite Inorganic materials 0.000 description 16
- 229910052682 stishovite Inorganic materials 0.000 description 16
- 229910052905 tridymite Inorganic materials 0.000 description 16
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 13
- 238000001308 synthesis method Methods 0.000 description 11
- 229940083957 1,2-butanediol Drugs 0.000 description 10
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 239000012265 solid product Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 2
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ZUPBPXNOBDEWQT-UHFFFAOYSA-N [Si].[Ni].[Cu] Chemical compound [Si].[Ni].[Cu] ZUPBPXNOBDEWQT-UHFFFAOYSA-N 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a dimethyl oxalate hydrogenation catalyst, a preparation method and application thereof. The dimethyl oxalate hydrogenation catalyst comprises a carrier and active components, wherein the carrier is silicon dioxide In various forms, the active components comprise a main active component and an auxiliary active component, the main active component is copper, the auxiliary active component is one metal selected from Ni, In, Mo, W, Fe and Zn and/or an oxide thereof, and the atomic ratio of the auxiliary active component to the main active component is 0.2-1.5 In terms of metal. The preparation method comprises ammonia evaporation, dipping, deposition and precipitation and sol-gel method. The catalyst of the invention can control the variety of products by adjusting the mixture ratio of each component in the catalyst and the reaction condition of dimethyl oxalate hydrogenation, and separately obtain high-selectivity methyl glycolate or ethylene glycol, thereby being beneficial to the switching production of products in industrial practical application.
Description
Technical Field
The invention relates to a dimethyl oxalate hydrogenation catalyst, a preparation method and application thereof, and relates to the technical field of coal chemical catalysts.
Background
Methyl glycolate has both chemical properties of alcohol and ester due to its unique molecular structure, can undergo carbonylation reaction, hydrolysis reaction, oxidation reaction and the like, and is an important chemical raw material. Can be widely used in chemical industry, medicine, pesticide, feed, spice, fuel and other fields. In particular, methyl glycolate can be used as a raw material of degradable plastics, and with the rapid development and application of degradable plastics, the market demand for methyl glycolate is rapidly increasing.
Ethylene Glycol (EG) is an important petrochemical basic organic raw material and is mainly used for producing polyester fibers, antifreeze, unsaturated polyester resins and the like. The global demand of ethylene glycol is about 2500 million tons/year, the demand is large, the ethylene glycol is a basic organic raw material for petrochemical industry, and downstream application relates to numerous fields.
Patent CN112717938A discloses a method for preparing a catalyst for preparing methyl glycolate by dimethyl oxalate, which comprises dissolving copper nitrate in deionized water, wherein the concentration of copper ions is 0.1-2 mol/L; adding the mixture into concentrated ammonia water with the mass fraction of 25-28% to obtain a first solution, wherein the pH value of the solution is 9-12; adding the powder silicon dioxide or silica sol into deionized water, stirring for 0.5-1 hour, then adding into the first solution, and stirring for 3-5 hours at 20-30 ℃; distilling ammonia at the temperature of 85-95 ℃ until the pH value of the first solution is 6-7; performing suction filtration, washing the solid product with deionized water for three times, drying the solid product in an oven at 100-120 ℃ for 8-12 hours, and baking the solid product in a muffle furnace at 300-500 ℃ for 3-10 hours in flowing air atmosphere to obtain a solid; dissolving the solid in deionized water, and stirring for 0.5-1 hour to obtain a second solution; dissolving nickel nitrate in deionized water, wherein the concentration of nickel ions is 0.1-2 mol/L, and obtaining a third solution; dropwise adding 25-28% of concentrated ammonia water into the third solution, wherein the pH value of the solution is 9-12; mixing the second solution and the third solution, and stirring for 3-5 hours at the temperature of 20-30 ℃; distilling ammonia at the temperature of 85-95 ℃ until the pH value of the mixed solution is 6-7; and (3) carrying out suction filtration, washing the solid product with deionized water for three times, drying the solid product in an oven at 100-120 ℃ for 8-12 hours, and roasting the dried product in a muffle furnace at 300-500 ℃ for 3-10 hours in flowing air atmosphere to obtain the catalyst. Wherein the using amount of the concentrated ammonia water meets the condition that the molar ratio of copper ions to ammonia molecules is 4: 1-12: 1.
Patent CN112717929A discloses a method for preparing an ethylene glycol catalyst by dimethyl oxalate liquid-phase hydrogenation, which comprises the steps of dissolving soluble copper salt with deionized water, wherein the concentration of copper ions is 0.1-2 mol/L, and obtaining a first dissolved solution; mixing sodium silicate and a precipitator, and then dissolving with deionized water to obtain a second dissolved solution; mixing the first solution and the second solution, dripping deionized water with the temperature of 75-85 ℃ in the stirring process for precipitation, keeping the pH of the system at 8.5-9.5 after the dripping is finished, and aging for half a hour; and (3) carrying out suction filtration on the mixed solution, washing the solid product with deionized water for six times, drying the solid product in an oven at 100-120 ℃ for 8-12 hours, and roasting the dried solid product in a muffle furnace at 300-500 ℃ for 3-10 hours in flowing air atmosphere to form the catalyst. The sodium silicate is used in an amount such that the molar ratio of copper ions to silicate groups is 1:1, and the precipitant is used in an amount such that the molar ratio of copper ions to precipitant molecules is 10: 1-15: 1. Wherein, the precipitator is any one of sodium silicate or sodium carbonate. Wherein the specific surface area of the catalyst is 300-500m2Per g, effective copper surface area of 24-28m2/g。
From these results, it is understood that the catalyst used in the liquid-phase hydrogenation of dimethyl oxalate for ethylene glycol production is a copper-silicon catalyst obtained by the coprecipitation method, and that the catalyst used in the liquid-phase hydrogenation of dimethyl oxalate for methyl glycolate production is a copper-nickel-silicon catalyst obtained by the ammonia distillation method.
Disclosure of Invention
The problems existing in the prior art are as follows: the preparation method is complex, and different catalysts are used for preparing the ethylene glycol and the methyl glycolate, so that the process is complicated. The invention provides a dimethyl oxalate hydrogenation catalyst aiming at the defects in the prior art, which can be suitable for preparing ethylene glycol or methyl glycolate by liquid phase hydrogenation of dimethyl oxalate by adjusting the atomic ratio of a co-active component to a main active component, namely, when the atomic ratio of the co-active component to the main active component is in a certain range, the selectivity of ethylene glycol is strong, and when the atomic ratio of the co-active component to the main active component is in another range, the selectivity of methyl glycolate is strong, and the selectivity of 1, 2-butanediol and ethanol as byproducts can be reduced to the minimum.
In one aspect, the invention provides a dimethyl oxalate hydrogenation catalyst, which comprises a carrier and an active component, wherein the carrier is silicon dioxide In various forms, the active component comprises a main active component and an auxiliary active component, the main active component is copper, the auxiliary active component is one metal selected from Ni, In, Mo, W, Fe and Zn and/or an oxide thereof, and the atomic ratio of the auxiliary active component to the main active component is 0.2-1.5 In terms of the atomic ratio of the metal.
Among them, preferably, according to the above dimethyl oxalate hydrogenation catalyst, wherein the silica is one or more from the following silica source group: silica sol, fumed silica, ethyl orthosilicate, amorphous silicon powder and an all-silicon molecular sieve.
Among them, preferably, the above dimethyl oxalate hydrogenation catalyst, wherein the atomic ratio of the co-active component to the main active component is 1 to 1.5.
Among them, preferably, the above dimethyl oxalate hydrogenation catalyst, wherein the atomic ratio of the co-active component to the main active component is 0.2 to 0.8.
Wherein, preferably, the dimethyl oxalate hydrogenation catalyst according to any one of the previous embodiments, wherein the content of silica accounts for 20-80 wt%, preferably 20-75 wt%, of the total mass of the catalyst.
In another aspect, the present invention provides a first preparation method of a dimethyl oxalate hydrogenation catalyst, comprising the steps of: respectively dissolving soluble copper salt and soluble metal salt in deionized water at the temperature of 20-30 ℃ to obtain salt solutions, respectively adding ammonia water to adjust the salt solutions into complex solutions, mixing the complex solutions, adding the mixed solution, a silicon dioxide source and a silicon dioxide source into a reaction kettle in a co-feeding manner, and heating to evaporate ammonia until the pH value in the kettle is 6-7; and carrying out aftertreatment to obtain the catalyst.
Among them, preferably, according to the above production method, wherein the concentration of the aqueous ammonia is 15 to 25 wt%.
In another aspect, the present invention provides a second preparation method of a dimethyl oxalate hydrogenation catalyst, comprising the steps of: dissolving soluble metal salt in deionized water to obtain a salt solution, adding a silicon dioxide source, carrying at 20-30 ℃ for 2-24h to obtain a mixture, and carrying out post-treatment to obtain the catalyst.
In another aspect, the present invention provides a third method for preparing a dimethyl oxalate hydrogenation catalyst, comprising the steps of: dissolving soluble copper salt and soluble metal salt in deionized water at the temperature of 20-30 ℃ to obtain a salt solution, adding a silicon dioxide source, dropwise adding a NaOH aqueous solution to obtain a mixed material after dropwise adding is finished, and performing aftertreatment to obtain the catalyst.
The above production method, wherein the concentration of the aqueous NaOH solution is 0.5 to 1.5 mol/l.
In another aspect, the present invention provides a fourth method for preparing a dimethyl oxalate hydrogenation catalyst, comprising the steps of: adding soluble copper salt and soluble metal salt into deionized water at 20-30 ℃ to obtain a salt solution, adding a silicon dioxide source, standing at 50-70 ℃ for hydrolysis (preferably hydrolysis for 12-72h) to obtain a mixture, and performing post-treatment to obtain the catalyst.
Wherein, preferably, in the preparation method, the post-treatment comprises the processes of drying, roasting and forming, the drying temperature of the catalyst is 80-120 ℃, and the drying time is 8-24 h; the calcination temperature is preferably 250 ℃ and 520 ℃, and the calcination time is more preferably 4 to 20 hours.
Wherein preferably the post-treatment further comprises reducing the catalyst in a hydrogen atmosphere after shaping.
Wherein, preferably, in the preparation method, the reduction is carried out for 1-5h at 200-450 ℃.
Wherein, the reduction can also be carried out in two steps, including reduction at 200-300 ℃ for 5-7h, and then reduction at 350-450 ℃ for 1-3 h.
On the other hand, the invention also provides a dimethyl oxalate hydrogenation catalyst prepared by the preparation method.
In another aspect, the present invention also provides a method for producing methyl glycolate or diethanol by hydrogenation of dimethyl oxalate, which is characterized in that: the dimethyl oxalate hydrogenation catalyst is used for the fixed bed dimethyl oxalate hydrogenation synthesis, the reaction temperature is 150-250 ℃, the reaction pressure is 0.1-6Mpa, and the mass space velocity of the dimethyl oxalate is 0.5-3h-1The hydrogen-oil ratio is 5-500: 1.
Wherein, preferably, the catalyst is reduced in a hydrogen atmosphere before the catalytic reaction is carried out.
Wherein, preferably, the reduction is carried out for 1-5h at 200-450 ℃;
wherein, the reduction is carried out for two steps, the two steps comprise reduction at 300 ℃ for 5-7h at 200 ℃ and reduction at 450 ℃ for 1-3h at 350 ℃.
In another aspect, the present invention also provides a method for controlling the ratio of methyl glycolate to ethylene glycol in a dimethyl oxalate hydrogenation reaction product by adjusting the ratio of active components of the catalyst of the present invention, characterized in that the catalyst of any one of the above embodiments is used, wherein the weight content of ethylene glycol generated in the dimethyl oxalate reaction product is 99.0% or more by controlling the content ratio of the co-active component to the main active component in terms of metal atom ratio to be in the range of 0.2 to 0.8; the content ratio of the auxiliary active component and the main active component is controlled within the range of 1-1.5, so that the weight content of the generated methyl glycolate in the dimethyl oxalate reaction product is more than 99.0 percent.
The invention provides a catalyst which can be applied to dimethyl oxalate hydrogenation, the phenomenon that 1, 2-butanediol and ethanol which are byproducts are difficult to separate in the main reaction is solved, the generation of byproducts is fundamentally solved, and the principle that the byproducts are not generated and are not separated is avoided.
Detailed Description
The dimethyl oxalate hydrogenation reaction formula is as follows:
the 1 st reaction formula is to produce methyl glycolate, and the second reaction formula is to produce ethylene glycol, both of which have 1, 2-butanediol and ethanol as by-products, wherein further hydrogenation of ethylene glycol produces ethanol, further reaction of ethylene glycol with ethanol produces 1, 2-butanediol, and both of these by-products are difficult to separate from the main product, and therefore, the production of these two by-products is suppressed as much as possible.
The dimethyl oxalate hydrogenation catalyst comprises a carrier and active components, wherein the carrier is silicon dioxide In various forms, the active components comprise a main active component and an auxiliary active component, the main active component is copper, the auxiliary active component is one metal selected from Ni, In, Mo, W, Fe and Zn and/or an oxide thereof, the atomic ratio of the auxiliary active component to the main active component is 0.2-1.5, when the atomic ratio is 1-1.5, the selectivity of methyl glycolate is extremely strong, the reaction represented by the reaction formula (1) mainly occurs, when the atomic ratio is 0.2-0.8, the selectivity of ethylene glycol is extremely strong, and the reaction represented by the reaction formula (2) mainly occurs. And can greatly inhibit the generation of 1, 2-butanediol and ethanol as byproducts.
The important discovery of the inventor is that the raw materials of the catalyst are the same in type, and the two products of methyl glycolate and ethylene glycol can be directly switched as required by adjusting the raw material ratio according to the atomic ratio, thereby greatly facilitating the production and reducing the production cost.
The present inventors also simplified the preparation of such a catalyst, both compared to the ammonia distillation process disclosed in CN112717938A and compared to the co-precipitation process disclosed in CN 112717929A.
Specifically, the invention provides four preparation methods, which are respectively as follows:
(1) ammonia distillation, namely, respectively adding soluble copper salt of a main active component source and soluble metal salt of an auxiliary active component source into deionized water at the temperature of 20-30 ℃ to obtain salt solutions, respectively adding ammonia water to prepare complex solutions, mixing, adding the mixed solution and the silicon dioxide source into a reaction kettle in a co-feeding manner, and heating to evaporate ammonia until the pH value in the kettle is 6-7; and carrying out aftertreatment to obtain the catalyst.
(2) And the impregnation method is that the main active component source soluble copper salt and the auxiliary active component source soluble metal salt are dissolved in deionized water to obtain a salt solution, a silicon dioxide source is added, the mixture is obtained after the mixture is loaded for 2 to 12 hours at the temperature of between 20 and 30 ℃, and the catalyst is obtained after post-treatment.
(3) And (2) a precipitation method, namely, under the condition of 20-30 ℃, adding soluble copper salt of a main active component source and soluble metal salt of an auxiliary active component source into deionized water to obtain a salt solution, adding a silicon dioxide source, dropwise adding an aqueous solution of NaOH to obtain a mixture after dropwise adding is finished, and carrying out post-treatment to obtain the catalyst.
(4) The sol-gel method is that under the condition of 20-30 ℃, soluble copper salt of an active component source and soluble metal salt of an auxiliary active component source are put into deionized water to obtain a salt solution, a silicon dioxide source is added, the mixture is kept stand and hydrolyzed at 50-70 ℃ to obtain a mixture, and the catalyst is obtained after post-treatment.
In the four preparation methods, the post-treatment comprises the processes of drying, roasting and forming, wherein the drying temperature of the catalyst is 80-120 ℃, and the drying time is 8-24 h; the roasting temperature is 250 ℃ and 520 ℃, and the roasting time is 4-20 h.
In the preparation method, when the main active component and the auxiliary active component loaded by the silicon dioxide are oxides, the catalyst is reduced In a hydrogen atmosphere to obtain a catalyst product which is used for the hydrogenation reaction of dimethyl oxalate, wherein In the catalyst product, the main active component is copper, and the auxiliary active component is one metal selected from Ni, In, Mo, W, Fe and Zn and/or an oxide thereof; preferably, the reduction is carried out at 200-450 ℃ for 1-5 h.
In addition, the reduction can also be carried out in two steps, wherein the two-step reduction comprises reduction at 200-450 ℃ for 5-7h and then reduction at 350-450 ℃ for 1-3 h.
When the catalyst is used for dimethyl oxalate hydrogenation reaction, the catalyst is used for fixed bed dimethyl oxalate hydrogenation synthesis, the reaction temperature is 150-250 ℃, the reaction pressure is 0.1-6mpa, and the mass space velocity of dimethyl oxalate is 0.5-3h-1. The hydrogen-oil ratio is 5-500.
The content of oxide in each component of the catalyst is measured by an X-ray fluorescence spectrometer (Pasnake, X' AXIOSmAX).
The raw material used in the preparation process of the catalyst and the hydrogenation raw material dimethyl oxalate are selected from any commercially available reagent or industrial grade raw material, and the purity of the dimethyl oxalate is required to be not less than 99%.
The indexes of dimethyl oxalate hydrogenation reaction are dimethyl oxalate conversion rate (X) and ethylene glycol selectivity (S)EG) Selectivity to methyl glycolate (S)MG) 1, 2-butanediol Selectivity (S)1.2-BDO) Ethanol selectivity (S)EtOH). The calculation method of each reaction index is as follows:
the conversion rate of dimethyl oxalate, X, is 100 percent of moles of dimethyl oxalate reacted per total moles of dimethyl oxalate;
ethylene glycol selectivity SEGReaction of ethylDiol moles/moles of dimethyl oxalate reacted x 100%;
methyl glycolate Selective SMG100% moles of methyl glycolate produced by the reaction/moles of dimethyl oxalate reacted;
1, 2-butanediol Selectivity S1.2-BDOThe molar amount of 1, 2-butanediol produced by the reaction/(molar amount of dimethyl oxalate reacted/2) × 100%;
ethanol selectivity SEtOHThe molar amount of ethanol formed in the reaction/the molar amount of dimethyl oxalate reacted was 100%
The catalyst provided by the invention has the advantages of excellent catalytic performance, high activity, high selectivity and good stability, mainly solves the problem that a byproduct 1, 2-butanediol which is difficult to separate is generated in the dimethyl oxalate hydrogenation synthesis process, and prolongs the service life of the catalyst. More importantly, the types of products can be controlled by adjusting the mixture ratio of each component in the catalyst and the reaction condition of dimethyl oxalate hydrogenation, and methyl glycolate or ethylene glycol with high selectivity can be independently obtained, thereby being beneficial to the switching production of the products in industrial practical application.
Examples the invention is further described below by way of examples, but is not limited thereto.
Example 1
Preparing a catalyst:
the catalyst is synthesized by adopting an immersion method, 60.75g of copper nitrate trihydrate and 19.12g of ammonium tungstate are dissolved in 600g of deionized water, 62.52g of full-silicon molecular sieve is added, after the mixture is aged for 12 hours at room temperature, the mixture is dried for 10 hours at 120 ℃ and roasted for 6 hours at 380 ℃, and 20 wt% of CuO-17.48WO of the catalyst with the tungsten-copper atomic ratio of 0.3 is obtained3/SiO2。
Placing the catalyst in a fixed bed reactor for carrying out dimethyl oxalate reaction, setting the flow rate of hydrogen at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, carrying out heat preservation reduction for 4 hours, and after the reduction is finished, controlling the temperature to be 190 ℃, wherein the airspeed of dimethyl oxalate is 2h-1The reaction results are shown in Table 1 when the pressure is 4MPa and the hydrogen-oil ratio is 200: 1;as used throughout this application, "hydrogen to oil ratio," also referred to as "hydrogen to ester ratio," refers to the molar ratio of hydrogen to dimethyl oxalate
Example 2
Preparing a catalyst:
the catalyst is synthesized by adopting an ammonia evaporation method, 91.12g of copper nitrate trihydrate is dissolved in 400g of deionized water, 307g of 20.88% ammonia water is added to prepare a copper ammonia complex solution; 24.14g of nickel nitrate hexahydrate is dissolved in 500g of deionized water, 65g of 20.88 percent ammonia water is added to prepare nickel-ammonia complex solution, the nickel-ammonia complex solution and 1000g of 6.25 percent silica sol are mixed and are simultaneously dripped into a kettle in a co-feeding mode, the mixture reacts for 2 hours at room temperature after the dripping is finished, ammonia is evaporated by heating until the pH value of slurry in the kettle is 6 to 7, the slurry is cooled, filtered and washed by water, dried for 16 hours at 120 ℃ and baked for 6 hours at 380 ℃ to obtain 30.39 weight percent CuO-6.28 weight percent NiO/SiO of catalyst with the nickel-copper atomic ratio of 0.222。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the speed of 2 ℃/min, reducing for 4 hours under the conditions of heat preservation and normal pressure, controlling the temperature at 200 ℃ after the reduction is finished, and controlling the space velocity of dimethyl oxalate at 2h-1The reaction results are shown in Table 1 at a pressure of 3MPa and a hydrogen-to-oil ratio of 100: 1.
Example 3
Preparing a catalyst:
the catalyst synthesis method adopts a precipitation method, 75.92g of copper nitrate trihydrate and 38g of ferric nitrate are dissolved in 1500g of deionized water, 312.3g of 20% silica sol is added and stirred for 1h, 1mol/L of sodium hydroxide 700g is dripped, stirring reaction is carried out for 15 h after the dripping is finished, filtering and washing are carried out, drying is carried out at 120 ℃ for 16h, and roasting is carried out at 380 ℃ for 6h to obtain the catalyst with the iron-copper atomic ratio of 0.5, namely 24.99% CuO-12.55% Fe2O3/SiO2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, preserving the heat, reducing for 4 hours, controlling the temperature at 200 ℃ after the reduction is finished, and controlling the space velocity of dimethyl oxalate at 2h-1The hydrogen to oil ratio was 120:1 at a pressure of 2MPa, and the reaction results are shown in Table 1.
Example 4
Preparing a catalyst:
the catalyst synthesis method adopts a sol-gel method, 60.73g of copper nitrate trihydrate and 19.04g of zinc nitrate are dissolved in 150g of deionized water, 250g of ethyl orthosilicate and 940g of ethanol are mixed, a metal salt solution is added, standing and hydrolysis are carried out for 48h at 60 ℃, drying is carried out for 16h at 120 ℃, and roasting is carried out for 6h at 380 ℃ to obtain the catalyst with the zinc-copper atomic ratio of 19.95 percent CuO-8.17 percent ZnO/SiO2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, preserving the heat, reducing for 4 hours, controlling the temperature at 205 ℃ after the reduction is finished, and controlling the space velocity of dimethyl oxalate at 2h-1The hydrogen to oil ratio was 120:1 at a pressure of 3MPa, and the reaction results are shown in Table 1.
Example 5
Preparing a catalyst:
the catalyst synthesis method adopts an immersion method, 45.55g of copper nitrate trihydrate and 25.02g of indium trichloride are dissolved In 700g of deionized water, 69.3g of amorphous silicon powder is added, after aging is carried out for 12h at room temperature, drying is carried out for 10h at 120 ℃, and roasting is carried out for 6h at 380 ℃, thus obtaining the catalyst with the indium-copper atomic ratio of 0.6, namely 14.99 percent CuO-15.7 percent In2O3/SiO2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, preserving the heat, reducing for 4 hours, controlling the temperature at 200 ℃ after the reduction is finished, and controlling the space velocity of dimethyl oxalate at 2h-1The hydrogen to oil ratio was 200:1 at a pressure of 4MPa, and the reaction results are shown in Table 1.
Example 6
Preparing a catalyst:
the catalyst synthesis method adopts an impregnation method, 121.47g of copper nitrate trihydrate and 17.75g of ammonium molybdate are dissolved in 700g of deionized water, 45.5g of fumed silica is added, after the mixture is aged for 12h at room temperature, the mixture is dried for 10h at 120 ℃ and roasted for 6h at 380 ℃, and the catalyst with the molybdenum-copper atomic ratio of 0.2, namely 40% CuO-14.48% MoO is obtained3/SiO2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, preserving the heat, reducing for 4 hours, controlling the temperature at 200 ℃ after the reduction is finished, and controlling the space velocity of dimethyl oxalate at 2h-1The reaction results are shown in Table 1 at a pressure of 4MPa and a hydrogen-to-oil ratio of 100: 1.
Example 7
Preparing a catalyst: in the same manner as in example 2, 30.39 wt% CuO-6.28 wt% NiO/SiO of a catalyst having a nickel-copper atomic ratio of 0.22 was obtained2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate to be 50mL/min, heating the temperature from room temperature to 250 ℃ at the speed of 2 ℃/min, keeping the temperature for 5h, then continuously heating the temperature to 400 ℃ at the speed of 2 ℃/min, continuously reducing the temperature for 2h in a hydrogen atmosphere under the normal pressure condition, after the reduction is finished, controlling the temperature to be 210 ℃ and the space velocity of dimethyl oxalate to be 2h-1The hydrogen-to-oil ratio was 150:1 at a pressure of 2MPa, and the reaction results are shown in Table 1.
Example 8
Preparing a catalyst: the same as in example 4.
The catalyst with the atomic ratio of zinc to copper of 0.4 is obtained, namely 19.95 percent of CuO-8.17 percent of ZnO/SiO2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, preserving the heat, reducing for 4 hours, controlling the temperature at 200 ℃ after the reduction is finished, and controlling the space velocity of dimethyl oxalate at 2h-1The hydrogen to oil ratio was 150:1 at a pressure of 4MPa, and the reaction results are shown in Table 1.
Example 9
Preparing a catalyst:
the catalyst synthesis method adopts an impregnation method, 60.75g of copper nitrate trihydrate and 63.75g of ammonium tungstate are dissolved in 600g of deionized water, 21.7g of full-silicon molecular sieve is added, after the mixture is aged for 12 hours at room temperature, the mixture is dried for 10 hours at 120 ℃ and roasted for 6 hours at 380 ℃, and 20 percent CuO-58.29WO catalyst with the tungsten-copper atomic ratio of 1 is obtained3/SiO2。
The reaction conditions were the same as in example 1, and the reaction results are shown in Table 1.
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the speed of 2 ℃/min, reducing for 4 hours, controlling the temperature at 175 ℃ after reduction, and controlling the space velocity of dimethyl oxalate at 2h-1The reaction results are shown in Table 1 at a pressure of 2MPa and a hydrogen-to-oil ratio of 100:1
Example 10
The catalyst synthesis method adopts an ammonia evaporation method, 54.67g of copper nitrate trihydrate is dissolved in 250g of deionized water, 192g of 20.88% ammonia water is added to prepare copper ammonia complex solution; 78.96g of nickel nitrate is dissolved in 500g of deionized water, 180g of 20% ammonia water is added to prepare nickel ammonia complex solution, 4.9% silica sol 1255g is simultaneously dripped into a reaction kettle in a cofeeding mode, the mixture reacts for 5 hours at room temperature after the dripping is finished, ammonia is distilled by heating until the pH value of slurry in the kettle is 6-7, the slurry is cooled, filtered and washed, dried for 16 hours at 120 ℃ and roasted for 6 hours at 400 ℃ to obtain the catalyst with the nickel-copper atomic ratio of 1.2, namely 18.04% CuO-20.32% NiO/SiO2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, preserving the heat, reducing for 4 hours, controlling the temperature at 180 ℃ after the reduction is finished, and controlling the space velocity of dimethyl oxalate at 2h-1The reaction results are shown in Table 1 at a pressure of 2MPa and a hydrogen-to-oil ratio of 100: 1.
Example 11
Preparing a catalyst:
the catalyst synthesis method adopts a precipitation method, 60.74g of copper nitrate trihydrate and 85.13g of ferric nitrate are dissolved in 1500g of deionized water, 346g of 15% silica sol is added and stirred for 1h, 1mol/L of sodium hydroxide 700g is dropwise added, stirring reaction is carried out for 15 h after the dropwise addition is finished, filtering and washing are carried out, drying is carried out for 16h at 120 ℃, and roasting is carried out for 6h at 380 ℃ to obtain the catalyst with the iron-copper atomic ratio of 1.4, namely 20% CuO-28.1% Fe2O3/SiO2。
The reaction conditions were the same as in example 3; the reaction results are shown in Table 1.
Example 12
Preparing a catalyst:
the catalyst synthesis method adopts a sol-gel method, 75.93g of copper nitrate trihydrate and 77.38g of zinc nitrate are dissolved in 1500g of deionized water, 145g of ethyl orthosilicate and 740g of ethanol are mixed, a metal salt solution is added, standing and hydrolysis are carried out for 48h at 60 ℃, drying is carried out for 16h at 120 ℃, and roasting is carried out for 6h at 380 ℃ to obtain the catalyst with the zinc-copper atomic ratio of 25 percent CuO-33.25 percent ZnO/SiO2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, preserving the heat, reducing for 4 hours, controlling the temperature at 190 ℃ after the reduction is finished, and controlling the space velocity of dimethyl oxalate at 2h-1The reaction results are shown in Table 1 at a pressure of 3MPa and a hydrogen-to-oil ratio of 100: 1.
Example 13
The catalyst synthesis method adopts an immersion method, 45.55g of copper nitrate trihydrate and 50g of indium trichloride are dissolved In 700g of deionized water, 53.55g of amorphous silicon powder is added, after the mixture is aged for 12h at room temperature, the mixture is dried for 10h at 120 ℃ and roasted for 6h at 380 ℃, and the catalyst with the indium-copper atomic ratio of 1.2, namely 15.01 percent CuO-31.4 percent In2O3/SiO2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, preserving the heat, reducing for 4 hours, controlling the temperature at 185 ℃ after the reduction, and controlling the space velocity of dimethyl oxalate at 2h-1The hydrogen-to-oil ratio was 150:1 at a pressure of 2MPa, and the reaction results are shown in Table 1.
Example 14
Preparing a catalyst:
the catalyst synthesis method adopts an immersion method, 30.36g of copper nitrate trihydrate and 33.27g of ammonium molybdate are dissolved in 700g of deionized water, 62.86g of fumed silica is added, after the mixture is aged for 12h at room temperature, the mixture is dried for 10h at 120 ℃ and roasted for 6h at 380 ℃, and the catalyst with the molybdenum-copper atomic ratio of 1.5, namely 10 percent CuO-27.14 percent MoO, is obtained3/SiO2。
The reaction conditions were the same as in example 6, and the reaction results are shown in Table 1.
Example 15
Preparing a catalyst: the catalyst was prepared as in example 10.
Catalyst with nickel-copper atomic ratio of 1.2 is 18.04 percent CuO-20.32 percent NiO/SiO2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the speed of 2 ℃/min, keeping the temperature for 6h, then continuously heating the temperature to 400 ℃ at the speed of 2 ℃/min, continuously reducing the temperature for 3h in a hydrogen atmosphere under normal pressure, after the reduction is finished, controlling the temperature to be 180 ℃ and the space velocity of dimethyl oxalate to be 1.8h-1At a pressure of 2 MPa; the hydrogen to oil ratio was 80:1 and the reaction results are shown in table 1.
Example 16
Preparing a catalyst: the catalyst was prepared as in example 12.
Catalyst with zinc-copper atomic ratio of 1.3 comprises 25% of CuO-33.25% of ZnO/SiO2
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, preserving the heat, reducing for 4 hours, controlling the temperature at 180 ℃ after the reduction is finished, and controlling the space velocity of dimethyl oxalate at 2h-1The hydrogen-oil ratio was 80:1 at a pressure of 2MPa, and the reaction results are shown in Table 1.
Comparative example
Preparing a catalyst:
the catalyst synthesis method adopts an ammonia evaporation method, 75.92g of copper nitrate trihydrate is dissolved in 500g of deionized water, 20% ammonia water is added to adjust the pH value to 10, 750g of 10% silica sol and salt solution are simultaneously dripped in a co-feeding mode, the mixture reacts for 5 hours at room temperature after the dripping is finished, ammonia evaporation is carried out by heating until the pH value of slurry in a kettle is 6-7, the slurry is cooled, filtered and washed, dried at 120 ℃ for 16 hours and roasted at 380 ℃ for 6 hours to obtain the catalyst 25% CuO-SiO2。
Putting the catalyst in a fixed bed reactor, setting the hydrogen flow rate at 50mL/min, heating the temperature from room temperature to 250 ℃ at the rate of 2 ℃/min, preserving the heat, reducing for 4 hours, controlling the temperature at 200 ℃ after the reduction is finished, and controlling the space velocity of dimethyl oxalate at 2h-1The reaction results are shown in Table 1 at a pressure of 3MPa and a hydrogen-to-oil ratio of 100: 1.
TABLE 1 results of the reaction
As can be seen from Table 1, when the catalyst of the present invention is used, the conversion of the raw materials is over 99.8%, which is close to 100%, in examples 1 to 8, the selectivity of ethylene glycol is higher than 99%, in examples 9 to 14, the selectivity of methyl glycolate is over 99%, and the selectivity of by-product 1, 2-butanediol and ethanol is very low.
In the above examples and comparative examples of the present invention, the composition of the catalyst prepared by the "catalyst preparation" section is represented as CuO-MO/SiO2Actually, the metal Cu and the metal M exist in oxide forms after the catalyst is roasted in the air, and when the catalyst is placed in a fixed bed reactor, the oxide of Cu is completely reduced into the metal Cu through reduction operation; for the oxide of M, the oxide formed by some metal M does not generate reduction reaction, and the oxide of M and the reduced metal Cu are loaded on silicon dioxide together to be used as a catalyst for catalytic reaction; oxides formed by some metals M can be completely reduced into a metal M simple substance which is loaded on silicon dioxide together with the reduced metal Cu simple substance to perform catalytic reaction; some of the oxide of the metal M is partially reduced to the metal M, and a part of the oxide of M which cannot be reduced is loaded on the silicon dioxide together with the metal Cu and the metal M to perform catalytic reaction. As for the catalyst for catalyzing the hydrogenation of dimethyl oxalate of the present invention, among the catalysts, the catalyst of the present invention can be used regardless of whether the oxide of the metal M is completely reduced, or partially reduced, or not reduced at all. Regulating and controlling the generation of dimethyl oxalate hydrogenation reaction product towards methyl glycolate or ethylene glycol, and whether M is in a metal M state or metal M and M partsThe oxide state, or the oxide state all in M, is independent of the size of the atomic ratio of metal Cu and metal M.
The above-mentioned embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (22)
1. A dimethyl oxalate hydrogenation catalyst comprises a carrier and active components, wherein the carrier is silicon dioxide In various forms, the active components comprise a main active component and an auxiliary active component, the main active component is copper, the auxiliary active component is one metal selected from Ni, In, Mo, W, Fe and Zn and/or an oxide thereof, and the content ratio of the auxiliary active component to the main active component is 0.2-1.5 In terms of metal atom ratio.
2. The dimethyl oxalate hydrogenation catalyst of claim 1, wherein the silica is from any one or more of the following silica source groups: silica sol, fumed silica, ethyl orthosilicate, amorphous silicon powder and an all-silicon molecular sieve.
3. The dimethyl oxalate hydrogenation catalyst according to claim 1 or 2, wherein the content ratio of the co-active component to the main active component is 1 to 1.5 in terms of metal atom ratio.
4. The dimethyl oxalate hydrogenation catalyst according to claim 1 or 2, wherein the content ratio of the co-active component and the main active component is 0.2 to 0.8 in terms of metal atom ratio.
5. The dimethyl oxalate hydrogenation catalyst of any one of claims 1 to 4, wherein the silica content is 20 to 80 wt% of the total mass of the catalyst.
6. The dimethyl oxalate hydrogenation catalyst of any one of claims 1-5, wherein the silica content is 20-75 wt% of the total mass of the catalyst.
7. The method for preparing a dimethyl oxalate hydrogenation catalyst according to any one of claims 1 to 6, which comprises the steps of: respectively dissolving a main active component source soluble copper salt and an auxiliary active component source soluble metal salt in deionized water at the temperature of 20-30 ℃ to obtain salt solutions, respectively adding ammonia water to form complex solutions, mixing, adding the mixed solution and a silicon dioxide source into a reaction kettle in a co-feeding manner, and heating to evaporate ammonia until the pH value in the kettle is 6-7; and carrying out aftertreatment to obtain the catalyst.
8. The production method according to claim 7, wherein the concentration of the aqueous ammonia is 15 to 25 wt%.
9. The method for preparing a dimethyl oxalate hydrogenation catalyst according to any one of claims 1 to 6, which comprises the steps of: dissolving main active component source soluble copper salt and auxiliary active source soluble metal salt in deionized water to obtain a salt solution, adding a silicon dioxide source, carrying for 2-24h at 20-30 ℃ to obtain a mixture, and carrying out post-treatment to obtain the catalyst.
10. The method for preparing a dimethyl oxalate hydrogenation catalyst according to any one of claims 1 to 6, which comprises the steps of: dissolving soluble copper salt of a main active component source and soluble metal salt of an auxiliary active component source in deionized water at the temperature of 20-30 ℃ to obtain a salt solution, adding a silicon dioxide source, dropwise adding an NaOH aqueous solution to obtain a mixture after dropwise adding is completed, and carrying out post-treatment to obtain the catalyst.
11. The method according to claim 10, wherein the concentration of the aqueous NaOH solution is 0.5 to 1.5 mol/l.
12. The method for preparing a dimethyl oxalate hydrogenation catalyst according to any one of claims 1 to 6, which comprises the steps of: adding soluble copper salt of a main active component source and soluble metal salt of an auxiliary active component source into deionized water at the temperature of 20-30 ℃ to obtain a salt solution, adding a silicon dioxide source, standing at the temperature of 50-70 ℃ for hydrolysis to obtain a mixture, and carrying out post-treatment to obtain the catalyst.
13. The preparation method according to any one of claims 7 to 12, wherein the post-treatment comprises drying, roasting and forming processes, wherein the drying temperature of the catalyst is 80-120 ℃, and the drying time is preferably 8-24 h; the calcination temperature is preferably 250 ℃ and 520 ℃, and the calcination time is preferably 4-20 h.
14. The production method according to any one of claims 7 to 13, wherein the post-treatment further comprises reducing the catalyst in a hydrogen atmosphere after the shaping.
15. The method according to claim 14, wherein the reduction is carried out at 200-450 ℃ for 1-5 h.
16. The method as claimed in claim 14, wherein the reduction is performed by a two-step reduction process, the two-step reduction process comprises a reduction process at 200-300 ℃ for 5-7h, and a reduction process at 350-450 ℃ for 1-3 h.
17. A dimethyl oxalate hydrogenation catalyst prepared by the preparation method of any one of claims 7-16.
18. A method for producing methyl glycolate or diethanol by hydrogenating dimethyl oxalate is characterized by comprising the following steps: the dimethyl oxalate hydrogenation catalyst of any one of claims 1-6 or 17 is used in fixed bed dimethyl oxalate hydrogenation synthesis, the reaction temperature is 150-250 ℃, the reaction pressure is 0.1-6Mpa, and the mass space velocity of dimethyl oxalate is 0.5-3h-1The hydrogen-oil ratio is 5-500: 1.
19. the method of claim 18, wherein the catalyst is reduced in a hydrogen atmosphere prior to performing the catalytic reaction.
20. The method as claimed in claim 19, wherein the reduction is carried out at 200-450 ℃ for 1-5 h.
21. The method as claimed in claim 19, wherein the reduction is performed by a two-step reduction process, the two-step reduction process comprises a reduction process at 200-300 ℃ for 5-7h, and a reduction process at 350-450 ℃ for 1-3 h.
22. A method for adjusting and controlling the proportion of methyl glycolate and ethylene glycol in a dimethyl oxalate hydrogenation reaction product by adjusting the proportion of active components of the catalyst according to any one of claims 1 to 6 or 17, characterized in that the catalyst according to any one of claims 1 to 6 or 17 is used, wherein the weight content of ethylene glycol generated in the dimethyl oxalate reaction product is 99.0% or more by controlling the content ratio of the co-active component and the main active component in terms of metal atomic ratio to be in the range of 0.2 to 0.8; the content ratio of the auxiliary active component and the main active component is controlled within the range of 1-1.5, so that the weight content of the generated methyl glycolate in the dimethyl oxalate reaction product is more than 99.0 percent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849705A (en) * | 2022-04-28 | 2022-08-05 | 沈阳化工大学 | Preparation method of catalyst for preparing methyl glycolate through selective hydrogenation of dimethyl oxalate |
| CN115709065A (en) * | 2022-11-23 | 2023-02-24 | 西安凯立新材料股份有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation method and application thereof |
| CN115894170A (en) * | 2022-11-07 | 2023-04-04 | 中触媒新材料股份有限公司 | Method for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474561A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylene glycol from hydrogenation of oxalic ester |
| CN102151568A (en) * | 2011-01-30 | 2011-08-17 | 山东华鲁恒升集团德化设计研究有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof |
| US20130331617A1 (en) * | 2011-02-25 | 2013-12-12 | Shanghai Research Institute Of Petrochemical Technology, Sinopec | Method for producing ethylene glycol from oxalate through the fluidized bed catalytic reaction |
| CN106607036A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Oxalate hydrogenation catalyst, preparation method and uses thereof |
| CN106861710A (en) * | 2017-02-20 | 2017-06-20 | 宁波中科远东催化工程技术有限公司 | Catalyst of dimethyl oxalate preparing ethylene glycol and preparation method thereof |
| CN109201059A (en) * | 2018-08-28 | 2019-01-15 | 华东师范大学 | A kind of dimethyl oxalate selective hydrogenation methyl glycollate catalyst and its preparation method and application |
| CN109772321A (en) * | 2017-11-13 | 2019-05-21 | 中国科学院福建物质结构研究所 | A kind of copper Si catalyst and its preparation and application based on metal organic frame |
| CN110624561A (en) * | 2019-10-17 | 2019-12-31 | 高化学（江苏）化工新材料有限责任公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation and preparation method and application thereof |
| CN111715226A (en) * | 2020-07-20 | 2020-09-29 | 大连瑞克科技有限公司 | Nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate and preparation method thereof |
| CN111774050A (en) * | 2020-07-17 | 2020-10-16 | 兰州理工大学 | Preparation method and application of supported catalyst for catalyzing dimethyl oxalate hydrogenation |
-
2021
- 2021-09-29 CN CN202111150411.5A patent/CN114054024A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474561A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylene glycol from hydrogenation of oxalic ester |
| CN102151568A (en) * | 2011-01-30 | 2011-08-17 | 山东华鲁恒升集团德化设计研究有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof |
| US20130331617A1 (en) * | 2011-02-25 | 2013-12-12 | Shanghai Research Institute Of Petrochemical Technology, Sinopec | Method for producing ethylene glycol from oxalate through the fluidized bed catalytic reaction |
| CN106607036A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Oxalate hydrogenation catalyst, preparation method and uses thereof |
| CN106861710A (en) * | 2017-02-20 | 2017-06-20 | 宁波中科远东催化工程技术有限公司 | Catalyst of dimethyl oxalate preparing ethylene glycol and preparation method thereof |
| CN109772321A (en) * | 2017-11-13 | 2019-05-21 | 中国科学院福建物质结构研究所 | A kind of copper Si catalyst and its preparation and application based on metal organic frame |
| CN109201059A (en) * | 2018-08-28 | 2019-01-15 | 华东师范大学 | A kind of dimethyl oxalate selective hydrogenation methyl glycollate catalyst and its preparation method and application |
| CN110624561A (en) * | 2019-10-17 | 2019-12-31 | 高化学（江苏）化工新材料有限责任公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation and preparation method and application thereof |
| CN111774050A (en) * | 2020-07-17 | 2020-10-16 | 兰州理工大学 | Preparation method and application of supported catalyst for catalyzing dimethyl oxalate hydrogenation |
| CN111715226A (en) * | 2020-07-20 | 2020-09-29 | 大连瑞克科技有限公司 | Nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849705A (en) * | 2022-04-28 | 2022-08-05 | 沈阳化工大学 | Preparation method of catalyst for preparing methyl glycolate through selective hydrogenation of dimethyl oxalate |
| CN115894170A (en) * | 2022-11-07 | 2023-04-04 | 中触媒新材料股份有限公司 | Method for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
| CN115709065A (en) * | 2022-11-23 | 2023-02-24 | 西安凯立新材料股份有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation method and application thereof |
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