CN109569601B - High-efficiency stable supported copper-based catalyst and preparation method thereof - Google Patents
High-efficiency stable supported copper-based catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109569601B CN109569601B CN201811476796.2A CN201811476796A CN109569601B CN 109569601 B CN109569601 B CN 109569601B CN 201811476796 A CN201811476796 A CN 201811476796A CN 109569601 B CN109569601 B CN 109569601B
- Authority
- CN
- China
- Prior art keywords
- copper
- solution
- catalyst
- dicarboxylic acid
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 239000010949 copper Substances 0.000 title claims abstract description 104
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000013110 organic ligand Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000012686 silicon precursor Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- -1 heterocyclic radical dicarboxylic acid compound Chemical class 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 150000001879 copper Chemical class 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 230000032683 aging Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- ZSVGGGCOTVOOSG-UHFFFAOYSA-N 5-methylpyrazine-2,3-dicarboxylic acid Chemical compound CC1=CN=C(C(O)=O)C(C(O)=O)=N1 ZSVGGGCOTVOOSG-UHFFFAOYSA-N 0.000 claims description 3
- JPIJMXOJEHMTPU-UHFFFAOYSA-N 5-methylpyridine-2,3-dicarboxylic acid Chemical compound CC1=CN=C(C(O)=O)C(C(O)=O)=C1 JPIJMXOJEHMTPU-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- MUYSADWCWFFZKR-UHFFFAOYSA-N cinchomeronic acid Chemical compound OC(=O)C1=CC=NC=C1C(O)=O MUYSADWCWFFZKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 claims description 2
- YYJNCOSWWOMZHX-UHFFFAOYSA-N triethoxy-(4-triethoxysilylphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=C([Si](OCC)(OCC)OCC)C=C1 YYJNCOSWWOMZHX-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 63
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 abstract description 27
- 239000011148 porous material Substances 0.000 abstract description 12
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001868 water Inorganic materials 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 64
- 239000000377 silicon dioxide Substances 0.000 description 34
- 229910052681 coesite Inorganic materials 0.000 description 19
- 229910052906 cristobalite Inorganic materials 0.000 description 19
- 229910052682 stishovite Inorganic materials 0.000 description 19
- 229910052905 tridymite Inorganic materials 0.000 description 19
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000002431 foraging effect Effects 0.000 description 6
- 239000002077 nanosphere Substances 0.000 description 6
- 238000004445 quantitative analysis Methods 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 229910017758 Cu-Si Inorganic materials 0.000 description 5
- 229910017931 Cu—Si Inorganic materials 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 229910017813 Cu—Cr Inorganic materials 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000013084 copper-based metal-organic framework Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- JBQCQPOKAIVLIF-UHFFFAOYSA-N [Cu]=O.[Si] Chemical compound [Cu]=O.[Si] JBQCQPOKAIVLIF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- YAGHEUQOAPDHKS-UHFFFAOYSA-N dimethyl oxalate;methanol Chemical compound OC.COC(=O)C(=O)OC YAGHEUQOAPDHKS-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 230000007246 mechanism Effects 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
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Images
Classifications
-
- 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
- B01J23/72—Copper
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/638—
-
- B01J35/647—
-
- 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
-
- 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
Abstract
The invention discloses a high-efficiency stable supported copper-based catalyst and a preparation method thereof, wherein a soluble copper solution is added into a mixed solution of hexahydric heterocyclic dicarboxylic acid, N-dimethylformamide and alcohol to react to form a copper-organic ligand material, and the copper-organic ligand material is crushed and ground into dry powder and added into water to form slurry; reacting the slurry with a silicon precursor compound, a triblock copolymer P123, monobasic acid and alcohol to obtain a high-efficiency stable supported copper-based catalyst, wherein the catalyst has a central radial mesoporous pore canal, the surface of the catalyst is in a corrugated shape, the copper content is 15-45% of the total weight of the catalyst, and the monovalent copper content is 40-80 mol% of the total mole of active copper; the specific surface area of the catalyst>500m2G, pore volume>1.0ml/g, and the average mesoporous size is 3.0-8.0 nm. The catalyst is used for the reaction of synthesizing the glycol by hydrogenating the dimethyl oxalate, wherein the conversion rate of the dimethyl oxalate>99% ethylene glycol selectivity>96％。
Description
Technical Field
The invention relates to an efficient and stable supported copper-based hydrogenation catalyst and a preparation method thereof, in particular to a Cu/SiO catalyst for synthesizing ethylene glycol by hydrogenating dimethyl oxalate2A catalyst and a preparation method thereof.
Background
Dimethyl oxalate (DMO) hydrogenation is the most critical step in the process of synthesizing ethylene glycol by CO coupling method. Meanwhile, dimethyl oxalate hydrogenation can be used for producing ethylene glycol, Methyl Glycolate (MG) and ethanol, which are important components of the coal chemical industry chain. U.S. UCC began to apply for two patents on the hydrogenation of dimethyl oxalate in 1985, and U.S. Pat. No. 4,467,7234 discloses a Cu-Si catalyst prepared by using copper carbonate and ammonium carbonate as raw materials; US4628128 describes a Cu-Si catalyst prepared by an impregnation process. US 4112242245 mainly adopts a coprecipitation method to prepare Cu-Zn-Cr and Cu-Cr system catalysts, and introduces auxiliaries such as Ca, Cr and the like. The dimethyl oxalate hydrogenation catalyst mainly comprises a Cu-Si system and a Cu-Cr system, and although the Cu-Cr catalyst has better activity, Cr is extremely toxic and has large pollution, so that the catalyst is basically eliminated at present. Therefore, the Cu-Si system catalyst has good development prospect. However, various auxiliaries are introduced into the Cu-Si system, and the action mechanism and the action effect of the auxiliaries are unclear. The preparation route of the catalyst is still mainly based on the traditional coprecipitation method, impregnation method, sol-gel method and the like.
The use of SiO in recent years2Research and application of a catalyst for preparing ethylene glycol by hydrogenation of copper-based oxalic acid vinegar prepared for a carrier become a hotspot in the research field and make certain progress. Japanese UBE corporation U.S. Pat. No. 4,85890 produced Cu/SiO by solvent evaporation2The catalyst is used for ensuring that the highest ethylene glycol selectivity reaches 99.5 percent when the oxalic ester conversion rate is 100 percent in the diethyl oxalate hydrogenation reaction; because copper metal has the defects of low activity, easy sintering at high temperature, poor strength and the like, pure Cu/SiO2The stability of the catalyst is poor, and the service life of the catalyst cannot meet the requirement of industrial application. Patent CN101455976A uses hexagonal mesoporous molecular sieve (HMS) as carrier to prepare an oxalate hydrogenation catalyst loaded with copper and other auxiliary metals, wherein Cu-Mn/SiO takes manganese as auxiliary2The catalyst is used in the hydrogenation reaction of dimethyl oxalate, the reaction pressure is 3.0MPa, the reaction temperature is 200 ℃, and H is2When the conversion rate of oxalate can reach 100%, the selectivity of glycol is 91%, and when other conditions are not changed, H is added when the conversion rate of oxalate is 50(mo1/mo1)2The ethylene glycol selectivity was 95% when the DMO rose to 180 (mol/mol). However, in practical applications, the hydrogen ester ratio is too high to meet the performance requirements of the recycle compressor, which can greatly increase the production cost.
Cu-Cr catalyst and Cu/SiO prepared by coprecipitation method and sol-gel method used in Fujian material structure research institute of Chinese academy of sciences2The catalyst is used at the reaction pressure of 2.5-3 MPa, the reaction temperature of 208-230 ℃ and the space velocity of 2500-6000 h-1And the operation can be stably carried out for 1134h under the condition that the molar ratio of hydrogen to ester is 20-60. The best results are a conversion of 99.8% for dimethyl oxalate and an average selectivity for ethylene glycol of 95.3%. The Tianjin university adopts Cu-Zn/SiO2Catalyst and process for preparing sameUnder the conditions of 2.0MPa and 220 ℃, the conversion rate of dimethyl oxalate reaches more than 90 percent, and the selectivity of ethylene glycol is also more than 90 percent. The university of eastern China science and technology adopts Cu/SiO2The catalyst is prepared by the following best conditions: the reaction temperature is 190-200 ℃, the reaction pressure is 2.5MPa, the molar ratio of hydrogen to ester is 60, the conversion rate of dimethyl oxalate reaches about 95%, and the selectivity of ethylene glycol reaches about 90%. The catalyst has high reaction temperature and pressure and low ethylene glycol selectivity, so that the heat and power consumption is high, the byproducts are increased, and in addition, the copper catalyst is easy to generate grain agglomeration and inactivation, so that the service life of the catalyst is difficult to meet the industrial requirement. Therefore, the oxalate hydrogenation catalyst suitable for industrial application firstly needs to have the stability capable of meeting the requirements of industrial application, and secondly has high oxalate conversion rate and high glycol selectivity on the basis of high stability.
Conventional Cu/SiO2In the preparation process of the catalyst, the silicon dioxide carrier can wrap a large amount of copper active components and reduce the dispersion degree of the copper active components, and the copper active components can be agglomerated in the high-temperature reaction process by loading a large amount of copper active components, so that the activity of the catalyst is reduced, the catalyst is more easily inactivated, and the service life is shortened. Recently, the mesoporous silica nanospheres with the radial center have excellent pore characteristics such as short diffusion distance, monodispersity, high pore volume and high accessible internal surface area; the synthesis method is different from the traditional soft/hard template method, and an unstable interface is formed through complex kinetic assembly between a silicon source and a surfactant. The special structure is beneficial to the diffusion of substances and the arrangement of active sites, and can be particularly applied to metal-loaded catalyst carriers, thereby improving the dispersion degree and the reaction center activity of metal active components, increasing the stability of industrial application and prolonging the service life. In addition, the Cu-MOFs structure is formed by copper and organic ligand materials, when the Cu-MOFs structure and silicon dioxide are loaded to form the catalyst, the Cu-MOFs structure can be difficult to be completely wrapped by a carrier silicon dioxide network in a larger space structure, more copper active species are easy to expose on a copper-oxygen-silicon interface, the copper agglomeration is difficult to cause due to the lower copper content, and the silicon dioxide plays a role in anchoring copper species,thereby improving the stability of the catalyst. The method can solve the problem that the low-copper-content copper is well dispersed but has low activity after being wrapped, and improve the activity and stability of the low-copper-content catalyst.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art of Cu/SiO2The copper active component in the catalyst has poor dispersibility, unstable structure and poor molecular dynamics diffusion performance, thereby providing a high-efficiency stable supported copper-based catalyst and a preparation method thereof. The catalyst prepared by the invention has good low-temperature activity, high selectivity and good stability; the method is mainly used for synthesizing the ethylene glycol by hydrogenating the dimethyl oxalate.
According to the invention, copper and a hexatomic heterocyclic dicarboxylic acid compound are reacted to form a copper-organic framework compound, and then the copper-organic framework compound is loaded on mesoporous silica nanospheres, so that the copper active component in the formed catalyst has a larger spatial structure, the copper active component is not easily and completely wrapped by a carrier silica network, more monovalent copper active components are easily exposed on a copper-oxygen-silicon interface, copper agglomeration is not easily caused due to low copper content, and silica plays a role in anchoring copper species, thereby improving the stability of the catalyst.
According to the invention, the silicon oxide nanospheres with the pore canals in the central radial shape are used as the carrier, the size and the dispersity of copper species in the final catalyst are regulated and controlled, and the synergistic effect of monovalent copper and zero-valent copper is improved to improve the catalytic performance of the catalyst.
The mesoporous silica nano particle with the central radial mesoporous channel has a central radial mesoporous channel structure, the size of the channel is gradually increased from the inside of the particle to the surface of the particle, and the mesoporous silica nano particle is a porous material with a novel structure. Compared with the traditional mesoporous silica particles with two-dimensional hexagonal ordered pore channel structures, the mesoporous silica particles have three-dimensional open dendritic framework structures, so that the mesoporous silica particles have unique structural advantages, namely high pore permeability and high accessibility of the inner surfaces of the particles, and are favorable for conveying substances (molecules or nanoparticles) along central radial pore channels, and the substances (molecules or nanoparticles) are loaded in the mesoporous silica or react with internal active sites.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-efficiency stable supported copper-based catalyst comprises the following steps: adding a soluble copper salt solution into a mixed solution of hexahydric heterocyclic dicarboxylic acid, N-dimethylformamide and alcohol to react to form a copper-organic ligand material; crushing and grinding the copper-organic ligand material into dry powder, and adding the dry powder into deionized water to form slurry; and stirring and mixing the obtained slurry with a silicon precursor compound, a triblock copolymer P123, monobasic acid and alcohol, and carrying out aging reaction to obtain the high-efficiency stable supported copper-based catalyst.
In the above technical scheme, the preparation method specifically comprises the following steps:
(1) preparing a copper-organic ligand material:
mixing N, N-dimethylformamide and alcohol to obtain a solution A, dissolving a hexatomic heterocyclic radical dicarboxylic acid compound in the mixed solution A, stirring until the hexatomic heterocyclic radical dicarboxylic acid compound is completely dissolved to form a solution B, slowly stirring, adding a copper salt solution into the solution B until the hexatomic radical dicarboxylic acid compound is completely dissolved, continuously stirring and dispersing at the rotating speed of 500-2000 rpm for 0.5-4 hours to obtain a mixed solution, transferring the mixed solution into a reaction kettle, and reacting at the temperature of 100-140 ℃ for 12-48 hours; after the reaction is completed, naturally cooling to room temperature, and sequentially carrying out suction filtration, washing with distilled water for three times and washing with absolute ethyl alcohol for three times to obtain a crystalline solid; drying the crystalline solid in a vacuum drying oven at 100-150 ℃ for 12-48 hours to obtain a blocky copper-organic ligand material, and grinding the blocky copper-organic ligand material into powder of 300-400 meshes for later use;
(2) preparing a catalyst:
dispersing the powder of the copper-organic ligand material obtained in the step (1) in deionized water to form a suspension, then adding a silicon precursor compound, a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 (molecular formula: EO20-PO70-EO20, number average molecular weight Mn: 5800, CAS: 9003-11-6), a monobasic acid and an alcohol into the suspension, stirring at 60-80 ℃ at 500-2000 rpm for 0.5-4 h to obtain a mixture, and then cooling to room temperature to age the mixture for 24-48 h; and washing the aging product with deionized water for 2-3 times, then sequentially carrying out vacuum drying at 60-90 ℃ for 12-48 hours, drying at 100-120 ℃ for 24-48 hours, raising the temperature to 450-550 ℃ at a heating rate of 1-5 ℃/min, and roasting at the temperature for 2-8 hours to obtain the high-efficiency stable supported copper-based catalyst.
In the above technical solution, in the step (1), when the N, N-dimethylformamide and the alcohol are mixed into the solution a, the volume ratio is 1: (1-10).
In the above technical solution, in the step (1), when the six-membered heterocyclic dicarboxylic acid compound is dissolved in the solution a, the amount of the six-membered heterocyclic dicarboxylic acid compound added is 2 wt% to 15 wt% of the solution a.
In the above technical solution, in the step (1), the soluble copper salt solution is added to the solution B, and a molar ratio of the hexahydric heterocyclic dicarboxylic acid compound to copper element in the soluble copper salt solution is 1: (0.5-5.0).
In the above technical scheme, in the step (1), the soluble copper salt solution is an aqueous solution of a soluble copper salt, wherein the concentration of the soluble copper salt is 0.5-5.0 mol/L, and the soluble copper salt is any one of copper nitrate, copper chloride, copper sulfate and copper acetate.
In the above technical scheme, in the step (1) and the step (2), the alcohol is any one of methanol, ethanol, isopropanol and butanol.
In the above technical means, in the step (1), the six-membered heterocyclic dicarboxylic acid compound is any one of 2, 3-pyridinedicarboxylic acid, 3, 4-pyridinedicarboxylic acid, 3, 5-pyridinedicarboxylic acid, 2 '-bipyridine-5, 5' -dicarboxylic acid, 2 '-bipyridine-3, 3' -dicarboxylic acid, 5-methylpyrazine-2, 3-dicarboxylic acid, 5-methylpyridine-2, 3-dicarboxylic acid, and pyrazine-2, 3-dicarboxylic acid.
In the technical scheme, in the step (2), when the powder of the copper-organic ligand material is dispersed in deionized water to form a suspension, the solid-liquid mass ratio of the powder of the copper-organic ligand material to the deionized water is (0.01-0.1): 1.
in the above technical solution, in the step (2), in the mixture, a molar ratio of the silicon precursor compound, the triblock copolymer P123, the monobasic acid, the alcohol, and the deionized water is 1: (0.01-0.05): (1.0-2.0): (1.0-2.0): (150-300).
In the above technical solution, in the step (2), the silicon precursor compound is a mixture of any one, two or more of methyl silicate, ethyl silicate, propyl silicate, butyl silicate, 1, 4-bis (triethoxysilyl) benzene, 1, 2-bis (triethoxysilyl) ethane, (2-cyanoethyl) triethoxysilane, and 3-aminopropyltrimethoxysilane, which are mixed in any ratio.
In the above technical scheme, in the step (2), the monoacid is an aqueous solution of any one of hydrochloric acid, nitric acid, acetic acid and formic acid, wherein the concentration of the acid is 15-35 wt%.
The invention provides a high-efficiency stable supported copper-based catalyst which is prepared by the preparation method.
In the technical scheme, the high-efficiency stable supported copper-based catalyst has a central radial mesoporous pore canal, and the surface of the catalyst is wrinkled; the copper content is 15-45% of the total weight of the catalyst; the content of the monovalent copper is 40-80 mol% of the total mole of the active copper; the specific surface area of the catalyst>500m2G, pore volume>1.0ml/g, and the average mesoporous size is 3.0-8.0 nm.
The invention also provides application of the high-efficiency stable supported copper-based catalyst in the reaction of synthesizing ethylene glycol by hydrogenating dimethyl oxalate.
In the technical scheme, the high-efficiency stable supported copper-based catalyst is placed in a constant-temperature section of a fixed bed reactor, then dimethyl oxalate methanol solution is introduced into a gasification chamber and mixed with hydrogen, the mass ratio of hydrogen to ester is 20-100, the air speed of hydrogen is 1500-5000 h < -1 >, the partial pressure of hydrogen is 1-3 MPa, and the reaction temperature is 180-230 ℃.
In the process of dimethyl oxalate hydrogenation reaction, Cu0The active site mainly acts to activate H2Action of molecules, and Cu+The active site plays a role in polarizing and activating ester groups in the dimethyl oxalate, and the high conversion rate of the dimethyl oxalate hydrogenation reaction and the high selectivity of a target product are realized by the synergistic effect of the active site and the ester groups. During the reaction, due to copperThe influence of factors such as the increase of the agglomeration of particles and the change of the metal-carrier interaction, Cu0/Cu+The ratio of (A) to (B) also varies greatly, and once the synergy is destroyed, the catalytic activity of the catalyst is reduced sharply, and the catalyst is apparently deactivated. In the sol-gel method preparation, under the same experimental conditions, when the copper loading capacity is increased, the main factors influencing the catalyst activity are the wrapping of copper species by silicon dioxide and the agglomeration of copper species, so that the surface area of the copper species on the surface of the catalyst is reduced and the catalyst activity is reduced. The preparation method of the catalyst provided by the invention can improve the loading capacity of the copper active component and the dispersity of the copper active component, reduce the diffusion resistance of reactant molecules and products on the catalyst, undoubtedly improve the conversion rate of dimethyl oxalate reaction and the selectivity of ethylene glycol products, reduce the inactivation rate and prolong the service life of the catalyst.
The invention aims to provide the catalyst for synthesizing the ethylene glycol by hydrogenating the dimethyl oxalate, which has the advantages of high activity, simple preparation process, low cost and environmental friendliness, wherein the conversion rate of the dimethyl oxalate can reach more than 99 percent, the selectivity of the ethylene glycol can reach more than 96 percent, and the catalyst is stable in reaction and easy to control.
Drawings
FIG. 1: SEM image of mesoporous silica nanospheres obtained in example 1;
FIG. 2: TEM image of mesoporous silica nanospheres obtained in example 1.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
example 1
A high-dispersion stable copper-based catalyst is prepared by the following method:
1) mixing 40ml of N, N-dimethylformamide and 100ml of ethanol to obtain a solution, adding 20g of 2, 3-dipicolinic acid, stirring until the solution is completely dissolved, and slowly adding 1.8mol/L Cu (NO) under stirring3)·3H2Dissolving O solution completely, stirring and dispersing at 1500rpm for 1 hr, and transferring the mixed solutionMoving the mixture into a reaction kettle to react for 12 hours at 120 ℃; and after the reaction is completed, naturally cooling to room temperature, carrying out suction filtration, washing with distilled water and absolute ethyl alcohol for three times respectively to obtain a crystalline solid, placing the sample in a vacuum drying oven at 120 ℃ for drying for 24 hours to obtain a blocky copper-organic coordination material, and grinding the blocky copper-organic coordination material into powder with the particle size of 400 meshes.
2) Dispersing 15g of the solid powder of the copper-organic coordination material obtained in the step 1) in 623ml of deionized water to form a suspension, then adding 50g of ethyl silicate, adding 25.06g of triblock copolymer P123, 35.59g of hydrochloric acid solution with the concentration of 30% and 26.51g of butanol, stirring at the rotating speed of 1000rpm at the temperature of 60 ℃ for 2h, then cooling to room temperature for aging for 24h, washing with deionized water for 3 times, drying in vacuum at the temperature of 80 ℃ for 24h, drying at the temperature of 120 ℃ for 24h, raising the temperature to 450 ℃ at the heating rate of 1 ℃/min, and roasting for 6 h to obtain the Cu/SiO with high dispersion stability of copper2A catalyst finished product; the surface of the catalyst is in a corrugated shape and has a central radial mesoporous pore channel, as shown in fig. 1 and fig. 2.
XRF quantitative analysis of the Cu/SiO2The mass fraction of Cu in the catalyst was 21.1 wt%, and it was designated as CuDMS-1. The types of raw materials for preparation and analytical data of the catalyst are shown in tables 1 and 2.
Example 2
A high-dispersion stable copper-based catalyst is prepared by the following method:
1) mixing 50ml of N, N-dimethylformamide and 300ml of isopropanol to obtain a solution, adding 20g of 3, 5-dipicolinic acid, stirring until the solution is completely dissolved, and slowly adding 1.08mol/L Cu (CH) under stirring3COO)2·H2The O solution is completely dissolved, stirring and dispersing are continuously carried out for 4 hours at the rotating speed of 600rpm, and the mixed solution is transferred into a reaction kettle to react for 24 hours at the temperature of 130 ℃; and naturally cooling to room temperature after complete reaction, performing suction filtration, washing with distilled water and absolute ethyl alcohol for three times respectively to obtain a crystalline solid, placing the sample in a vacuum drying oven at 105 ℃ for drying for 48 hours to obtain a blocky copper-organic coordination material, and grinding the blocky copper-organic coordination material into 350-mesh powder.
2) Dispersing 10g of copper-organic coordination material solid powder obtained in the step 1) in 305ml of deionized water to form a suspension, then adding 20.0g of ethyl silicate, adding 13.92g of triblock copolymer P123, 50.21g of nitric acid solution with the concentration of 20% and 7.26g of isopropanol, stirring at the rotating speed of 1500rpm at the temperature of 80 ℃ for 1h, then cooling to room temperature for aging for 24 hours, washing with deionized water for 3 times, drying in vacuum at the temperature of 60 ℃ for 24 hours, drying at the temperature of 100 ℃ for 48 hours, and roasting at the temperature rising rate of 2 ℃/min to 500 ℃ for 4 hours to obtain a finished product of the copper high-dispersion stable Cu/SiO2 catalyst; the mass fraction of Cu in the Cu/SiO2 catalyst was 30.9 wt% as measured by XRF quantitative analysis and is designated as CuDMS-2. The types of raw materials for preparation and analytical data of the catalyst are shown in tables 1 and 2.
Example 3
A high-dispersion stable copper-based catalyst is prepared by the following method:
1) mixing 60ml of N, N-dimethylformamide and 100ml of butanol to form a solution, adding 20g of 2,2 '-bipyridine-5, 5' -dicarboxylic acid into the solution, stirring until the solution is completely dissolved, and slowly stirring the solution and adding 0.41mol/L CuCl2·2H2The O solution is completely dissolved, stirring and dispersing are continuously carried out for 3 hours at the rotating speed of 1200rpm, and the mixed solution is transferred into a reaction kettle to react for 48 hours at the temperature of 105 ℃; and naturally cooling to room temperature after complete reaction, performing suction filtration, washing with distilled water and absolute ethyl alcohol for three times respectively to obtain a crystalline solid, placing the sample in a vacuum drying oven at 145 ℃ for drying for 12 hours to obtain a blocky copper-organic coordination material, and grinding the blocky copper-organic coordination material into powder of 325 meshes.
2) Dispersing 20g of the solid powder of the copper-organic coordination material obtained in the step 1) in 777ml of deionized water to form a suspension, then adding 28.0g of methyl silicate, adding 37.34g of triblock copolymer P123, 68.04g of acetic acid solution with the concentration of 25% and 15.51g of ethanol, stirring at 1800rpm for 1h at 60 ℃, then cooling to room temperature for aging for 24 hours, washing with deionized water for 3 times, drying in vacuum at 80 ℃ for 24 hours, drying at 120 ℃ for 24 hours, and roasting at the temperature rising rate of 4 ℃/min to 550 ℃ for 4 hours to obtain a finished product of the copper high-dispersion stable Cu/SiO2 catalyst; the mass fraction of Cu in the Cu/SiO2 catalyst was found to be 26.2 wt% by XRF quantitative analysis and is designated as CuDMS-3. The types of raw materials for preparation and analytical data of the catalyst are shown in tables 1 and 2.
Example 4
A high-dispersion stable copper-based catalyst is prepared by the following method:
1) mixing 40ml of N, N-dimethylformamide and 400ml of methanol to form a solution, adding 20g of 5-methylpyrazine-2, 3-dicarboxylic acid into the solution, stirring until the solution is completely dissolved, slowly stirring and adding a 0.55mol/L CuSO 4.5H2O solution until the solution is completely dissolved, continuously stirring and dispersing at the rotating speed of 1400rpm for 1 hour, and transferring the mixed solution into a reaction kettle for reaction at the temperature of 140 ℃ for 12 hours; and naturally cooling to room temperature after complete reaction, performing suction filtration, washing with distilled water and absolute ethyl alcohol for three times respectively to obtain a crystalline solid, placing the sample in a vacuum drying oven at 125 ℃ for drying for 24 hours to obtain a blocky copper-organic coordination material, and grinding the blocky copper-organic coordination material into 400-mesh powder.
2) Dispersing 20g of the copper-organic coordination material solid powder obtained in the step 1) in 730ml of deionized water to form a suspension, then adding 24.0g of methyl silicate, adding 41.15g of triblock copolymer P123, 76.17g of hydrochloric acid solution with the concentration of 15% and 15.78g of butanol, stirring at 1200rpm at 70 ℃ for 2h, then cooling to room temperature for aging for 24h, washing with deionized water for 3 times, drying at 70 ℃ for 36 h in vacuum, drying at 115 ℃ for 36 h, and roasting at the temperature rising rate of 2 ℃/min to 500 ℃ for 6 h to obtain a finished product of the copper high-dispersion stable Cu/SiO2 catalyst; the mass fraction of Cu in the Cu/SiO2 catalyst was 33.9 wt% as measured by XRF quantitative analysis and was designated CuDMS-4. The types of raw materials for preparation and analytical data of the catalyst are shown in tables 1 and 2.
Example 5
A high-dispersion stable copper-based catalyst is prepared by the following method:
1) mixing 70ml of N, N-dimethylformamide and 400ml of ethanol to obtain a solution, adding 20g of 5-methylpyridine-2, 3-dicarboxylic acid into the solution, stirring until the solution is completely dissolved, slowly stirring, adding a 0.59mol/L Cu (NO 3). 3H2O solution until the solution is completely dissolved, continuously stirring and dispersing at the rotating speed of 1000rpm for 2 hours, and transferring the mixed solution into a reaction kettle to react at 110 ℃ for 36 hours; and naturally cooling to room temperature after complete reaction, performing suction filtration, washing with distilled water and absolute ethyl alcohol for three times respectively to obtain a crystalline solid, placing the sample in a vacuum drying oven at 135 ℃ for drying for 36 hours to obtain a blocky copper-organic coordination material, and grinding the blocky copper-organic coordination material into 350-mesh powder.
2) Dispersing 20g of the copper-organic coordination material solid powder obtained in the step 1) in 729ml of deionized water to form a suspension, then adding 30.0g of (2-cyanoethyl) triethoxysilane, then adding 12.01g of triblock copolymer P123, 22.81g of hydrochloric acid solution with the concentration of 30% and 13.84g of isopropanol, stirring at the rotating speed of 1600rpm for 2h at the temperature of 75 ℃, then cooling to room temperature for aging for 24h, washing with deionized water for 3 times, then carrying out vacuum drying at the temperature of 90 ℃ for 12 h, then drying at the temperature of 120 ℃ for 48 h, and roasting at the temperature rising rate of 2 ℃/min to 500 ℃ for 6 h to obtain a finished product of the copper high-dispersion stable Cu/SiO2 catalyst; the mass fraction of Cu in the Cu/SiO2 catalyst was 38.2 wt% as measured by XRF quantitative analysis and is designated CuDMS-5. The types of raw materials for preparation and analytical data of the catalyst are shown in tables 1 and 2.
Example 6
A high-dispersion stable copper-based catalyst is prepared by the following method:
1) mixing 200ml of N, N-dimethylformamide and 400ml of isopropanol to obtain a solution, adding 20g of 2, 3-pyrazine-dicarboxylic acid into the solution, stirring until the solution is completely dissolved, slowly stirring, adding a 0.55mol/L Cu (CH3COO) 2. H2O solution until the solution is completely dissolved, continuously stirring and dispersing at 1600rpm for 1 hour, and transferring the mixed solution into a reaction kettle to react at 125 ℃ for 24 hours; and naturally cooling to room temperature after complete reaction, performing suction filtration, washing with distilled water and absolute ethyl alcohol for three times respectively to obtain a crystalline solid, placing the sample in a vacuum drying oven at 120 ℃ for drying for 24 hours to obtain a blocky copper-organic coordination material, and grinding the blocky copper-organic coordination material into powder of 325 meshes.
2) Preparation of mesoporous silica nanosphere supported copper catalyst
Dispersing 20g of the copper-organic coordination material solid powder obtained in the step 1) in 1032ml of deionized water to form a suspension, then adding 50.0g of 3-aminopropyltrimethoxysilane, then adding 51.76g of triblock copolymer P123, 88.43g of 18% formic acid solution and 31.42g of butanol, stirring at the rotating speed of 1400rpm for 1h at the temperature of 80 ℃, then cooling to room temperature for aging for 24 hours, washing with deionized water for 3 times, drying in vacuum at the temperature of 80 ℃ for 24 hours, drying at the temperature of 110 ℃ for 36 hours, and roasting at the temperature rising rate of 5 ℃/min to 550 ℃ for 4 hours to obtain a finished product of the copper high-dispersion stable Cu/SiO2 catalyst; the mass fraction of Cu in the Cu/SiO2 catalyst was 22.5 wt% as measured by XRF quantitative analysis and is designated as CuDMS-6. The types of raw materials for preparation and analytical data of the catalyst are shown in tables 1 and 2.
Comparative example 1: the catalyst was prepared according to the method described in the example of patent CN 103816915A:
7.6g of Cu (NO)3)2·3H2Dissolving O in 500ml of deionized water to form a solution, adjusting the pH value of the solution to 2-3 by using nitric acid, adding 10g of urea, and then adding 7.89g of mesoporous SiO2Support (HMS), stirred vigorously for 4 hours to form a mixed solution.
The three-necked flask containing the mixed solution was put in an oil bath at 90 ℃ and stirred, and heated to reflux the vapor. The pH value of the solution gradually rises along with the decomposition of the urea, stirring is stopped when the pH value of the solution rises to 7.0, the solution is filtered while the solution is hot, the obtained filter cake (precipitate) is washed by deionized water, the precipitate is dried at 120 ℃ for 12 hours, then the dried precipitate is moved to a muffle furnace, the temperature is raised to 450 ℃ at the speed of 1 ℃/min under the air atmosphere, and then the dried precipitate is roasted at constant temperature for 4 hours, so that the Cu/HMS catalyst with the copper mass percentage content of 20.3 percent is obtained, and the Cu/HMS catalyst is marked as CuSiVS-1.
Comparative example 2: the catalyst was prepared according to the procedure described in the example of patent CN 10656449A:
dissolving 10.6g of copper nitrate and 0.5g of mannitol in 100g of distilled water, fully dissolving, and then placing in an ultrasonic instrument for ultrasonic oscillation for 20min, wherein the ultrasonic frequency is 25 kHz. 5.0g of urea was added to the above solution and dissolved by stirring, and then 20m of 1m of ammonia water was added thereto and stirred sufficiently for 30 min. Finally, 21g of an alkaline silica sol containing 40% SiO2 was added dropwise, the mixture was mechanically stirred and placed in a water bath at 80 ℃ for 5 hours, and heating was stopped until the pH of the solution reached approximately 7. Filtering to obtain filter cake, washing the filter cake with distilled water for multiple times, drying the obtained filter cake in air at 120 ℃ for 24h, and roasting at 450 ℃ for 4h in air atmosphere to obtain Cu/SiO2The catalyst, wherein the mass fraction of Cu is 24.9 wt%, is designated CuSiVS-2.
Table 1: raw material types and feeding molar ratios in examples
Table 2: analytical data of catalysts in examples and comparative examples
The application example is as follows:
the application of the catalysts obtained in examples 1 to 6 and comparative examples 1 to 2 was examined:
respectively taking 10ml of the catalysts obtained in the examples 1-6 and the comparative examples 1-2 and filling the catalysts into a tubular reactor; the reaction tube is heated to 250 ℃ from room temperature at the speed of 2 ℃/min, the hydrogen content is gradually increased to 100 percent from 10 percent, after the temperature of the reaction tube is heated to 250 ℃, the reaction tube is reduced for 5 hours by hydrogen with the flow rate of 50m1/(min ml cat.)99.99 percent, and the reduction pressure is 1.2 MPa; then the prepared 0.2g/ml dimethyl oxalate methanol solution is introduced into a gasification chamber and mixed with hydrogen. Dimethyl oxalate is taken as a raw material, and the hydrogen/ester molar ratio is 50: 1, the space velocity of hydrogen is 2000h < -1 >, the reaction temperature is controlled between 180 and 230 ℃, the reaction pressure is about 2.0MPa, the operation is carried out for 500 hours, and various data of the catalyst are measured, wherein the result is shown in a table 3, wherein DMO represents dimethyl oxalate, EG represents ethylene glycol, and MG represents methyl glycolate.
Table 3: catalytic performance of different catalysts
| Examples | Catalyst code | Reaction temperature/. degree.C | DMO conversion% | EG selectivity% | MG selectivity% |
| Example 1 | CuDMS-1 | 200 | 99.9 | 96.3 | 2.8 |
| Example 2 | CuDMS-2 | 190 | 99.8 | 96.8 | 2.0 |
| Example 3 | CuDMS-3 | 205 | 99.8 | 97.0 | 2.1 |
| Example 4 | CuDMS-4 | 200 | 99.8 | 96.6 | 2.4 |
| Example 5 | CuDMS-5 | 215 | 99.9 | 97.4 | 1.4 |
| Example 6 | CuDMS-6 | 230 | 99.8 | 96.7 | 2.2 |
| Comparative example 1 | CuSiVS-1 | 200 | 95.0 | 86.4 | 13.4 |
| Comparative example 2 | CuSiVS-2 | 200 | 99.0 | 84.5 | 15.1 |
As can be seen from the analysis of Table 3, the catalyst prepared by the embodiment of the invention has the conversion rate of more than 99 percent and the selectivity of ethylene glycol of more than 96 percent in the hydrogenation reaction of dimethyl oxalate; in the reaction of the catalyst obtained in the comparative example under the same conditions, the conversion rate of dimethyl oxalate is less than 99 percent, and the selectivity of ethylene glycol is less than 87 percent; this demonstrates the significant advantages of the catalysts prepared according to the invention.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. The preparation method of the high-efficiency stable supported copper-based catalyst is characterized by comprising the following steps: adding a soluble copper salt solution into a mixed solution of hexahydric heterocyclic dicarboxylic acid, N-dimethylformamide and alcohol to react to form a copper-organic ligand material; crushing and grinding the copper-organic ligand material into dry powder, and adding the dry powder into deionized water to form slurry; and stirring and mixing the obtained slurry with a silicon precursor compound, a triblock copolymer P123, monobasic acid and alcohol, and carrying out aging reaction to obtain the high-efficiency stable supported copper-based catalyst.
2. The preparation method according to claim 1, comprising the following steps:
(1) preparing a copper-organic ligand material:
mixing N, N-dimethylformamide and alcohol to obtain a solution A, dissolving a hexatomic heterocyclic radical dicarboxylic acid compound in the mixed solution A, stirring until the hexatomic heterocyclic radical dicarboxylic acid compound is completely dissolved to form a solution B, slowly stirring, adding a copper salt solution into the solution B until the hexatomic radical dicarboxylic acid compound is completely dissolved, continuously stirring and dispersing at the rotating speed of 500-200 rpm for 0.5-4 hours to obtain a mixed solution, transferring the mixed solution into a reaction kettle, and reacting at the temperature of 100-140 ℃ for 12-48 hours; after the reaction is completed, naturally cooling to room temperature, and sequentially carrying out suction filtration, washing with distilled water for three times and washing with absolute ethyl alcohol for three times to obtain a crystalline solid; drying the crystalline solid in a vacuum drying oven at 100-150 ℃ for 12-48 hours to obtain a blocky copper-organic ligand material, and grinding the blocky copper-organic ligand material into powder of 300-400 meshes for later use;
(2) preparing a catalyst:
dispersing the powder of the copper-organic ligand material obtained in the step (1) in deionized water to form a suspension, then adding a silicon precursor compound, a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123, a monoacid and an alcohol into the suspension, stirring at the rotating speed of 500-2000 rpm at the temperature of 60-80 ℃ for 0.5-4 h to obtain a mixture, and then cooling to room temperature to age the mixture for 24-48 h; and washing the aging product with deionized water for 2-3 times, then sequentially carrying out vacuum drying at 60-90 ℃ for 12-48 hours, drying at 100-120 ℃ for 24-48 hours, raising the temperature to 450-550 ℃ at a heating rate of 1-5 ℃/min, and roasting at the temperature for 2-8 hours to obtain the high-efficiency stable supported copper-based catalyst.
3. The method according to claim 2, wherein in the step (1), when the N, N-dimethylformamide and the alcohol are mixed to form the solution A, the volume ratio of the N, N-dimethylformamide to the alcohol is 1: (1-10); when the hexatomic heterocyclic radical dicarboxylic acid compound is dissolved in the solution A, the adding amount of the hexatomic heterocyclic radical dicarboxylic acid compound is 2-15 wt% of the solution A; and adding a soluble copper salt solution into the solution B, wherein the molar ratio of the hexahydric heterocyclic dicarboxylic acid compound to copper element in the soluble copper salt solution is 1: (0.5-5.0).
4. The method according to claim 2, wherein in the step (1), the soluble copper salt solution is an aqueous solution of a soluble copper salt, wherein the concentration of the soluble copper salt is 0.5 to 5.0mol/L, and the soluble copper salt is any one of copper nitrate, copper chloride, copper sulfate and copper acetate.
5. The method according to claim 2, wherein in the step (1) and the step (2), the alcohol is any one of methanol, ethanol, isopropanol and butanol.
6. The production method according to claim 2, wherein in step (1), the six-membered heterocyclic dicarboxylic acid compound is any one of 2, 3-pyridinedicarboxylic acid, 3, 4-pyridinedicarboxylic acid, 3, 5-pyridinedicarboxylic acid, 2 '-bipyridine-5, 5' -dicarboxylic acid, 2 '-bipyridine-3, 3' -dicarboxylic acid, 5-methylpyrazine-2, 3-dicarboxylic acid, 5-methylpyridine-2, 3-dicarboxylic acid, and pyrazine-2, 3-dicarboxylic acid.
7. The preparation method according to claim 2, wherein in the step (2), when the powder of the copper-organic ligand material is dispersed in deionized water to form a suspension, the solid-liquid mass ratio of the powder of the copper-organic ligand material to the deionized water is (0.01-0.1): 1; in the mixture, the molar ratio of the silicon precursor compound, the triblock copolymer P123, the monobasic acid, the alcohol and the deionized water is 1: (0.01-0.05): (1.0-2.0): (1.0-2.0): (150-300).
8. The method according to claim 2, wherein in the step (2), the silicon precursor compound is a mixture of one, two or more selected from the group consisting of methyl silicate, ethyl silicate, propyl silicate, butyl silicate, 1, 4-bis (triethoxysilyl) benzene, 1, 2-bis (triethoxysilyl) ethane, (2-cyanoethyl) triethoxysilane, and 3-aminopropyltrimethoxysilane; the monoacid is an aqueous solution of any one of hydrochloric acid, nitric acid, acetic acid and formic acid, wherein the concentration of the acid is 15-35 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811476796.2A CN109569601B (en) | 2018-12-05 | 2018-12-05 | High-efficiency stable supported copper-based catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811476796.2A CN109569601B (en) | 2018-12-05 | 2018-12-05 | High-efficiency stable supported copper-based catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109569601A CN109569601A (en) | 2019-04-05 |
| CN109569601B true CN109569601B (en) | 2021-07-13 |
Family
ID=65927380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811476796.2A Active CN109569601B (en) | 2018-12-05 | 2018-12-05 | High-efficiency stable supported copper-based catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109569601B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110975926B (en) * | 2019-11-28 | 2023-05-30 | 上海应用技术大学 | Preparation method and application of diphenyl methanol dehydrogenation synthetic diphenyl ketone catalyst |
| CN111013592A (en) * | 2019-12-05 | 2020-04-17 | 河北大学 | Hydrotalcite nickel-based nano catalyst with intercalation structure and preparation method and application thereof |
| CN113020614B (en) * | 2021-02-26 | 2022-09-02 | 中国科学技术大学 | Copper-based monatomic alloy catalyst, preparation method and application thereof, and membrane electrode electrolyte battery for preparing formic acid through carbon dioxide electroreduction |
| CN113332989B (en) * | 2021-05-28 | 2023-01-10 | 浙江工业大学 | Alumina supported copper-rare earth metal oxide catalyst and preparation method and application thereof |
| CN113828319B (en) * | 2021-10-13 | 2024-03-26 | 江苏扬农化工集团有限公司 | Cu-Zn-M composite oxide catalyst and preparation method and application thereof |
| CN114984952B (en) * | 2022-05-19 | 2023-11-21 | 广东工业大学 | Carbon-coated copper material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551197A (en) * | 2013-11-11 | 2014-02-05 | 北京化工大学 | Magnetic metal-organic framework material with pocket-channel structure and preparation and reaction for acylation thereof |
| CN105056895A (en) * | 2015-08-17 | 2015-11-18 | 中国科学院上海高等研究院 | Preparation method and application of metal organic frameworks-mesoporous silica composite material |
| CN106268656A (en) * | 2016-09-28 | 2017-01-04 | 中国石油大学(北京) | Porous alumina ceramic loaded Cu MOF adsorbent and preparation method thereof |
| CN103769095B (en) * | 2014-01-07 | 2017-01-04 | 沈阳化工大学 | Hydrogenation of Dimethyl Oxalate reaction generates ethylene glycol catalyst and preparation method thereof |
| CN109433205A (en) * | 2018-11-28 | 2019-03-08 | 中触媒新材料股份有限公司 | A kind of copper-based catalysts of Hydrogenation of Dimethyl Oxalate and the preparation method and application thereof |
| CN109482184A (en) * | 2018-11-28 | 2019-03-19 | 中触媒新材料股份有限公司 | A kind of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol method for preparing catalyst |
-
2018
- 2018-12-05 CN CN201811476796.2A patent/CN109569601B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551197A (en) * | 2013-11-11 | 2014-02-05 | 北京化工大学 | Magnetic metal-organic framework material with pocket-channel structure and preparation and reaction for acylation thereof |
| CN103769095B (en) * | 2014-01-07 | 2017-01-04 | 沈阳化工大学 | Hydrogenation of Dimethyl Oxalate reaction generates ethylene glycol catalyst and preparation method thereof |
| CN105056895A (en) * | 2015-08-17 | 2015-11-18 | 中国科学院上海高等研究院 | Preparation method and application of metal organic frameworks-mesoporous silica composite material |
| CN106268656A (en) * | 2016-09-28 | 2017-01-04 | 中国石油大学(北京) | Porous alumina ceramic loaded Cu MOF adsorbent and preparation method thereof |
| CN109433205A (en) * | 2018-11-28 | 2019-03-08 | 中触媒新材料股份有限公司 | A kind of copper-based catalysts of Hydrogenation of Dimethyl Oxalate and the preparation method and application thereof |
| CN109482184A (en) * | 2018-11-28 | 2019-03-19 | 中触媒新材料股份有限公司 | A kind of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol method for preparing catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109569601A (en) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109569601B (en) | High-efficiency stable supported copper-based catalyst and preparation method thereof | |
| CN109433205B (en) | Copper-based catalyst for dimethyl oxalate hydrogenation and preparation method and application thereof | |
| CN109482185B (en) | High-dispersion stable copper-based catalyst and preparation method thereof | |
| CN107597109A (en) | Load type gold catalyst of nano-metal-oxide doping and preparation method and application | |
| CN113101933B (en) | Supported nickel-cobalt bimetallic nano catalyst and application thereof in catalyzing selective hydrogenation reaction of vanillin | |
| Keshipour et al. | Nanocomposite of hydrophobic cellulose aerogel/graphene quantum dot/Pd: Synthesis, characterization, and catalytic application | |
| CN108855095B (en) | Methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO2Preparation method of (1) | |
| CN105170151A (en) | Core-shell structure type copper-based catalyst as well as preparation method and application thereof | |
| CN109772321B (en) | Copper-silicon catalyst based on metal organic framework and preparation and application thereof | |
| CN109433204B (en) | Mesoporous silica nanosphere supported copper-silicon catalyst and preparation method thereof | |
| Qi et al. | Solvent-free aerobic oxidation of alcohols over palladium supported on MCM-41 | |
| CN106693989B (en) | Metal wire mesh loaded nano composite catalyst, preparation method thereof and application thereof in preparation of aldehyde and ketone from alcohol | |
| CN103657643A (en) | Method for preparing nano palladium metal catalyst | |
| CN102728380A (en) | Catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis, preparation method thereof, and application thereof | |
| CN109482184B (en) | Preparation method of catalyst for synthesizing ethylene glycol by dimethyl oxalate hydrogenation | |
| CN109046379A (en) | A kind of perovskite composite oxides load platinum catalyst and its preparation and application | |
| CN111905755A (en) | Catalyst for hydrogenation of 2,2,4, 4-tetramethyl-1, 3-cyclobutanedione and preparation method and application thereof | |
| CN101028599A (en) | Production of NiB amorphous alloy catalyst by chitose medium dispersing method | |
| CN109433206B (en) | Preparation method of mesoporous silica supported copper catalyst with central radial pore passage | |
| CN104445340B (en) | By the preparation method of the octahedra cerium oxide of nanometer blocks self-assembly | |
| KR101868904B1 (en) | MESOPOROUS IRON OXIDE COMPLEX COMPRISING Pt ATOM AND METHOD FOR PREPARING THE SAME | |
| CN113083299A (en) | Yolk-shell bifunctional catalyst, preparation method thereof and application thereof in preparation of ethylene glycol by hydrogenolysis of glucose | |
| CN105749908A (en) | Photocatalyst of Au@TiO2 hollow core-shell structure and preparation method of photocatalyst of Au@TiO2 hollow core-shell structure | |
| CN113083309A (en) | Catalyst for preparing glyceric acid by efficiently catalyzing glycerol oxidation, preparation method and application thereof | |
| CN110813364B (en) | Preparation method of bimetallic nano-catalyst and application of bimetallic nano-catalyst in preparation of pyruvic acid and hydroxyacetone by catalytic oxidation of 1, 2-propylene glycol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |