CN109569601A - A kind of efficient stable carried copper-base catalyst and preparation method thereof - Google Patents
A kind of efficient stable carried copper-base catalyst and preparation method thereof Download PDFInfo
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- CN109569601A CN109569601A CN201811476796.2A CN201811476796A CN109569601A CN 109569601 A CN109569601 A CN 109569601A CN 201811476796 A CN201811476796 A CN 201811476796A CN 109569601 A CN109569601 A CN 109569601A
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- copper
- catalyst
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- alcohol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 96
- 229910052802 copper Inorganic materials 0.000 claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 30
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 23
- -1 six-membered heterocyclic group dicarboxylic acids Chemical class 0.000 claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 239000013110 organic ligand 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 10
- 239000012686 silicon precursor Substances 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000009938 salting Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 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 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 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
- 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 class 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 class CC1=CN=C(C(O)=O)C(C(O)=O)=C1 JPIJMXOJEHMTPU-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 claims description 3
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 2
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical class N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 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
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims 2
- KNVZVRWMLMPTTJ-UHFFFAOYSA-N 2-(3-carboxy-2-pyridinyl)-3-pyridinecarboxylic acid Chemical class OC(=O)C1=CC=CN=C1C1=NC=CC=C1C(O)=O KNVZVRWMLMPTTJ-UHFFFAOYSA-N 0.000 claims 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims 1
- 238000005815 base catalysis Methods 0.000 claims 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims 1
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical group [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 claims 1
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 45
- 239000000377 silicon dioxide Substances 0.000 description 27
- 229910052681 coesite Inorganic materials 0.000 description 20
- 229910052906 cristobalite Inorganic materials 0.000 description 20
- 229910052682 stishovite Inorganic materials 0.000 description 20
- 229910052905 tridymite Inorganic materials 0.000 description 20
- 230000000694 effects Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 235000012239 silicon dioxide Nutrition 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 241000894007 species Species 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 229910017758 Cu-Si Inorganic materials 0.000 description 5
- 229910017931 Cu—Si Inorganic materials 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 5
- 229910017813 Cu—Cr Inorganic materials 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
- 238000002242 deionisation method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 150000003901 oxalic acid esters Chemical class 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- JBQCQPOKAIVLIF-UHFFFAOYSA-N [Cu]=O.[Si] Chemical compound [Cu]=O.[Si] JBQCQPOKAIVLIF-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 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
- 238000004090 dissolution Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#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
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229910021591 Copper(I) 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
- 229910016374 CuSO45H2O 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
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000470 constituent 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
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 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
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 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
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 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
- 238000005648 named reaction Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical class OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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 kind of efficient stable carried copper-base catalysts and preparation method thereof, soluble copper solution is added to six-membered heterocyclic group dicarboxylic acids, N, dinethylformamide, alcohol mixed solution in reaction formed copper-organic ligand material and smash and grind at dry powder, be added to the water to form slurries；Slurries react to obtain efficient stable carried copper-base catalyst with silicon precursor compounds, triblock copolymer P123, monoacid, alcohol, catalyst has the radial mesopore orbit in center, accordion is presented in surface, copper content is the 15~45% of overall catalyst weight, and monovalence copper content is 40~80mol% of active copper total mole number；Specific surface area of catalyst > the 500m2/ g, Kong Rong > 1.0ml/g, 3.0~8.0nm of average mesopore size.The catalyst is reacted for hydrogenation of dimethyl oxalate to synthesizing ethylene glycol, dimethyl oxalate in preparation conversion ratio > 99%, glycol selectivity > 96%.
Description
Technical field
The present invention relates to a kind of efficient stable carried copper-base hydrogenation catalysts and preparation method thereof, and in particular to Yi Zhongyong
In the Cu/SiO of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol2Catalyst and preparation method thereof.
Background technique
Dimethyl oxalate (DMO) hydrogenation reaction is the most essential steps during CO coupling method synthesizing glycol.Meanwhile grass
Dimethyl phthalate hydrogenation reaction can also be used to production methyl glycollate (MG) and ethyl alcohol, they are all in addition to producing ethylene glycol
The important component of Chemical Industry chain.UCC company, the U.S. started to have applied for that two add about dimethyl oxalate in 1985
Hydrogen patent, the Cu-Si catalyst that US4677234 technology is mainly prepared using copper carbonate and ammonium carbonate as raw material；US4628128 is introduced
A kind of Cu-Si catalyst prepared by infusion process.US4112245 mainly uses coprecipitation to prepare Cu-Zn-Cr and Cu-Cr body
Series catalysts, and introduce the auxiliary agents such as Ca and Cr.Hydrogenation of Dimethyl Oxalate catalyst is mainly with two systems of Cu-Si and Cu-Cr
Main, although Cu-Cr catalyst activity is preferably, Cr severe toxicity, pollution are big, eliminate substantially at present.So Cu-Si system is catalyzed
Agent has good development prospect.But various auxiliary agents, and the mechanism of action of auxiliary agent are all introduced in report Cu-Si system mostly
It is all indefinite with function and effect.Catalyst preparation route is still based on traditional coprecipitation, infusion process, sol-gal process etc..
SiO is used in recent years2Copper-based oxalic acid vinegar for carrier preparation adds the research of hydrogen ethylene glycol catalyst and applies oneself
As this research field hot spot and obtain certain progress.Japanese UBE house journal US4585890 uses the side of solvent evaporated
Method is prepared for Cu/SiO2Catalyst, in diethy-aceto oxalate hydrogenation reaction, when oxalic acid ester conversion rate 100%, glycol selectivity
Up to 99.5%；The disadvantages of due to the active low and high temperature easy-sintering of copper metal itself, intensity difference, pure Cu/SiO2Catalysis
The stability of agent is poor, and the needs of industrial applications are not achieved in service life.Patent CN101455976A is with hexagonal mesoporous molecule
Sieve (HMS) is that carrier is prepared for a kind of oxalate hydrogenation catalyst for being loaded with copper He other promoter metals, wherein using manganese as auxiliary agent
Cu-Mn/SiO2Catalyst is in Hydrogenation of Dimethyl Oxalate reaction, reaction pressure 3.0MPa, and reaction temperature is 200 DEG C, H2/
When DMO=50 (mo1/mo1), when oxalic acid ester conversion rate is up to 100%, glycol selectivity 91%, when other conditions are constant,
Work as H2When/DMO rises to 180 (mol/mol), glycol selectivity 95%.But excessively high hydrogen ester comparison in practical applications follows
The performance requirement of ring compressor is also high, production cost can be made to have greatly increased.
The preparation such as Fujian Inst. of Matter Structure, Chinese Academy of Sciences's coprecipitation and sol-gal process Cu-Cr catalyst,
Cu/SiO2Catalyst, in 2.5~3MPa of reaction pressure, 208~230 DEG C of reaction temperature, 2500~6000h of air speed-1, hydrogen/ester rubs
You can steady running 1134h under the conditions of comparing 20~60.Optimum is dimethyl oxalate conversion ratio 99.8%, and ethylene glycol averagely selects
Selecting property is 95.3%.University Of Tianjin uses Cu-Zn/SiO2Catalyst, under conditions of 2.0MPa, 220 DEG C, dimethyl oxalate
Conversion ratio reaches 90% or more, and the selectivity of ethylene glycol is also 90% or more.East China University of Science uses Cu/SiO2Catalyst,
Study to obtain optimum condition are as follows: 190~200 DEG C of reaction temperature, reaction pressure 2.5MPa, hydrogen ester molar ratio 60, dimethyl oxalate
Conversion ratio reaches 95% or so, and the selectivity of ethylene glycol reaches 90% or so.The reaction temperature and pressure of above-mentioned catalyst are high, second
The selectivity of glycol is low, thus causes heat and power consumption high, and by-product increases, and furthermore grain colony easily occurs for Cu-series catalyst
Gather and inactivate, the service life of catalyst is caused to be difficult to meet industrial requirement.It can be seen that being suitble to the oxalic acid ester through hydrogenation of industrial application
Catalyst first has to the stability for being able to satisfy industrial application needs, secondly has the conversion of high oxalate on the basis of high stable
Rate and high glycol selectivity.
Conventional Cu/SiO2During the preparation process, silica supports may wrap up a large amount of copper activity component to catalyst
And reduce the dispersion degree of copper activity component, load the copper activity component of more amount in high-temperature reaction process meeting so that copper component
Reunite, not only reduces the activity of catalyst in this way and be easier to be allowed to inactivate, shorten the working life.Recently, there is center spoke
The duct monox nanometer ball for penetrating shape has fabulous duct characteristic, such as short diffusion length, monodispersity, high Kong Rong and Gao Ke
Proximity internal surface area；Its synthetic method is different from traditional soft/hard template method, be need by silicon source and surfactant it
Between complicated dynamics assemble to form unstable interface.This special structure is conducive to diffusion and the active site of substance
Arrangement, be applied more especially to metal-supported catalyst carrier, improve the dispersion degree and reaction center of metal active constituent
Activity increases the stability of industrial application and prolongs the service life.In addition, copper and organic ligand material form Cu-MOFs structure,
When with silicon dioxide carried formation catalyst, it can be made to be not easy in biggish space structure complete by carrier silicas network
Package is easy the more copper activity species of exposure in copper oxygen silicon interface, and due to the lower reunion for being also not easy to cause copper of copper content,
Silica plays the role of being anchored copper species, to improve the stability of catalyst.This can solve low copper levels copper point
The low problem of activity, improves the activity and stability of low copper levels catalyst after scattered good but package.
Summary of the invention
The technical problem to be solved by the present invention is to for Cu/SiO in the prior art2Copper activity component is dispersed in catalyst
Property poor, the problem of structural instability and molecular dynamics diffusion difference, and provide a kind of catalysis of efficient stable carried copper-base
Agent and preparation method thereof.Catalyst prepared by the present invention, low temperature active is good, selectivity is high, stability is good；It is mainly used for oxalic acid two
Methyl ester hydrogenation synthesizing glycol.
The present invention reacts to form copper-organic frame compound with six-membered heterocyclic group dicarboxylic acid compound using copper, then loads
Onto mesoporous silica nanosphere, copper activity component has biggish space structure in the catalyst of formation, is not easy it
It is fully wrapped around by carrier silicas network, the more cupprous active components of exposure are easy in copper oxygen silicon interface, and due to copper
The lower reunion for being also not easy to cause copper of content, silica plays the role of being anchored copper species, to improve the stabilization of catalyst
Property.
The present invention, which selects, has the radial duct monox nanometer ball in center as carrier, regulates and controls copper in final catalyst
The size and dispersion degree of species improve the catalytic performance of the synergistic effect raising catalyst of monovalence copper and zerovalent copper.
It is of the present invention that there is radial Jie in center with the radial mesopore orbit mesoporous monox nanometer particle in center
Hole cellular structure and pore size is gradually increased from inside particles to particle surface, is a kind of porous material with novel structure
Material.It is compared with traditional meso-porous titanium dioxide silicon particle with the orderly cellular structure of two-dimentional six sides, this particle is opened with three-dimensional
The dendritic network structure of putting property, thus there is unique structural advantage, i.e., high hole permeability and high particle inner surface
Accessible property, is conveyed to be conducive to substance (molecule or nanoparticle) along the radial duct in center, in this Jie
Hole silica internal load reacts with internal active site.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of efficient stable carried copper-base catalyst, comprising the following steps: by soluble copper salting liquid
It is added in the mixed solution of six-membered heterocyclic group dicarboxylic acids, N,N-dimethylformamide, alcohol react and forms copper-organic ligand
Material；Copper-organic ligand material disintegrating is ground into after dry powder and is add to deionized water to form slurries；By obtained slurries with
Silicon precursor compounds, triblock copolymer P123, monoacid, alcohol are stirred and carry out ageing reaction, obtain efficient stable
Carried copper-base catalyst.
In above-mentioned technical proposal, the preparation method, specifically includes the following steps:
(1) copper-organic ligand material is prepared:
N,N-Dimethylformamide and alcohol are mixed into solution A, then six-membered heterocyclic group dicarboxylic acid compound dissolution A is mixed
In solution, stirring to form solution B to being completely dissolved, then is slowly stirred and copper salt solution is added into solution B to being completely dissolved, and continues
It is dispersed with stirring 0.5~4 hour with 500~2000rpm revolving speed and obtains mixed liquor, mixed liquor is transferred in reaction kettle 100~
It is reacted 12~48 hours at 140 DEG C；After fully reacting, cooled to room temperature, successively filtered, distill water washing three times, nothing
Water-ethanol washing obtains crystalline solid afterwards three times；Crystalline solid is placed in 100~150 DEG C of vacuum oven drying 12~
48 hours, blocky copper-organic ligand material is obtained, and be ground into 300~400 mesh powders, for use；
(2) catalyst is prepared:
Copper-organic ligand material powder dispersion that step (1) obtains is formed into suspension in deionized water, then to
Silicon precursor compounds, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 are added in suspension
(molecular formula: EO20-PO70-EO20, number-average molecular weight Mn=5800, CAS:9003-11-6), monoacid, alcohol, at 60~80 DEG C
Under 0.5~4h stirred with 500~2000rpm revolving speed obtain mixture, then drop at room temperature that mixture ageing is 24~48 small
When；After ageing product is washed with deionized 2-3 times, 12~48 hours, 100~120 are successively dried in vacuo at 60~90 DEG C
24~48 hours are dried at DEG C, 450~550 DEG C are risen to 1~5 DEG C/min heating rate and roasts 2~8 is at this temperature small
When after obtain efficient stable carried copper-base catalyst.
In above-mentioned technical proposal, in step (1), when the n,N-Dimethylformamide and alcohol are mixed into solution A, volume
Than for 1:(1~10).
It is described that six-membered heterocyclic group dicarboxylic acid compound is dissolved in solution A in step (1) in above-mentioned technical proposal
When, the additive amount of six-membered heterocyclic group dicarboxylic acid compound is 2wt%~15wt% of solution A.
It is described that soluble copper salting liquid, six-membered heterocyclic group are added into solution B in step (1) in above-mentioned technical proposal
The molar ratio of copper is 1:(0.5~5.0 in dicarboxylic acid compound and soluble copper salting liquid).
In above-mentioned technical proposal, in step (1), the soluble copper salting liquid is the aqueous solution of soluble copper salt,
The concentration of middle soluble copper salt is 0.5~5.0mol/L, and the soluble copper salt is copper nitrate, copper chloride, copper sulphate, acetic acid
Any one in copper.
In above-mentioned technical proposal, in step (1) and step (2), the alcohol is methanol, appoints in ethyl alcohol, isopropanol, butanol
It anticipates one kind.
In above-mentioned technical proposal, in step (1), the six-membered heterocyclic group dicarboxylic acid compound be 2,3- pyridinedicarboxylic acid,
3,4- pyridinedicarboxylic acid, 3,5- pyridinedicarboxylic acid, 2,2'- bipyridyl -5,5'- dicarboxylic acids, 2,2'- bipyridyl -3,3'- dicarboxyl
Any one in acid, 5- methylpyrazine -2,3- dicarboxylic acids, 5- picoline -2,3- dicarboxylic acids, pyrazine -2,3- dicarboxylic acids.
In above-mentioned technical proposal, in step (2), the dispersion of copper-organic ligand material powder is formed in deionized water
When suspension, the solid-liquid mass ratio of the copper-organic ligand material powder and deionized water is (0.01~0.1): 1.
In above-mentioned technical proposal, in step (2), in the mixture, silicon precursor compounds, triblock copolymer
P123, monoacid, pure and mild deionized water molar ratio be 1:(0.01~0.05): (1.0~2.0): (1.0~2.0): (150~
300)。
In above-mentioned technical proposal, in step (2), the silicon precursor compounds are methyl silicate, silester, silicic acid
Bis- (triethoxy silicon substrate) benzene of propyl ester, butyl silicate, Isosorbide-5-Nitrae-, bis- (triethoxy silicon substrate) ethane of 1,2-, (2- cyanoethyl) three second
In oxysilane, 3- aminopropyl trimethoxysilane any one, two kinds or more the mixing being mixed in any proportion
Object.
In above-mentioned technical proposal, in step (2), the monoacid is hydrochloric acid, nitric acid, acetic acid, any one in formic acid
Aqueous solution, wherein acid concentration be 15~35wt%.
A kind of efficient stable carried copper-base catalyst provided by the present invention, is prepared by above-mentioned preparation method
's.
In above-mentioned technical proposal, the efficient stable carried copper-base catalyst has the radial mesopore orbit in center,
Accordion is presented in surface；The copper content is the 15~45% of overall catalyst weight；Monovalence copper content is active copper total mole number
40~80mol%；Specific surface area of catalyst > the 500m2/ g, Kong Rong > 1.0ml/g, 3.0~8.0nm of average mesopore size.
The present invention also provides a kind of above-mentioned efficient stable carried copper-base catalysts to synthesize second in Hydrogenation of Dimethyl Oxalate
Application in glycol reaction.
In above-mentioned technical proposal, the efficient stable carried copper-base catalyst is placed in fixed bed reactors constant temperature
Section, then dimethyl oxalate methanol solution is passed through vaporizer and is mixed with hydrogen, hydrogen/ester the mass ratio of the material is 20~100, hydrogen
For air speed in 1500~5000h-1, hydrogen partial pressure is 1~3MPa, is reacted at 180~230 DEG C of reaction temperature.
In Hydrogenation of Dimethyl Oxalate reaction process, Cu0Active sites primarily serve activation H2The effect of molecule, and Cu+Activity
Position plays the role of polarization and activates the ester group in dimethyl oxalate, and the synergistic effect of the two realizes that Hydrogenation of Dimethyl Oxalate is anti-
The high conversion and target product answered are highly selective.During the reaction, the reunion increase due to copper particle and Metal-Support
The influence of the factors such as interaction variation, Cu0/Cu+Ratio huge variation can also occur, once the synergistic effect is by broken
Bad, the catalytic activity of catalyst will appear violent decline therewith, and deactivation phenomenom is apparently presented.Sol-gel method preparation, it is identical
Under experiment condition, when copper load capacity increases, the principal element for influencing catalyst activity be silica to the package of copper species and
The reunion of copper species, cause catalyst surface copper species surface area to reduce reduces with catalyst activity.Catalysis provided by the invention
Agent preparation method can be improved the load capacity of copper activity component and improve its dispersion degree, reduce reactant molecule and product
Diffusional resistance on catalyst, the conversion ratio of the dimethyl oxalate reaction undoubtedly improved and the selectivity of ethylene glycol product, and
And reduce deactivation rate, extend catalyst life.
That the purpose of the present invention is to provide a kind of activity is high, preparation process is simple, at low cost, environmental-friendly is used for oxalic acid
The catalyst of dimethyl ester hydrogenation synthesizing of ethylene glycol, the conversion ratio of dimethyl oxalate can reach 99% or more, the selection of ethylene glycol
Performance reaches 96% or more, and reacting balance is easily controllable.
Detailed description of the invention
Fig. 1: the mesoporous monox nanometer ball SEM figure that embodiment 1 obtains；
Fig. 2: the mesoporous monox nanometer ball TEM figure that embodiment 1 obtains.
Specific embodiment
The specific embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold:
Embodiment 1
A kind of high dispersive stable type copper-based catalysts, are prepared by following methods:
1) n,N-Dimethylformamide of 40ml and 100ml ethyl alcohol are mixed into solution, by 20g 2,3- pyridinedicarboxylic acid
Stirring is added thereto to being completely dissolved, then is slowly stirred the Cu (NO that 1.8mol/L concentration is added3)·3H2O solution to completely it is molten
Solution, continuation are dispersed with stirring 1 hour with 1500rpm revolving speed, and mixed liquor is transferred in reaction kettle and is reacted 12 hours for 120 DEG C；Reaction
Cooled to room temperature after completely, suction filtration, distilled water and dehydrated alcohol washing are each three times, obtain crystalline solid, sample is placed in 120
DEG C vacuum oven in dry 24 hours, obtain blocky copper-organic coordination material, and be ground into partial size be 400 mesh powder.
2) 1) 15g obtained copper-organic coordination material solid powder is dispersed in be formed in 623ml deionized water and is suspended
50g silester is then added in liquid, adds 25.06g triblock copolymer P123,35.59g concentration is 30% hydrochloric acid solution
With 26.51g butanol, 2h is stirred with 1000rpm revolving speed at 60 DEG C, then drops to and is aged 24 hours at room temperature, use deionized water
After washing 3 times, it is dried in vacuo drying 24 hours at 24 hours, then 120 DEG C at 80 DEG C, is risen to 1 DEG C/min heating rate
The Cu/SiO of copper high dispersive stable type is obtained after roasting 6 hours at 450 DEG C2Finished catalyst；Pleat is presented in the catalyst surface
Corrugation has the radial mesopore orbit in center, as depicted in figs. 1 and 2.
XRF quantitative analysis measures the Cu/SiO2The mass fraction of Cu is 21.1wt% in catalyst, is denoted as CuDMS-1.System
Standby raw material type and catalyst analysis data are as shown in Table 1 and Table 2.
Embodiment 2
A kind of high dispersive stable type copper-based catalysts, are prepared by following methods:
1) n,N-Dimethylformamide of 50ml and 300ml isopropanol are mixed into solution, by 20g 3,5- pyridine dicarboxyl
Acid is added thereto stirring to being completely dissolved, then is slowly stirred the Cu (CH that 1.08mol/L concentration is added3COO)2·H2O solution is to complete
Fully dissolved, continuation are dispersed with stirring 4 hours with 600rpm revolving speed, and mixed liquor is transferred in reaction kettle and is reacted 24 hours for 130 DEG C；Instead
Cooled to room temperature after answering completely, suction filtration, distilled water and dehydrated alcohol washing are each three times, obtain crystalline solid, sample is placed in
It is dried 48 hours in 105 DEG C of vacuum oven, obtains blocky copper-organic coordination material, and be ground into 350 mesh powder.
2) 1) 10g obtained copper-organic coordination material solid powder is dispersed in be formed in 305ml deionized water and is suspended
20.0g silester is then added in liquid, adds 13.92g triblock copolymer P123,50.21g concentration is that 20% nitric acid is molten
Liquid and 7.26g isopropanol stir 1h at 80 DEG C with 1500rpm revolving speed, then drop to and are aged 24 hours at room temperature, use deionization
After water washing 3 times, drying 48 hours at 24 hours, then 100 DEG C are dried in vacuo at 60 DEG C, with the rising of 2 DEG C/min heating rate
The Cu/SiO2 finished catalyst of copper high dispersive stable type is obtained after roasting 4 hours to 500 DEG C；XRF quantitative analysis measures this
The mass fraction of Cu is 30.9wt% in Cu/SiO2 catalyst, is denoted as CuDMS-2.Prepare raw material type and catalyst analysis number
According to as shown in Table 1 and Table 2.
Embodiment 3
A kind of high dispersive stable type copper-based catalysts, are prepared by following methods:
1) n,N-Dimethylformamide of 60ml and 100ml butanol are mixed into solution, by 20g 2, bipyridyl -5 2'-,
5'- dicarboxylic acids is added thereto stirring to being completely dissolved, then is slowly stirred the CuCl that 0.41mol/L concentration is added2·2H2O solution is extremely
It is completely dissolved, continuation is dispersed with stirring 3 hours with 1200rpm revolving speed, and it is small that mixed liquor is transferred to 105 DEG C of reactions 48 in reaction kettle
When；Cooled to room temperature after fully reacting, suction filtration, distilled water and dehydrated alcohol washing are each three times, obtain crystalline solid, sample
It is placed in 145 DEG C of vacuum oven and dries 12 hours, obtain blocky copper-organic coordination material, and be ground into 325 mesh powder.
2) 1) 20g obtained copper-organic coordination material solid powder is dispersed in be formed in 777ml deionized water and is suspended
28.0g methyl silicate is then added in liquid, adds 37.34g triblock copolymer P123,68.04g concentration is that 25% acetic acid is molten
Liquid and 15.51g ethyl alcohol stir 1h at 60 DEG C with 1800rpm revolving speed, then drop to and are aged 24 hours at room temperature, use deionization
After water washing 3 times, drying 24 hours at 24 hours, then 120 DEG C are dried in vacuo at 80 DEG C, with the rising of 4 DEG C/min heating rate
The Cu/SiO2 finished catalyst of copper high dispersive stable type is obtained after roasting 4 hours to 550 DEG C；XRF quantitative analysis measures this
The mass fraction of Cu is 26.2wt% in Cu/SiO2 catalyst, is denoted as CuDMS-3.Prepare raw material type and catalyst analysis number
According to as shown in Table 1 and Table 2.
Embodiment 4
A kind of high dispersive stable type copper-based catalysts, are prepared by following methods:
1) n,N-Dimethylformamide of 40ml and 400ml methanol are mixed into solution, by 20g 5- methylpyrazine -2,3-
Dicarboxylic acids is added thereto stirring to being completely dissolved, then is slowly stirred and the CuSO45H2O solution of 0.55mol/L concentration is added to complete
Fully dissolved, continuation are dispersed with stirring 1 hour with 1400rpm revolving speed, and mixed liquor is transferred in reaction kettle and is reacted 12 hours for 140 DEG C；
Cooled to room temperature after fully reacting, suction filtration, distilled water and dehydrated alcohol washing are each three times, obtain crystalline solid, sample is set
It is dried 24 hours in 125 DEG C of vacuum oven, obtains blocky copper-organic coordination material, and be ground into 400 mesh powder.
2) 1) 20g obtained copper-organic coordination material solid powder is dispersed in be formed in 730ml deionized water and is suspended
24.0g methyl silicate is then added in liquid, adds 41.15g triblock copolymer P123,76.17g concentration is that 15% hydrochloric acid is molten
Liquid and 15.78g butanol stir 2h at 70 DEG C with 1200rpm revolving speed, then drop to and are aged 24 hours at room temperature, use deionization
After water washing 3 times, drying 36 hours at 36 hours, then 115 DEG C are dried in vacuo at 70 DEG C, with the rising of 2 DEG C/min heating rate
The Cu/SiO2 finished catalyst of copper high dispersive stable type is obtained after roasting 6 hours to 500 DEG C；XRF quantitative analysis measures this
The mass fraction of Cu is 33.9wt% in Cu/SiO2 catalyst, is denoted as CuDMS-4.Prepare raw material type and catalyst analysis number
According to as shown in Table 1 and Table 2.
Embodiment 5
A kind of high dispersive stable type copper-based catalysts, are prepared by following methods:
1) n,N-Dimethylformamide of 70ml and 400ml ethyl alcohol are mixed into solution, by 20g 5- picoline -2,3-
Dicarboxylic acids is added thereto stirring to being completely dissolved, then is slowly stirred and Cu (NO3) the 3H2O solution of 0.59mol/L concentration is added extremely
It is completely dissolved, continuation is dispersed with stirring 2 hours with 1000rpm revolving speed, and it is small that mixed liquor is transferred to 110 DEG C of reactions 36 in reaction kettle
When；Cooled to room temperature after fully reacting, suction filtration, distilled water and dehydrated alcohol washing are each three times, obtain crystalline solid, sample
It is placed in 135 DEG C of vacuum oven and dries 36 hours, obtain blocky copper-organic coordination material, and be ground into 350 mesh powder.
2) 1) 20g obtained copper-organic coordination material solid powder is dispersed in be formed in 729ml deionized water and is suspended
Liquid is then added 30.0g (2- cyanoethyl) triethoxysilane, it is dense to add 12.01g triblock copolymer P123,22.81g
Degree is 30% hydrochloric acid solution and 13.84g isopropanol, stirs 2h at 75 DEG C with 1600rpm revolving speed, then drops to and be aged at room temperature
24 hours, after being washed with deionized 3 times, be dried in vacuo at 90 DEG C at 12 hours, then 120 DEG C dry 48 hours, with 2 DEG C/
Min heating rate rises at 500 DEG C roast 6 hours after obtain the Cu/SiO2 finished catalyst of copper high dispersive stable type；XRF
The mass fraction that quantitative analysis measures Cu in the Cu/SiO2 catalyst is 38.2wt%, is denoted as CuDMS-5.Prepare raw material type
It is as shown in Table 1 and Table 2 with catalyst analysis data.
Embodiment 6
A kind of high dispersive stable type copper-based catalysts, are prepared by following methods:
1) n,N-Dimethylformamide of 200ml and 400ml isopropanol are mixed into solution, by 20g 2,3- pyrazine-two
Carboxylic acid is added thereto stirring to being completely dissolved, then is slowly stirred Cu (CH3COO) 2H2O solution that 0.55mol/L concentration is added
To being completely dissolved, continuation is dispersed with stirring 1 hour with 1600rpm revolving speed, and it is small that mixed liquor is transferred to 125 DEG C of reactions 24 in reaction kettle
When；Cooled to room temperature after fully reacting, suction filtration, distilled water and dehydrated alcohol washing are each three times, obtain crystalline solid, sample
It is placed in 120 DEG C of vacuum oven and dries 24 hours, obtain blocky copper-organic coordination material, and be ground into 325 mesh powder.
2) prepared by mesoporous monox nanometer ball copper-loading catalyst
1) 20g obtained copper-organic coordination material solid powder is dispersed in 1032ml deionized water and forms suspension,
50.0g 3- aminopropyl trimethoxysilane is then added, adds 51.76g triblock copolymer P123,88.43g concentration is
18% formic acid solution and 31.42g butanol stir 1h at 80 DEG C with 1400rpm revolving speed, and it is small then to drop to ageing 24 at room temperature
When, after being washed with deionized 3 times, drying 36 hours at 24 hours, then 110 DEG C are dried in vacuo, at 80 DEG C with 5 DEG C/min liter
Warm rate rises at 550 DEG C roast 4 hours after obtain the Cu/SiO2 finished catalyst of copper high dispersive stable type；XRF quantitatively divides
The mass fraction that analysis measures Cu in the Cu/SiO2 catalyst is 22.5wt%, is denoted as CuDMS-6.Prepare raw material type and catalysis
It is as shown in Table 1 and Table 2 that data are analyzed in agent.
Comparative example 1: catalyst is prepared according to embodiment the method in patent CN103816915 A:
By 7.6g Cu (NO3)2·3H2O is dissolved in 500ml deionized water and forms solution, adjusts solution ph with nitric acid
It is 2~3, then 10g urea is added thereto, adds the mesoporous SiO of 7.89g2Carrier (HMS) is vigorously stirred 4 hours, is formed mixed
Close solution.
Three-necked flask equipped with above-mentioned mixed solution is moved in 90 DEG C of oil baths and is stirred, is heated opposing steam flow.
With the decomposition of urea, the pH value of solution is gradually risen, and stops stirring when the pH value of solution rises to 7.0, while hot by solution mistake
Filter, obtained filter cake (sediment) is washed with deionized, then dry sediment 12 hours at 120 DEG C, then then moves to horse
Not in furnace, in air atmosphere, after being warming up to 450 DEG C with the speed of 1 DEG C/min, then constant temperature calcining 4 hours, obtain copper mass hundred
Dividing content is 20.3% Cu/HMS catalyst, is denoted as CuSiVS-1.
Comparative example 2: it carries out preparing catalyst according to patent CN106563449 A embodiment the method:
10.6g copper nitrate and 0.5g mannitol are dissolved in 100g distilled water, sets in Ultrasound Instrument and carries out after completely dissolution
Sonic oscillation 20min, supersonic frequency 25kHz.5.0g urea stirring and dissolving is added into above-mentioned solution, adds 20m1 ammonium hydroxide
30min is sufficiently stirred.The alkaline silica sol of 21g SiO2 content 40%, the mixed solution in mechanical stirring is finally added dropwise
It is placed in 80 DEG C of water-bath after 5h until solution ph stops heating close to 7.Filter cake is obtained by filtration, and multiple with distilled water
It washs filter cake and for 24 hours, 450 DEG C of roasting 4h, obtains Cu/ in air atmosphere by drying at resulting filter cake in air 120 DEG C
SiO2Catalyst, wherein the mass fraction of Cu is 24.9wt%, is denoted as CuSiVS-2.
Table 1: the raw material type in embodiment and the mol ratio that feeds intake
Table 2: the analysis data of the catalyst in embodiment and comparative example
Application Example:
Applicating expedition is carried out to the catalyst that above-described embodiment 1~6 and comparative example 1~2 obtain:
The catalyst 10ml that Example 1-6 and comparative example 1~2 obtain respectively is fitted into tubular reactor；By reaction tube
250 DEG C are raised to from room temperature with the rate of 2 DEG C/min, during which, hydrogen content progressively increases to 100% from 10%, tube temperature to be reacted
The hydrogen reducing 5h for being 50m1/ (minmlcat.) 99.99% with flow velocity after being raised to 250 DEG C is spent, reduction pressure is
1.2Mpa；The 0.2g/ml dimethyl oxalate methanol solution prepared is passed through vaporizer again and is mixed with hydrogen.With oxalic acid diformazan
Ester is raw material, and hydrogen/ester molar ratio is 50:1, and hydrogen gas space velocity 2000h-1, reaction temperature control is at 180~230 DEG C, reaction pressure
Power is about 2.0MPa, run 500 hours, measure catalyst all data, the results are shown in Table 3, wherein DMO represent dimethyl oxalate,
EG represents ethylene glycol, MG as methyl glycollate.
Table 3: the catalytic performance of different catalysts
| Embodiment | Catalyst code name | Reaction temperature/DEG C | DMO conversion ratio % | EG selectivity % | MG selectivity % |
| Embodiment 1 | CuDMS-1 | 200 | 99.9 | 96.3 | 2.8 |
| Embodiment 2 | CuDMS-2 | 190 | 99.8 | 96.8 | 2.0 |
| Embodiment 3 | CuDMS-3 | 205 | 99.8 | 97.0 | 2.1 |
| Embodiment 4 | CuDMS-4 | 200 | 99.8 | 96.6 | 2.4 |
| Embodiment 5 | CuDMS-5 | 215 | 99.9 | 97.4 | 1.4 |
| Embodiment 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 |
From the analysis of table 3 as can be seen that the catalyst of preparation of the embodiment of the present invention is in Hydrogenation of Dimethyl Oxalate reaction, conversion
Rate > 99%, selectivity > 96% of ethylene glycol；And in the reaction of the catalyst that comparative example obtains under the same conditions, oxalic acid diformazan
Ester conversion rate < 99%, selectivity < 87% of ethylene glycol；This illustrates that catalyst prepared by the present invention has apparent advantage.
Examples detailed above is technical conception and technical characteristics to illustrate the invention, can not be limited with this of the invention
Protection scope.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
1. a kind of preparation method of efficient stable carried copper-base catalyst, which comprises the following steps: will be soluble
Copper salt solution, which is added in the mixed solution of six-membered heterocyclic group dicarboxylic acids, N,N-dimethylformamide, alcohol react, forms copper-
Organic ligand material；Copper-organic ligand material disintegrating is ground into after dry powder and is add to deionized water to form slurries；It will obtain
Slurries be stirred with silicon precursor compounds, triblock copolymer P123, monoacid, alcohol and carry out ageing and react, obtain
Efficient stable carried copper-base catalyst.
2. preparation method according to claim 1, which is characterized in that the preparation method, specifically includes the following steps:
(1) copper-organic ligand material is prepared:
N,N-Dimethylformamide and alcohol are mixed into solution A, then six-membered heterocyclic group dicarboxylic acid compound is dissolved into A mixed solution
In, stirring to being completely dissolved to form solution B, then is slowly stirred and copper salt solution is added into solution B to being completely dissolved, continue with
500~200rpm revolving speed is dispersed with stirring 0.5~4 hour and obtains mixed liquor, and mixed liquor is transferred in reaction kettle 100~140
It is reacted 12~48 hours at DEG C；After fully reacting, cooled to room temperature, successively filtered, distill water washing three times, anhydrous second
Alcohol washing obtains crystalline solid afterwards three times；It is small that crystalline solid is placed in drying 12~48 in 100~150 DEG C of vacuum oven
When, blocky copper-organic ligand material is obtained, and be ground into 300~400 mesh powders, for use；
(2) catalyst is prepared:
Copper-organic ligand material powder dispersion that step (1) obtains is formed into suspension in deionized water, then to suspension
Silicon precursor compounds, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123, unitary are added in liquid
Acid, alcohol stir 0.5~4h at 60~80 DEG C with 500~2000rpm revolving speed and obtain mixture, and then dropping to will mix at room temperature
Object is closed to be aged 24~48 hours；Ageing product be washed with deionized 2-3 time after, successively at 60~90 DEG C be dried in vacuo 12~
450~550 DEG C and herein are risen to dry 24~48 hours at 48 hours, 100~120 DEG C, with 1~5 DEG C/min heating rate
Roasting temperature obtains efficient stable carried copper-base catalyst after 2~8 hours.
3. preparation method according to claim 2, which is characterized in that in step (1), the n,N-Dimethylformamide
When being mixed into solution A with alcohol, volume ratio is 1:(1~10)；Described is dissolved in solution A for six-membered heterocyclic group dicarboxylic acid compound
When middle, the additive amount of six-membered heterocyclic group dicarboxylic acid compound is 2wt%~15wt% of solution A；Described adds into solution B
The molar ratio of copper is 1:(0.5 in soluble copper salting liquid, six-membered heterocyclic group dicarboxylic acid compound and soluble copper salting liquid
~5.0).
4. preparation method according to claim 2, which is characterized in that in step (1), the soluble copper salting liquid is
The aqueous solution of soluble copper salt, wherein the concentration of soluble copper salt is 0.5~5.0mol/L, and the soluble copper salt is nitric acid
Copper, copper chloride, copper sulphate, any one in copper acetate.
5. preparation method according to claim 2, which is characterized in that in step (1) and step (2), the alcohol is first
Alcohol, ethyl alcohol, isopropanol, any one in butanol.
6. preparation method according to claim 2, which is characterized in that in step (1), the six-membered heterocyclic group dicarboxylic
Conjunction object be 2,3- pyridinedicarboxylic acid, 3,4- pyridinedicarboxylic acid, 3,5- pyridinedicarboxylic acid, 2,2'- bipyridyl -5,5'- dicarboxylic acids, 2,
2'- bipyridyl -3,3'- dicarboxylic acids, 5- methylpyrazine -2,3- dicarboxylic acids, 5- picoline -2,3- dicarboxylic acids, pyrazine -2,3- two
Any one in carboxylic acid.
7. preparation method according to claim 2, which is characterized in that in step (2), by copper-organic ligand material powder
When end dispersion forms suspension in deionized water, the solid-liquid matter of the copper-organic ligand material powder and deionized water
Amount is than being (0.01~0.1): 1；In the mixture, silicon precursor compounds, triblock copolymer P123, monoacid, alcohol
Molar ratio with deionized water is 1:(0.01~0.05): (1.0~2.0): (1.0~2.0): (150~300).
8. preparation method according to claim 2, which is characterized in that in step (2), the silicon precursor compounds are
Bis- (triethoxy silicon substrate) benzene of methyl silicate, silester, silicic acid propyl ester, butyl silicate, Isosorbide-5-Nitrae-, the bis- (triethoxysilicanes of 1,2-
Base) ethane, (2- cyanoethyl) triethoxysilane, in 3- aminopropyl trimethoxysilane any one, two kinds or more with
The mixture that arbitrary proportion mixes；The monoacid be hydrochloric acid, nitric acid, acetic acid, any one in formic acid aqueous solution,
Wherein sour concentration is 15~35wt%.
9. a kind of efficient stable carried copper-base catalysis being prepared by the described in any item preparation methods of claim 1-8
Agent, which is characterized in that the efficient stable carried copper-base catalyst has the radial mesopore orbit in center, and pleat is presented in surface
Corrugation；The copper content is the 15~45% of overall catalyst weight；Monovalence copper content be active copper total mole number 40~
80mol%；Specific surface area of catalyst > the 500m2/ g, Kong Rong > 1.0ml/g, 3.0~8.0nm of average mesopore size.
10. a kind of efficient stable carried copper-base catalyst as claimed in claim 9 is in hydrogenation of dimethyl oxalate to synthesizing ethylene glycol
Application in reaction.
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