CN109569615B - Catalyst composition, preparation method and application - Google Patents
Catalyst composition, preparation method and application Download PDFInfo
- Publication number
- CN109569615B CN109569615B CN201710904382.4A CN201710904382A CN109569615B CN 109569615 B CN109569615 B CN 109569615B CN 201710904382 A CN201710904382 A CN 201710904382A CN 109569615 B CN109569615 B CN 109569615B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 205
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 170
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 96
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 229910052804 chromium Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052701 rubidium Inorganic materials 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 4
- 229910052792 caesium Inorganic materials 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 78
- 239000011701 zinc Substances 0.000 description 45
- 230000009467 reduction Effects 0.000 description 35
- 229910052783 alkali metal Inorganic materials 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- 150000001340 alkali metals Chemical class 0.000 description 24
- 230000004048 modification Effects 0.000 description 22
- 238000012986 modification Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000001035 drying Methods 0.000 description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000001354 calcination Methods 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000011572 manganese Substances 0.000 description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 6
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 5
- -1 organic acid salt Chemical class 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910017813 Cu—Cr Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 3
- CYPRMUMKDSHJER-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.[Na] Chemical compound O.O.O.O.O.O.O.O.O.[Na] CYPRMUMKDSHJER-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 102100031083 Uteroglobin Human genes 0.000 description 2
- 108090000203 Uteroglobin Proteins 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QYAPHLRPFNSDNH-MRFRVZCGSA-N (4s,4as,5as,6s,12ar)-7-chloro-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O QYAPHLRPFNSDNH-MRFRVZCGSA-N 0.000 description 1
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical group [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention relates to a catalyst composition, a preparation method and application thereof, and mainly solves the technical problems of low activity and selectivity and poor stability in the prior art. The catalyst composition has a chemical formula of M-Cu-X/SiO2‑ZrO2(ii) a Wherein M is at least one selected from the group consisting of oxides of Li, Na, K, Rb and Cs; x is at least one selected from the group consisting of oxides of Ti, V, Cr, Zn, Fe, Ni, Co and Mn; the weight portion of M is 1-10 portions, Cu element is 10-40 portions, X is 2-20 portions, SiO2‑ZrO2The content of (A) is 30-87 parts; SiO 22‑ZrO2Medium, ZrO2Is SiO2‑ZrO2The weight ratio of (A) is 1-20%. The catalyst can be used in the industrial production of ethylene glycol by hydrogenation of oxalate.
Description
Technical Field
The invention relates to a catalyst composition, a preparation method and application.
Background
Ethylene glycol (EG for short) is an important petrochemical basic organic raw material, and more than 100 chemicals can be derived from the ethylene glycol. Wherein, the polyester (including polyester fiber, polyester bottle, polyester film, etc.) is the main consumption field of ethylene glycol in China, and the consumption amount of the polyester (including polyester fiber, polyester bottle, polyester film, etc.) accounts for about 90 percent of the total domestic consumption amount; and the other 10% is used for antifreeze, adhesive, paint solvent, cold-resistant lubricating oil, surfactant and the like. The current route for the industrial production of ethylene glycol is the cracking of naphtha to produce ethylene, the oxidation of ethylene to produce ethylene oxide (EO for short), and finally the hydration of ethylene oxide to obtain ethylene glycol. Under the economic environment that the price of petroleum is high, people increasingly recognize the limitation of petroleum resources, and various countries begin to research the production of ethylene glycol by using coal and natural gas as primary raw materials. The route for preparing the ethylene glycol from the synthesis gas has the advantages of wide raw materials, good economical efficiency and more reasonable process, and gradually becomes a research hotspot for synthesizing the ethylene glycol by a non-petroleum route. The route of preparing glycol from synthetic gas is to synthesize oxalate through CO gas phase catalytic coupling from the synthetic gas, and then prepare glycol through hydrogenation. The method gets rid of the dependence on petroleum resources from raw materials, actively conforms to the development trend of ethylene glycol production technology, and particularly has an extremely important significance for developing a coal process route in China with more coal and less oil.
One of the key technologies for preparing ethylene glycol from coal-based synthesis gas is the development of a catalyst for synthesizing ethylene glycol by hydrogenating oxalate. The American ARCO company in patent US54112245 suggests that the Cu-Cr series catalyst has better hydrogenation activity and selectivity, and adopts Al loaded2O3、SiO2Or the Cu-Cr catalyst on the glass beads, the reaction temperature is 200 ℃ and 230 ℃, but the yield of the ethylene glycol is only 11.7-18.9 percent. In order to improve the selectivity and yield of the reaction, researchers have developed oxalate gas phase hydrogenation catalysts, and EP46983 proposed a route for the gas phase hydrogenation of oxalate over a copper-chromium based catalyst to ethylene glycol.
In the 80 s of the last century, the Japanese ministry of Japan disclosed a lot of patents (Sho 57-122939, Sho 57-122946, Sho 57-123127, etc.), which examined a carrier (Al) for a catalyst mainly composed of copper2O3、SiO2、La2O3Etc.), auxiliaries (K, Zn, Ag, Mo, Ba, etc.), production methods, etc., on the activity and selectivity of the catalyst. The selectivity of reaction is changed by adding an auxiliary agent into a catalyst taking copper as a main body, the selectivity of ethylene glycol can be improved by adding Zn, the selectivity of methyl glycolate can be improved by adding Ag, and the distribution of products can be adjusted by changing reaction conditions (temperature, pressure, space velocity, hydrogen-ester ratio and the like) under the same catalyst, so that products taking methyl glycolate and ethylene glycol as main bodies can be obtained.
The related research institutions in China begin to research oxalate hydrogenation catalysts from the last 80 th century. A Cu-Cr catalyst adopted in the literature (Industrial catalysis 1996, 4: 24-29) is subjected to a model study of diethyl oxalate hydrogenation under the conditions of 208 ℃ and 230 ℃ and 2.5-3.0MPa, and the reaction result is that the conversion rate of diethyl oxalate is 998%, average ethylene glycol selectivity 95.3%, the catalyst can run for 1134 hours. In recent years, the research on oxalate hydrogenation catalysts is vigorous in China. Document CN101524646A proposes using Al2O3A copper-based catalyst which is used as a carrier and takes one or more of Zn, Mn, Mg and Cr as an auxiliary agent, the reaction pressure is 0.1 to 1.0MPa, the reaction temperature is 145-220 ℃, and the hourly space velocity of oxalate solution is 0.1 to 0.6h-1The conversion rate of oxalate is more than 99%, and the selectivity of glycol is more than 90%. Document CN101342489A discloses a copper-silicon hydrogenation catalyst containing an auxiliary agent, wherein the auxiliary agent is selected from one or more of alkaline earth metal, transition metal elements or rare earth metal elements, and under the process conditions of 3.0MPa reaction pressure and 0.7h-1 of polyacid ester liquid hourly space velocity, the conversion rate of the raw material is more than 99%, and the selectivity of ethylene glycol is more than 95%. Document CN101138725A discloses a catalyst for synthesizing ethylene glycol from oxalate and a preparation method thereof, wherein the catalyst is prepared by using copper as an active component and zinc as an auxiliary agent by an impregnation method, the conversion rate of oxalate of the catalyst is about 95%, and the selectivity of ethylene glycol is about 90%. In the latter, there are many patents reporting that a catalyst composed of Mo, Ni, Ba, Fe, Ag, La and other additives is added to the catalyst components, and is applied to a process for synthesizing ethylene glycol from oxalate.
The current state of the prior art still needs an oxalate hydrogenation catalyst with higher activity and selectivity and better stability. Meanwhile, the catalyst also meets the requirements of simple preparation process and cheap and easily-obtained raw materials.
Disclosure of Invention
Based on the prior art, the inventors of the present invention have assiduously studied and found that by using SiO2-ZrO2The composite as a catalyst carrier using a copper catalyst in which an alkali metal and at least one selected from the group consisting of Ti, V, Cr, Zn, Fe, Ni, Co and Mn are used as an auxiliary, can solve at least one of the aforementioned problems, and thus the present invention has been accomplished.
Specifically, the present invention relates to the following aspects.
The present invention relates to a catalyst composition. The catalyst composition has a chemical formula of M-Cu-X/SiO2-ZrO2(ii) a Wherein M is at least one selected from the group consisting of oxides of Li, Na, K, Rb and Cs;
x is at least one selected from the group consisting of oxides of Ti, V, Cr, Zn, Fe, Ni, Co and Mn;
the weight portion of M is 1-10 portions, Cu element is 10-40 portions, X is 2-20 portions, SiO2-ZrO2The content of (A) is 30-87 parts; SiO 22-ZrO2Medium, ZrO2Is SiO2-ZrO2The weight ratio of (A) is 1-20%.
According to one aspect of the present invention, the content of M is 1 to 8 parts, the content of Cu element is 15 to 35 parts, the content of X is 5 to 15 parts, SiO is2-ZrO2The content of (A) is 42-79 parts; SiO 22-ZrO2Medium, ZrO2Is SiO2-ZrO2The weight ratio of (A) is 5-20%.
According to one aspect of the present invention, the content of M is 2 to 7 parts, the content of Cu element is 20 to 33 parts, the content of X is 7 to 13 parts, SiO is2-ZrO2The content of (A) is 47-71 parts; SiO 22-ZrO2Medium, ZrO2Is SiO2-ZrO2The weight ratio of (A) is 5-15%.
According to one aspect of the invention, SiO2-ZrO2Medium, ZrO2The crystal phase structure of (a) is at least one of the group consisting of monoclinic, tetragonal and cubic crystals.
According to one aspect of the invention, M is at least one selected from the group consisting of oxides of Na, K and Rb.
According to one aspect of the invention, M is at least one selected from the group consisting of oxides of Na and K.
According to an aspect of the present invention, X is at least one selected from the group consisting of oxides of Zn, Fe, Ni, Co, and Mn.
According to an aspect of the present invention, X is at least one selected from the group consisting of oxides of Zn, Co, and Mn.
According to an aspect of the present invention, X is at least one selected from the group consisting of oxides of Zn and Mn.
According to one aspect of the invention, the catalyst composition does not contain rare earth oxides.
According to an aspect of the present invention, the rare earth element is at least one selected from the group consisting of La, Eu, Gd, and Tb.
The invention also relates to a method for producing said catalyst composition. The method comprises the following steps:
a) hydrolyzing a mixture containing silicon source solution, zirconate and zirconia to obtain a carrier SiO2-ZrO2(ii) a Wherein the pH value of the silicon source solution is 6-7, and the pH value of the mixture is 8-9;
b) making copper salt, X salt and carrier SiO2-ZrO2Coprecipitating with a precipitator to obtain CuO-X/SiO2-ZrO2；
c) M is supported on CuO-X/SiO2-ZrO2Thereby obtaining M-CuO-X/SiO2-ZrO2；
d) Making M-CuO-X/SiO2-ZrO2Contacting with reducing gas to obtain the catalyst composition M-Cu-X/SiO2-ZrO2。
The invention also relates to application of the catalyst composition in catalyzing oxalate hydrogenation reaction.
According to one aspect of the invention, the hydrogenation reaction conditions include: the reaction temperature is 160 ℃ and 260 ℃, and the weight space velocity of the oxalic ester is 0.1-1.0 h－1The molar ratio of hydrogen to oxalate (60-150) is 1, and the reaction pressure is 2.0-5.0 MPa.
According to one aspect of the invention, the hydrogenation reaction conditions include: the reaction temperature is 180 ℃ and 240 ℃, and the weight space velocity of the oxalic ester is 0.3-0.7 h－1The molar ratio of hydrogen to oxalate is (80-120):1, and the reaction pressure is 2.5-3.5 MPa.
The invention has the beneficial effects that: the catalyst has higher activity, selectivity and stability in the reaction of synthesizing the ethylene glycol by hydrogenating the dimethyl oxalate. For example, by adopting the method, the conversion rate of the oxalic ester can reach 99.9 percent, the corresponding selectivity of the glycol can reach 96.1 percent, the stability of the catalyst is good, and the performance of the catalyst does not decline after 6000 hours of operation.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
Where not explicitly stated, all pressures mentioned in this specification are gauge pressures.
The invention relates toA catalyst composition. The catalyst composition has the chemical formula M-Cu-X/SiO2-ZrO2. Wherein Cu is an active component, M and X are auxiliary agents, SiO2-ZrO2Is a carrier.
According to the present invention, M is at least one selected from the group consisting of oxides of Li, Na, K, Rb and Cs; preferably at least one of the group consisting of oxides of Na, K and Rb; more preferably at least one of the group consisting of oxides of Na and K.
According to the present invention, X is at least one selected from the group consisting of oxides of Ti, V, Cr, Zn, Fe, Ni, Co and Mn; preferably at least one of the group consisting of oxides of Zn, Fe, Ni, Co and Mn; more preferably at least one of the group consisting of oxides of Zn, Co and Mn; most preferably at least one of the group consisting of oxides of Zn and Mn.
According to the invention, the content of M is 1-10 parts, the content of Cu element is 10-40 parts, the content of X is 2-20 parts, and SiO is calculated by weight parts2-ZrO2The content of (A) is 30-87 parts; preferably, the content of M is 1-8 parts, the content of Cu element is 15-35 parts, the content of X is 5-15 parts, SiO2-ZrO2The content of (A) is 42-79 parts; more preferably, the content of M is 2 to 7 parts, the content of Cu element is 20 to 33 parts, the content of X is 7 to 13 parts, SiO2-ZrO2The content of (B) is 47-71 parts.
According to the invention, the support is SiO2-ZrO2Composites, not SiO2And ZrO2The mechanical mixture of (1). SiO carrier2-ZrO2Medium, ZrO2Is SiO2-ZrO2Is 1 to 20% by weight, preferably 5 to 20% by weight, more preferably 5 to 15% by weight.
According to the invention, SiO2-ZrO2Medium, ZrO2The crystal phase structure of (a) is at least one of the group consisting of monoclinic (m), tetragonal (t) and cubic (c).
According to the invention, the catalyst composition does not contain oxides of rare earth elements. In particular, oxides of La, Eu, Gd and Tb are not contained.
The invention also relates to a method for producing the catalyst composition. The manufacturing method comprises the following steps:
a) hydrolyzing a mixture containing silicon source solution, zirconate and zirconia to obtain a carrier SiO2-ZrO2(ii) a Wherein the pH value of the silicon source solution is 6-7, and the pH value of the mixture is 8-9;
b) making copper salt, X salt and carrier SiO2-ZrO2Coprecipitating with a precipitator to obtain CuO-X/SiO2-ZrO2；
c) M is supported on CuO-X/SiO2-ZrO2Thereby obtaining M-CuO-X/SiO2-ZrO2；
d) Making M-CuO-X/SiO2-ZrO2Contacting with reducing gas to obtain the catalyst composition M-Cu-X/SiO2-ZrO2。
According to the present invention, the silicon source solution may be an aqueous sodium silicate solution in step a). The zirconate can be tetraethyl zirconate, tetra-n-propyl zirconate, tetra-isopropyl zirconate, tetra-n-butyl zirconate, and tetra-isobutyl zirconate, or mixtures thereof. The pH of the silicon source solution is controlled to 6-7 by methods well known to those skilled in the art, such as adjustment with an acid, which may be hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, or an aqueous solution thereof. Including mixtures of silicon source solutions, zirconates, and zirconia, controlled to a pH of 8 to 9, again by methods well known to those skilled in the art, such as adjustment with a base, such as ammonia, sodium hydroxide, potassium hydroxide, rubidium hydroxide, or aqueous solutions thereof. The hydrolysis time of the mixture is 4-24 hours.
According to the invention, after the hydrolysis step has been completed in step a), the prepared SiO support can be separated from the product mixture obtained by any separation method known in the art2-ZrO2. The separation method includes, for example, a method of filtering, washing, drying and calcining the obtained product mixture. Here, the filtering, washing, drying and calcining may be performed in any manner conventionally known in the art. Specifically, for example, the filtration may be performed by simply suction-filtering the filtrateThe product mixture obtained. Examples of the washing include washing with deionized water. The drying temperature is, for example, 80 to 160 ℃ and the drying time is, for example, 4 to 24 hours. The drying may be carried out under normal pressure or under reduced pressure. The calcination temperature may be, for example, 350-650 ℃ and the calcination time may be, for example, 2-8 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
According to the invention, step b) is the preparation of CuO-X/SiO by coprecipitation2-ZrO2. Coprecipitation methods are also well known in the art, i.e. copper salts, X salts, SiO as a carrier2-ZrO2And precipitating agent coprecipitation. Specifically, adding copper salt and X salt into water to obtain a mixed solution A; adding a precipitant into water to obtain a solution B; SiO the carrier obtained in the step a)2-ZrO2Dispersing in water, heating the suspension to 40-80 deg.C, adding solution A and solution B into the suspension, maintaining pH at 6-7, and aging to obtain precipitate CuO-X/SiO2-ZrO2. Wherein, the copper salt and the X salt can be nitrate, organic acid salt or the mixture thereof. The precipitant may be aqueous ammonia, ammonium carbonate, ammonium bicarbonate, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, or a mixture thereof. The aging temperature is 40-90 deg.C, and the aging time is 2-24 hr.
According to the invention, in step b), after the end of the coprecipitation step, the intermediate CuO-X/SiO prepared can be separated from the product mixture obtained by any separation method known in the art2-ZrO2. The separation method includes, for example, a method of filtering, washing, drying and calcining the obtained product mixture. Here, the filtering, washing, drying and calcining may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply filtered with suction. Examples of the washing include washing with deionized water. The drying temperature may be, for example, 80 deg.CThe drying time is, for example, 4 to 24 hours at-160 ℃. The drying may be carried out under normal pressure or under reduced pressure. The calcination temperature may be, for example, 350-650 ℃ and the calcination time may be, for example, 2-8 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
According to the invention, step c) consists in loading the intermediate CuO-X/SiO with an alkali metal M2-ZrO2The above. The method for supporting M may employ impregnation methods well known in the art. Specifically, the intermediate CuO-X/SiO2-ZrO2Dispersing in M salt solution to obtain precursor M-CuO-X/SiO2-ZrO2。
According to the invention, in step c), after the end of the impregnation step, the precursor M-CuO-X/SiO prepared can be separated from the product mixture obtained by any separation method known in the art2-ZrO2. The separation method includes, for example, a method of filtering, washing, drying and calcining the obtained product mixture. Here, the filtering, washing, drying and calcining may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply filtered with suction. Examples of the washing include washing with deionized water. The drying temperature is, for example, 80 to 160 ℃ and the drying time is, for example, 4 to 24 hours. The drying may be carried out under normal pressure or under reduced pressure. The calcination temperature may be, for example, 350-650 ℃ and the calcination time may be, for example, 2-8 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
According to the invention, step d) consists in making the precursor M-CuO-X/SiO2-ZrO2Contacting with reducing gas to obtain the catalyst composition M-Cu-X/SiO2-ZrO2. The reducing gas being H2A mixture of inert gases, which may be N2Or in ArAt least one of the catalyst, the volume content of hydrogen in the mixed gas is 5-30%, and the flow rate of the mixed gas is 10-150 ml/min/g; the reduction temperature is preferably 200 ℃ to 400 ℃, and the reduction time is preferably 8 to 20 hours.
The invention also relates to application of the catalyst composition in catalyzing oxalate hydrogenation reaction. The raw material oxalate and hydrogen contact with a catalyst under the condition of hydrogenation reaction to obtain an effluent containing ethylene glycol.
According to the invention, the hydrogenation reaction conditions include: the reaction temperature is 160 ℃ and 260 ℃, and the weight space velocity of the oxalic ester is 0.1-1.0 h－1The molar ratio of hydrogen to oxalate (60-150) is 1, and the reaction pressure is 2.0-5.0 MPa; preferably, the reaction temperature is 180 ℃ and 240 ℃, and the weight space velocity of the oxalic ester is 0.3-0.7 h－1The molar ratio of hydrogen to oxalate is (80-120):1, and the reaction pressure is 2.5-3.5 MPa.
The invention is further illustrated by the following examples.
[ example 1 ]
234.5 g of sodium silicate nonahydrate are dissolved in 800 ml of water, 5 wt% of dilute sulfuric acid is added with stirring to adjust the pH to 6 to 7, and then 17.1 g of tetra-n-butyl zirconate and 5 g of c-ZrO are added2Uniformly stirring the powder, adjusting the pH value to 8-9 by using a 5 wt% sodium hydroxide solution, hydrolyzing for 12h, filtering, washing with deionized water, drying at 120 ℃ for 16h, and roasting at 500 ℃ for 4h to obtain SiO2-ZrO2The catalyst support SZ-1.
Dissolving 113.4 g of copper nitrate trihydrate and 36.7 g of zinc nitrate hexahydrate in 500 ml of water to obtain a solution A1; 65.9 g of anhydrous sodium carbonate are dissolved in 500 ml of water to obtain a solution B1; dispersing 55.0g of carrier SZ-1 in 300 ml of water, heating to 60 ℃, simultaneously dropwise adding the solution A1 and the solution B1 into the dispersion under vigorous stirring, keeping the temperature at 60 ℃ and the pH value at 6-7 in the dropwise adding process, aging for 10h at 60 ℃ after finishing, filtering, washing precipitates with deionized water, drying for 16h at 120 ℃, and roasting for 4h at 450 ℃ to obtain an intermediate PSZ-1.
95 g of intermediate PSZ-1 is dispersed in 500 ml of water, 10.7 g of potassium nitrate is added into the water, the temperature is raised to 80 ℃, the solvent is evaporated to dryness, the mixture is dried at 120 ℃ for 16h and then roasted at 450 ℃ for 4h to obtain a catalyst precursor MPSZ-1.
With H having a hydrogen content of 25% by volume2-N2Reducing the solid with mixed gas at 320 deg.c for 10 hr to obtain M-Cu-X/SiO in the flow rate of 140 ml/min/g catalyst2-ZrO2Catalyst C1.
In the catalyst C1, the weight portion of M (K) is 5.1, the weight portion of Cu is 29.9, the weight portion of X (Zn) is 10.0, and the carrier SiO2-ZrO2Is 55 parts by weight of ZrO in a carrier2The content of (B) was 9.8% by weight.
[ example 2 ]
The catalyst carrier SZ-2 was prepared in the same manner as in example 1 except that sodium nonahydrate and tetra-n-butyl zirconate were used in amounts of 255.1 g and 3.4 g, respectively, and t-ZrO was added2Powder 2.5 g, m-ZrO22.5 g of powder, intermediate PSZ-2, precursor MPSZ-2 and the reduction method were the same as in example 1, to obtain catalyst C2.
In the catalyst C2, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55 parts by weight of ZrO in a carrier2The content of (B) was 1.8% by weight.
[ example 3 ]
The catalyst carrier SZ-3 was prepared in the same manner as in example 1 except that sodium nonahydrate and tetra-n-butyl zirconate were used in amounts of 247.3 g and 8.6 g, respectively, and t-ZrO was added2Powder 2.5 g, c-ZrO22.5 g of powder, intermediate PSZ-3, precursor MPSZ-3 and the reduction method were the same as in example 1, to obtain catalyst C3.
In the catalyst C3, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55 parts by weight of ZrO in a carrier2The content of (B) was 5.1% by weight.
[ example 4 ]
The catalyst support SZ-4 was prepared in the same manner as in example 1 except that sodium silicate nonahydrate and tetra-n-butyl zirconate were usedThe amount of ester was 221.3 g and 25.7 g, respectively, and m-ZrO was added25 g of powder, intermediate PSZ-4, precursor MPSZ-4 and the reduction method were the same as in example 1, to obtain catalyst C4.
In the catalyst C4, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55 parts by weight of ZrO in a carrier2The content of (b) was 15.1% by weight.
[ example 5 ]
The catalyst support SZ-5 was prepared in the same manner as in example 1 except that sodium silicate nonahydrate and tetra-n-butyl zirconate were used in amounts of 210.9 g and 32.5 g, respectively, and the intermediate PSZ-5, the precursor MPSZ-5 and the reduction method were the same as in example 1 to obtain catalyst C5.
In the catalyst C5, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55 parts by weight of ZrO in a carrier2The content of (B) was 19.1% by weight.
Comparative example 1
The catalyst carrier CSZ-1 was prepared in the same manner as in example 1 except that sodium silicate nonahydrate was used in an amount of 260.3 g and that zirconium zirconate tetra-n-butyl ester and zirconium oxide powder were not added. The intermediate CPSZ-1, the precursor CMPSZ-1 and the reduction method were the same as in example 1, yielding catalyst CC 1.
In the catalyst CC1, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier is SiO2Is free of ZrO2And the weight portion is 55.
[ example 6 ]
234.5 g of sodium nonahydrate was dissolved in 800 ml of water, and 5 wt% of dilute hydrochloric acid was added under stirring to adjust pH to 6 to 7, followed by addition of 14.6 g of tetraisopropyl zirconate and 5 g of c-ZrO2Uniformly stirring the powder, adjusting the pH value to 8-9 by using 5 wt% ammonia water, hydrolyzing for 24h, filtering, washing by using deionized water, drying at 150 ℃ for 20h, and roasting at 600 ℃ for 7h to obtain SiO2-ZrO2The catalyst carrier SZ-6.
93.8 g of copper acetate monohydrate and 27.0 g of zinc acetate dihydrate were dissolved in 500 ml of water to give a solution A6; 75.5 g of 28 wt% concentrated ammonia water was added to 500 ml of water to obtain a solution B6; dispersing 55.0g of carrier SZ-6 in 300 ml of water, heating to 80 ℃, simultaneously dropwise adding the solution A6 and the solution B6 into the dispersion under vigorous stirring, keeping the temperature at 80 ℃ and the pH value at 6-7 in the dropwise adding process, aging at 90 ℃ for 23h after finishing, filtering, washing precipitates with deionized water, drying at 90 ℃ for 24h, and roasting at 600 ℃ for 8h to obtain an intermediate PSZ-6.
Dispersing 95 g of intermediate PSZ-1 in 500 ml of water, adding 10.4 g of potassium acetate, heating to 95 ℃, evaporating the solvent, drying at 150 ℃ for 22h, and roasting at 600 ℃ for 4h to obtain a catalyst precursor MPSZ-6.
With H having a hydrogen content of 10% by volume2Reducing the solid for 18 hours at 250 ℃ by using-Ar mixed gas, wherein the flow rate of the mixed gas is 30 ml/min-g of the catalyst, and then obtaining the M-Cu-X/SiO2ZrO2 catalyst C6.
In the catalyst C6, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55 parts by weight of ZrO in a carrier2The content of (B) was 9.8% by weight.
[ example 7 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in example 1 to obtain SZ-1, and the procedure of preparing intermediate PSZ was the same as in example 1 except that the amount of SZ-1 used was 62.1 g, the amount of zinc nitrate hexahydrate was 11.0 g, and the amount of precipitant anhydrous sodium carbonate was 56.3 g to obtain intermediate PSZ-7.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C7.
In the catalyst C7, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 3.1, and the carrier SiO is2-ZrO2Is 61.9 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 8 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in example 1 to obtain SZ-1, and the procedure of preparing intermediate PSZ was the same as in example 1 except that the amount of SZ-1 used was 58.0 g, the amount of zinc nitrate hexahydrate was 25.7 g, and the amount of precipitant anhydrous sodium carbonate was 61.8 g to obtain intermediate PSZ-8.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C8.
In the catalyst C8, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 7.0, and the carrier SiO2-ZrO2Is 58.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 9 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in example 1 to obtain SZ-1, and the procedure of preparing intermediate PSZ was the same as in example 1 except that the amount of SZ-1 used was 52.0 g, the amount of zinc nitrate hexahydrate was 47.7 g, and the amount of precipitant anhydrous sodium carbonate was 70.0 g to obtain intermediate PSZ-9.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C9.
In the catalyst C9, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 13.0, and the carrier SiO is2-ZrO2Is 52.0 parts by weight, ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 10 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in example 1 to obtain SZ-1, and the procedure of preparing intermediate PSZ was the same as in example 1 except that the amount of SZ-1 used was 46.0 g, the amount of zinc nitrate hexahydrate was 69.7 g, and the amount of precipitant anhydrous sodium carbonate was 78.3 g to obtain intermediate PSZ-10.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C10.
In catalyst C10, M was 5.1 parts by weight, Cu was 29.9 parts by weight, X was 19.0 parts by weight, and S was a carrieriO2-ZrO246.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
Comparative example 2
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in example 1 to obtain SZ-1, and the procedure of preparation of intermediate CPSZ was the same as in example 1 except that 65.0 g of SZ-1 was used, zinc nitrate hexahydrate was not added, and 52.2 g of anhydrous sodium carbonate as a precipitant was used to obtain intermediate CPSZ-2.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst CC 2.
In the catalyst CC2, the weight portion of M is 5.1, the weight portion of Cu is 29.9, X is not contained, and SiO is a carrier2-ZrO2Is 65.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight. [ example 11 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in example 1 to obtain SZ-1, and the procedure of preparing intermediate PSZ was the same as in example 1 except that the amount of SZ-1 used was 74.0 g, the amount of copper nitrate trihydrate was 41.6 g, and the amount of precipitant anhydrous sodium carbonate was 32.9 g to obtain intermediate PSZ-11.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C11.
In the catalyst C11, the weight portion of M is 5.1, the weight portion of Cu is 10.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO274.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 12 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in example 1 to obtain SZ-1, and the procedure of preparing intermediate PSZ was the same as in example 1 except that the amount of SZ-1 used was 66.0 g, the amount of copper nitrate trihydrate was 71.8 g, and the amount of precipitant anhydrous sodium carbonate was 46.8 g to obtain intermediate PSZ-12.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C12.
In the catalyst C12, the weight portion of M is 5.1, the weight portion of Cu is 18.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 66.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 13 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in example 1 to obtain SZ-1, and the procedure of preparing intermediate PSZ was the same as in example 1 except that the amount of SZ-1 used was 60.0 g, the amount of copper nitrate trihydrate was 94.5 g, and the amount of precipitant anhydrous sodium carbonate was 57.2 g to obtain intermediate PSZ-13.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C13.
In the catalyst C13, the weight portion of M is 5.1, the weight portion of Cu is 24.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO260.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 14 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in example 1 to obtain SZ-1, and the procedure of preparing intermediate PSZ was the same as in example 1 except that the amount of SZ-1 used was 46.0 g, the amount of copper nitrate trihydrate was 147.5 g, and the amount of precipitant anhydrous sodium carbonate was 81.6 g to obtain intermediate PSZ-14.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C14.
In the catalyst C14, the weight portion of M is 5.1, the weight portion of Cu is 38.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO246.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 15 ]
Catalyst carrier SiO2-ZrO2The preparation method of (1) was the same as in example 1 to obtain SZ-1, and the intermediate PSZ was prepared in the same manner as in example 1 except thatThe amount of SZ-1 used was 58.0 g, giving intermediate PSZ-15.
The alkali metal modification and catalyst reduction procedure was the same as in example 1, except that KNO was used3In an amount of 4.3 g and PSZ-15 in an amount of 97.9 g, to give catalyst C15.
In the catalyst C15, the weight portion of M is 2.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 58.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 16 ]
Catalyst carrier SiO2-ZrO2Was prepared in the same manner as in example 1 to obtain SZ-1, and intermediate PSZ was prepared in the same manner as in example 1 except that the amount of used SZ-1 was 57.0 g to obtain intermediate PSZ-16.
The alkali metal modification and catalyst reduction procedure was the same as in example 1, except that KNO was used3In an amount of 6.5 g and PSZ-16 in an amount of 96.9 g, affording catalyst C16.
In the catalyst C16, the weight portion of M is 3.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 57.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 17 ]
Catalyst carrier SiO2-ZrO2Was prepared in the same manner as in example 1 to obtain SZ-1, and intermediate PSZ was prepared in the same manner as in example 1 except that the amount of SZ-1 used was 53.0 g to obtain intermediate PSZ-17.
The alkali metal modification and catalyst reduction procedure was the same as in example 1, except that KNO was used3In an amount of 15.1 g and PSZ-17 in an amount of 92.9 g, affording catalyst C17.
In the catalyst C17, the weight portion of M is 7.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 53.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 18 ]
Catalyst carrier SiO2-ZrO2Was prepared in the same manner as in example 1 to obtain SZ-1, and intermediate PSZ was prepared in the same manner as in example 1 except that the amount of SZ-1 used was 51.0 g to obtain intermediate PSZ-18.
The alkali metal modification and catalyst reduction procedure was the same as in example 1, except that KNO was used3In an amount of 19.3 g and PSZ-18 in an amount of 90.9 g, affording catalyst C18.
In the catalyst C18, the weight portion of M is 9.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO2-ZrO251.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
Comparative example 3
Catalyst carrier SiO2-ZrO2Was prepared in the same manner as in example 1 to obtain SZ-1, and intermediate CPSZ was prepared in the same manner as in example 1 except that the amount of SZ-1 used was 60.0 g to obtain intermediate CPSZ-3.
In this example, the catalyst was reduced in the same manner as in [ example 1 ] without modification with an alkali metal to obtain catalyst CC 3.
In the catalyst CC3, the weight portion of M is 0, the weight portion of Cu is 30.0, the weight portion of X is 10.0, and the carrier SiO is2-ZrO260.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 19 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in example 1 to obtain SZ-1, and intermediate PSZ was prepared in the same manner as in example 1 except that 36.7 g of zinc nitrate hexahydrate was replaced with 41.4 g of a 50% by weight aqueous solution of manganese nitrate and the amount of precipitant anhydrous sodium carbonate was 65.0 g, to obtain intermediate PSZ-19.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C19.
In catalyst C19, the weight portion of M was 5.1, the weight portion of Cu was 29.9, and the weight of X wasPart is 10.0, carrier SiO2-ZrO2Is 55.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 20 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in (1) to obtain SZ-1, and the procedure of preparation of intermediate PSZ was the same as in (1), except that 36.7 g of zinc nitrate hexahydrate was replaced with 50.5 g of iron nitrate nonahydrate, and the amount of precipitant anhydrous sodium carbonate was 73.1 g to obtain intermediate PSZ-20.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C20.
In the catalyst C20, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 21 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in (1) to obtain SZ-1, and the procedure of preparation of intermediate PSZ was the same as in (1), except that 36.7 g of zinc nitrate hexahydrate was replaced with 35.1 g of cobalt nitrate hexahydrate, and the amount of precipitant anhydrous sodium carbonate was 65.6 g, to obtain intermediate PSZ-21.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C21.
In the catalyst C21, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 22 ]
Catalyst carrier SiO2-ZrO2The procedure of (1) was the same as in (1) to obtain SZ-1, and the procedure of preparation of intermediate PSZ was the same as in (1), except that 36.7 g of zinc nitrate hexahydrate was replaced with 35.1 g of nickel nitrate hexahydrate, and the amount of precipitant anhydrous sodium carbonate was 65.6 g, to obtain intermediate PSZ-22.
The alkali metal modification and catalyst reduction methods were the same as in [ example 1 ], to obtain catalyst C22.
In the catalyst C22, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 23 ]
Catalyst carrier SiO2-ZrO2The intermediate PSZ was prepared in the same manner as in example 1 to give SZ-1 and PSZ-1.
The alkali metal modification and catalyst reduction procedure was the same as in example 1 except that 23.0 g of lithium nitrate was used as the alkali metal salt to give catalyst C23.
In the catalyst C23, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 24 ]
Catalyst carrier SiO2-ZrO2The intermediate PSZ was prepared in the same manner as in example 1 to give SZ-1 and PSZ-1.
The alkali metal modification and catalyst reduction procedure was the same as in example 1 except that the alkali metal salt used was 13.7 g of sodium nitrate to give catalyst C24.
In the catalyst C24, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 25 ]
Catalyst carrier SiO2-ZrO2The intermediate PSZ was prepared in the same manner as in example 1 to give SZ-1 and PSZ-1.
The alkali metal modification and catalyst reduction procedure was the same as in example 1 except that 7.9 grams of rubidium nitrate was used as the alkali metal salt to provide catalyst C25.
Catalyst C25M5.1 weight parts, Cu 29.9 weight parts, X10.0 weight parts, and SiO carrier2-ZrO2Is 55.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
[ example 26 ]
Catalyst carrier SiO2-ZrO2The intermediate PSZ was prepared in the same manner as in example 1 to give SZ-1 and PSZ-1.
The alkali metal modification and catalyst reduction procedure was the same as in example 1 except that the alkali metal salt used was 6.9 g of cesium nitrate to give catalyst C26.
In the catalyst C26, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier SiO is2-ZrO2Is 55.0 parts by weight of ZrO in the carrier2The content of (B) was 9.8% by weight.
The compositions of catalysts C1-26, examples 1-26, and CC1-3, comparative examples 1-3 are shown in table 1.
Comparative example 4
The catalyst carrier CSZ-4 was prepared in the same manner as in example 1, except that sodium silicate nonahydrate was not added and the c-zirconia powder was replaced with m-zirconia powder. The intermediate CPSZ-4, the precursor CMPSZ-4 and the reduction method are the same as in example 1, and the catalyst CC4 is obtained.
In the catalyst CC4, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier is M-ZrO2Is free of SiO2And the weight portion is 55.
Comparative example 5
The catalyst carrier CSZ-5 was prepared in the same manner as in example 1, except that sodium silicate nonahydrate was not added and the c-zirconia powder was replaced with t-zirconia powder. The intermediate CPSZ-5, the precursor CMPSZ-5 and the reduction method were the same as in example 1, yielding catalyst CC 5.
In the catalyst CC5, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier is t-ZrO2Is free of SiO2And the weight portion is 55.
Comparative example 6
The catalyst support CSZ-6 was prepared in the same manner as in example 1 except that sodium silicate nonahydrate was not added. The intermediate CPSZ-6, the precursor CMPSZ-6 and the reduction method were the same as in example 1, yielding catalyst CC 6.
In the catalyst CC6, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and the carrier is c-ZrO2Is free of SiO2And the weight portion is 55.
Comparative example 7
The catalyst carrier CSZ-7 was prepared in the same manner as in example 1 except that the zinc nitrate used was replaced by lanthanum nitrate. The intermediate CPSZ-7, the precursor CMPSZ-7 and the reduction method were the same as in example 1, yielding catalyst CC 7.
In the catalyst CC7, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of La is 10.0, Zn is not contained, and SiO is a carrier2-ZrO2Is 55 parts by weight of ZrO in a carrier2The content of (B) was 9.8% by weight.
Comparative example 8
The catalyst carrier CSZ-8 was prepared in the same manner as in example 1 except that the zinc nitrate used was replaced with europium nitrate. The intermediate CPSZ-8, the precursor CMPSZ-8 and the reduction method were the same as in example 1, yielding catalyst CC 8.
In the catalyst CC8, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of Eu is 10.0, Zn is not contained, and a carrier SiO is2-ZrO2Is 55 parts by weight of ZrO in a carrier2The content of (B) was 9.8% by weight.
Comparative example 9
The preparation of the catalyst support CSZ-9 was the same as in [ example 1 ] except that the pH of the silicon source solution was adjusted to 8; the pH was adjusted to 9 during the preparation with 5 wt% sodium hydroxide solution. The intermediate CPSZ-9, the precursor CMPSZ-9 and the reduction method were the same as in example 1, yielding catalyst CC 9.
In the catalyst CC9, the weight portion of M is 5.1, the weight portion of Cu is 29.9, and the weight portion of X is 5Number 10.0, support SiO2-ZrO2Is 55 parts by weight of ZrO in a carrier2The content of (B) was 9.8% by weight.
Comparative example 10
The preparation of the catalyst support CSZ-10 was the same as in [ example 1 ] except that the pH of the silicon source solution was adjusted to 5; the pH was adjusted to 6 during the preparation with 5 wt% sodium hydroxide solution. The intermediate CPSZ-10, the precursor CMPSZ-10 and the reduction method were the same as in example 1, yielding catalyst CC 10.
In the catalyst CC10, the weight portion of M is 5.1, the weight portion of Cu is 29.9, the weight portion of X is 10.0, and a carrier SiO is2-ZrO2Is 55 parts by weight of ZrO in a carrier2The content of (B) was 9.8% by weight.
The compositions of catalysts C1-26, examples 1-26, and catalysts CC1-10, comparative examples 1-10 are shown in table 1.
[ examples 27 to 52 ]
This example illustrates the use of the catalysts obtained in [ examples 1-26 ] in the hydrogenation of oxalic esters to Ethylene Glycol (EG).
The catalysts C1 to C26 obtained in the present invention [ examples 1 to 26 ] were each charged in an amount of 10 g into a stainless steel reaction tube having an inner diameter of 20 mm, and fed with dimethyl oxalate (DMO) and hydrogen gas to conduct a reaction and evaluation. The catalyst is at the pressure of 3.0MPa, the temperature of 210 ℃ and the space velocity of 0.5h-1The reaction is carried out under the condition that the molar ratio of hydrogen to ester is 100, and the hydrogenation products comprise Methyl Glycolate (MG), Ethanol (ET), 1, 2-Butanediol (BDO) and the like. The reaction results are shown in Table 2. TABLE 1
| Catalyst and process for preparing same | Cu fraction | M number of copies | X number of parts | Ratio of zirconia in the support |
| C1 | 29.9 | K 5.1 | Zn 10 | 9.8 |
| C2 | 29.9 | K 5.1 | Zn 10 | 1.8 |
| C3 | 29.9 | K 5.1 | Zn 10 | 5.1 |
| C4 | 29.9 | K 5.1 | Zn 10 | 15.1 |
| C5 | 29.9 | K 5.1 | Zn 10 | 19.1 |
| CC1 | 29.9 | K 5.1 | Zn 10 | 0 |
| C6 | 29.9 | K 5.1 | Zn 10 | 9.8 |
| C7 | 29.9 | K 5.1 | Zn 3.1 | 9.8 |
| C8 | 29.9 | K 5.1 | Zn 7 | 9.8 |
| C9 | 29.9 | K 5.1 | Zn 13 | 9.8 |
| C10 | 29.9 | K 5.1 | Zn 19 | 9.8 |
| CC2 | 29.9 | K 5.1 | 0 | 9.8 |
| C11 | 10.9 | K 5.1 | Zn 10 | 9.8 |
| C12 | 18.9 | K 5.1 | Zn 10 | 9.8 |
| C13 | 24.9 | K 5.1 | Zn 10 | 9.8 |
| C14 | 38.9 | K 5.1 | Zn 10 | 9.8 |
| C15 | 29.9 | K 2.1 | Zn 10 | 9.8 |
| C16 | 29.9 | K 3.1 | Zn 10 | 9.8 |
| C17 | 29.9 | K 7.1 | Zn 10 | 9.8 |
| C18 | 29.9 | K 9.1 | Zn 10 | 9.8 |
| CC3 | 30 | 0 | Zn 10 | 9.8 |
| C19 | 29.9 | K 5.1 | Mn 10 | 9.8 |
| C20 | 29.9 | K 5.1 | Fe 10 | 9.8 |
| C21 | 29.9 | K 5.1 | Co 10 | 9.8 |
| C22 | 29.9 | K 5.1 | Ni 10 | 9.8 |
| C23 | 29.9 | Li 5.1 | Zn 10 | 9.8 |
| C24 | 29.9 | Na 5.1 | Zn 10 | 9.8 |
| C25 | 29.9 | Rb 5.1 | Zn 10 | 9.8 |
| C26 | 29.9 | Cs 5.1 | Zn 10 | 9.8 |
| CC4 | 29.9 | K 5.1 | Zn 10 | 100 |
| CC5 | 29.9 | K 5.1 | Zn 10 | 100 |
| CC6 | 29.9 | K 5.1 | Zn 10 | 100 |
| CC7 | 29.9 | K 5.1 | La 10 | 9.8 |
| CC8 | 29.9 | K 5.1 | Eu 10 | 9.8 |
| CC9 | 29.9 | K 5.1 | Zn 10 | 9.8 |
| CC10 | 29.9 | K 5.1 | Zn 10 | 9.8 |
TABLE 2
Comparative examples 11 to 20
The evaluation conditions of the catalyst were the same as in example 27, and the results obtained are shown in Table 3.
TABLE 3
[ examples 53-57 ]
The conditions used for evaluation of the catalyst were changed, and the other conditions were the same as [ example 27 ], and the results obtained are shown in Table 4.
TABLE 4
[ example 58 ]
The life of the catalyst C1 was evaluated under the same conditions as in example 27, and the results obtained are shown in table 5.
TABLE 5
| Reaction time (h) | XDMO(％) | SEG(％) |
| 1000 | 100 | 96.1 |
| 2000 | 100 | 96 |
| 3000 | 100 | 96 |
| 4000 | 100 | 96 |
| 5000 | 99.9 | 95.7 |
| 6000 | 99.8 | 95.8 |
Comparative example 21
The lifetime of the catalyst CC1 was evaluated under the same conditions as in example 27, and the results obtained are shown in table 6.
TABLE 6
| Reaction time (h) | XDMO(％) | SEG(％) |
| 100 | 92.1 | 90.1 |
| 200 | 90.1 | 89 |
| 300 | 87.5 | 84.1 |
Claims (10)
1. A catalyst composition for preparing ethanediol by hydrogenating oxalate has the chemical formula of M-Cu-X/SiO2-ZrO2(ii) a Wherein M consists of at least one of the group consisting of oxides of Na or K;
x is composed of at least one of the group consisting of oxides of Zn or Mn;
the weight portion of M is 1-10 portions, Cu element is 10-40 portions, X is 2-20 portions, SiO2-ZrO2The content of (A) is 30-87 parts; SiO 22-ZrO2Medium, ZrO2Is SiO2-ZrO2The weight ratio of (A) is 1-20%;
the preparation method of the catalyst composition comprises the following steps:
a) hydrolyzing a mixture containing silicon source solution, zirconate and zirconia to obtain a carrier SiO2-ZrO2(ii) a Wherein the pH value of the silicon source solution is 6-7, and the pH value of the mixture is 8-9;
b) making copper salt, X salt and carrier SiO2-ZrO2Coprecipitating with a precipitator to obtain CuO-X/SiO2-ZrO2；
c) M is supported on CuO-X/SiO2-ZrO2Thereby obtaining M-CuO-X/SiO2-ZrO2；
d) Making M-CuO-X/SiO2-ZrO2Contacting with reducing gas to obtain the catalyst composition M-Cu-X/SiO2-ZrO2。
2. The catalyst composition of claim 1, wherein the amount of M is 1-8 parts, the amount of Cu is 15-35 parts, the amount of X is 5-15 parts, and SiO is calculated by weight parts2-ZrO2In an amount of 42-79Preparing; SiO 22-ZrO2Medium, ZrO2Is SiO2-ZrO2The weight ratio of (A) is 5-20%.
3. The catalyst composition of claim 1, wherein the amount of M is 2 to 7 parts, the amount of Cu is 20 to 33 parts, the amount of X is 7 to 13 parts, and SiO is calculated by weight parts2-ZrO2The content of (A) is 47-71 parts; SiO 22-ZrO2Medium, ZrO2Is SiO2-ZrO2The weight ratio of (A) is 5-15%.
4. The catalyst composition of claim 1, wherein the SiO is2-ZrO2Medium, ZrO2The crystal phase structure of (a) is at least one selected from the group consisting of monoclinic, tetragonal and cubic crystals.
5. The catalyst composition of claim 1, wherein the catalyst composition is free of rare earth oxides.
6. The catalyst composition according to claim 5, wherein the rare earth element is at least one selected from the group consisting of La, Eu, Gd, and Tb.
7. A process for preparing the catalyst composition of any of claims 1-6, comprising the steps of:
a) hydrolyzing a mixture containing silicon source solution, zirconate and zirconia to obtain a carrier SiO2-ZrO2(ii) a Wherein the pH value of the silicon source solution is 6-7, and the pH value of the mixture is 8-9;
b) making copper salt, X salt and carrier SiO2-ZrO2Coprecipitating with a precipitator to obtain CuO-X/SiO2-ZrO2；
c) M is supported on CuO-X/SiO2-ZrO2Thereby obtaining M-CuO-X/SiO2-ZrO2；
d) Making M-CuO-X/SiO2-ZrO2Contacting with reducing gas to obtain the catalyst composition M-Cu-X/SiO2-ZrO2。
8. Use of the catalyst composition according to any one of claims 1 to 6 for catalyzing the reaction of hydrogenation of oxalate to ethylene glycol.
9. The use of the catalyst composition according to claim 8 for catalyzing the reaction of hydrogenating oxalate to ethylene glycol, wherein the hydrogenation reaction conditions comprise: the reaction temperature is 160 ℃ and 260 ℃, and the weight space velocity of the oxalic ester is 0.1-1.0 h－1The molar ratio of hydrogen to oxalate (60-150) is 1, and the reaction pressure is 2.0-5.0 MPa.
10. Use of the catalyst composition according to claim 9 for catalyzing the reaction of hydrogenating oxalate to ethylene glycol, wherein the hydrogenation reaction conditions comprise: the reaction temperature is 180 ℃ and 240 ℃, and the weight space velocity of the oxalic ester is 0.3-0.7 h－1The molar ratio of hydrogen to oxalate is (80-120):1, and the reaction pressure is 2.5-3.5 MPa.
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| JPS58159433A (en) * | 1982-03-18 | 1983-09-21 | Mitsubishi Gas Chem Co Inc | Preparation of ethylene glycol |
| CN101474561A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylene glycol from hydrogenation of oxalic ester |
| CN101856615A (en) * | 2010-06-04 | 2010-10-13 | 天津大学 | Catalyst for hydrogenation of oxalate to ethylene glycol and preparation method thereof |
| CN102350358A (en) * | 2011-08-10 | 2012-02-15 | 天津大学 | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation |
| CN104043455A (en) * | 2013-03-13 | 2014-09-17 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparation of glycol by oxalate hydrogenation |
| CN106607036A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Oxalate hydrogenation catalyst, preparation method and uses thereof |
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| JPS58159433A (en) * | 1982-03-18 | 1983-09-21 | Mitsubishi Gas Chem Co Inc | Preparation of ethylene glycol |
| CN101474561A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylene glycol from hydrogenation of oxalic ester |
| CN101856615A (en) * | 2010-06-04 | 2010-10-13 | 天津大学 | Catalyst for hydrogenation of oxalate to ethylene glycol and preparation method thereof |
| CN102350358A (en) * | 2011-08-10 | 2012-02-15 | 天津大学 | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation |
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