CN111715226A - Nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate and preparation method thereof - Google Patents
Nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate and preparation method thereof Download PDFInfo
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- CN111715226A CN111715226A CN202010695862.6A CN202010695862A CN111715226A CN 111715226 A CN111715226 A CN 111715226A CN 202010695862 A CN202010695862 A CN 202010695862A CN 111715226 A CN111715226 A CN 111715226A
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000003054 catalyst Substances 0.000 claims abstract description 81
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002071 nanotube Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 230000008020 evaporation Effects 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 34
- 229910052681 coesite Inorganic materials 0.000 claims description 33
- 229910052906 cristobalite Inorganic materials 0.000 claims description 33
- 229910052682 stishovite Inorganic materials 0.000 claims description 33
- 229910052905 tridymite Inorganic materials 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 31
- 239000012018 catalyst precursor Substances 0.000 claims description 22
- 229910002651 NO3 Inorganic materials 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000010335 hydrothermal treatment Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical group [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 13
- 239000003245 coal Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 54
- 239000010949 copper Substances 0.000 description 38
- 238000004821 distillation Methods 0.000 description 31
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 29
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 14
- 239000000499 gel Substances 0.000 description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000536 complexating effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910017985 Cu—Zr Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052914 metal silicate Inorganic materials 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- VOVZXURTCKPRDQ-CQSZACIVSA-N n-[4-[chloro(difluoro)methoxy]phenyl]-6-[(3r)-3-hydroxypyrrolidin-1-yl]-5-(1h-pyrazol-5-yl)pyridine-3-carboxamide Chemical compound C1[C@H](O)CCN1C1=NC=C(C(=O)NC=2C=CC(OC(F)(F)Cl)=CC=2)C=C1C1=CC=NN1 VOVZXURTCKPRDQ-CQSZACIVSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 230000003335 steric effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- KMIOJWCYOHBUJS-HAKPAVFJSA-N vorolanib Chemical compound C1N(C(=O)N(C)C)CC[C@@H]1NC(=O)C1=C(C)NC(\C=C/2C3=CC(F)=CC=C3NC\2=O)=C1C KMIOJWCYOHBUJS-HAKPAVFJSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B01J35/615—
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- B01J35/617—
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- B01J35/635—
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- B01J35/638—
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- B01J35/643—
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- B01J35/647—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—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 oxides of carbon exclusively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate and a preparation method thereof relate to the technical field of coal chemical industry catalysts. The catalyst has a nanotube structure and consists of an active component CuO or an oxide of a metal auxiliary agent and silicon oxide, and the catalyst is prepared by adopting a hydrothermal-ammonia evaporation precipitation method: preparing CuO or assistant into metal ammonia complex solution, adding silica sol or mixed sol of the silica sol and the assistant, transferring into a hydrothermal kettle, aging at high temperature, cooling, evaporating ammonia, filtering,Washing, drying and roasting to obtain the high-efficiency nano catalyst. The catalyst has a uniform nanotube structure with the diameter of about 4 nm, smooth microscopic channels, uniform distribution of metal, high thermal stability and large specific surface area. Pipe curved surface adsorbs H2The catalyst has good catalytic activity and selectivity due to good confinement effect. In the reaction of oxalate hydrogenation, the conversion rate reaches more than 99.9 percent, the selectivity of ethylene glycol is more than 96 percent, the running time is long, and the requirement of industrial production is met.
Description
Technical Field
The invention relates to a nano catalyst for preparing ethylene glycol by dimethyl oxalate gas-phase hydrogenation and a preparation method thereof, and relates to the technical field of coal chemical industry catalysts.
Background
Ethylene glycol is a valuable industrial chemical, is a basic organic raw material in petrochemical industry, is widely applied to the production of polyethylene terephthalate (PET), antifreeze, deicers, solvents of dyes and inks, alkyd resins and the like, and relates to a plurality of fields in downstream application. And China is the largest ethylene glycol demand market in the world and is an important production base of the textile industry in the world, and meanwhile, the consumption of polyester also occupies the largest market, so that the dependence of ethylene glycol on external import is still large. Currently, the ethylene glycol industry production routes are roughly divided into two types: ethylene process and coal-based syngas oxalate process. The petroleum ethylene process route in China mostly adopts imported technology, has long process flow and high energy consumption, and has no cost advantage due to shortage of petroleum resources; the abundant coal resources are in line with the technology for preparing ethylene glycol by the oxalate method of coal-based synthesis gas which is vigorously developed in China, and the production technology which is provided in the eighties of the last century is developed rapidly so far, but the prior art is not completely mature, so that the activity, selectivity and stability of the dimethyl oxalate hydrogenation catalyst are improved, the service life of the catalyst is prolonged, and the quality of EG products is improved, which is an important problem in industrial production.
The Cu-based catalyst is widely applied to the reaction of preparing the ethylene glycol by hydrogenating dimethyl oxalate, and SiO2Due to the characteristics of large specific surface area, good pore structure, surface modification, better dispersibility and the like, the Cu/SiO material ensures that the Cu/SiO material has high specific surface area and good surface property2The catalyst has good catalytic performance in the reaction of preparing the ethylene glycol by hydrogenating the dimethyl oxalate. Day(s)The Utility company of the ministry of Japan proposed a route to ethylene glycol from the hydrogenation of oxalic ester, and earlier proposed a copper-based catalyst of the cuprammonium-silica gel method in U.S. Pat. No. 4440873,4585890, unlike the Cr-type catalyst of ARCO company U.S. Pat. No. 5,4112245, which is contaminated by the toxic nature of Cr, and proposed a Cu/SiO catalyst in the gas phase hydrogenation of oxalic ester2The catalyst has high conversion rate and selectivity.
Cu/SiO in domestic oxalate hydrogenation2The catalyst has a plurality of patents, Cu is soaked on macroporous solid silica gel by an ion exchange method given by Fujian institute CN102247847A Yaoyuan root and the like, the activity is high, the reaction is stable, the DMO conversion rate reaches more than 98%, and the EG selectivity is more than 94%. The Henan coal industry CN102350348A Jiang Yuan Li and the like propose that CuO nano-particles are coated by mesoporous silicon shells to form the core-shell catalyst, and the catalyst has high activity and selectivity and good stability. Zhang Heng et al CN108479798A proposes that hollow silicon dioxide is used as a carrier catalyst structure except an active component added with an auxiliary agent manganese, and the conversion rate of DMO reaches more than 98 percent; CN102151568A, CN102814184A and the like are also disclosed in Cu/SiO2Different assistants such as metal Zn, Mg and the like are added to improve and improve the activity, selectivity and stability of the catalyst and prolong the service life of the catalyst.
Disclosure of Invention
The invention provides a high-efficiency nano catalyst with high activity, selectivity and large specific surface area, and has higher stability. The catalyst is prepared by a hydrothermal-vapor ammonia precipitation method to obtain the copper silicate catalyst with a nanotube structure, wherein the inner diameter of the nanotube is about 4 nm, the wall thickness is about 1.3nm, and the length of the nanotube is 40-200 nm. The catalyst with the structure has the advantages of uniform structure, smooth microscopic channels, uniform distribution of metal, high thermal stability and large specific surface area. The curved surface of the tube has good H2 adsorption effect, and the surface H2/ester ratio is improved during hydrogenation reaction. The catalyst has good catalytic activity and selectivity due to the good confinement effect. Under certain reaction conditions, the conversion rate of the oxalate reaches more than 99.9 percent, the selectivity of the glycol is more than 96 percent, the operation time is more than 5000 hours, and the requirement of industrial production is met.
The invention discloses a nanotube structure catalyst with high oxalate hydrogenation efficiency, which adopts the following technical scheme:
the catalyst is a copper silicate catalyst with a nanotube structure, the catalyst comprises an active component and a carrier, the active component is CuO and an oxide of a metal auxiliary agent, the metal auxiliary agent is one or more of Ni, Zr, Mg or Ag, the CuO accounts for 25-50% of the total amount of the catalyst, and the oxide of the metal auxiliary agent accounts for 1-5%.
CuO accounts for 25-35% of the total catalyst, oxide of the metal auxiliary accounts for 1-5%, and the metal auxiliary is Zr.
The catalyst is prepared by a hydrothermal-ammonia evaporation precipitation method, is a copper silicate catalyst with a nanotube structure, and due to high-temperature aging treatment, layered silicate is curled due to stress generated by structural asymmetry to form a metal silicate tubular structure, and a sufficient Cu amount is required to support the generation and the growth of the nanotubes in the process, under the condition that a metal additive exists, the minimum content of CuO needs to reach 25% of the total amount of the catalyst, and the addition of the additive metal can reduce the addition amount of CuO.
A preparation method of a nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate comprises the following steps:
(1) dissolving nitrate of copper and metal additives in deionized water at normal temperature to obtain a mixed solution, adding ammonia water into the mixed solution under stirring to prepare a blue transparent metal ammonia complex solution, and uniformly stirring; the pH value of the metal ammonia complex solution is 10-11, and the ion concentration =0.1-1.0 mol/l;
(2) slowly adding the silica sol into the metal ammonia complex solution in the step (1), and stirring and mixing uniformly; the content of silicon dioxide in the silica sol is 5-15wt%, and the particle size is less than 20 nm;
(3) transferring the mixture obtained in the step (2) into a hydrothermal kettle, sealing, and carrying out hydrothermal aging treatment to obtain catalyst precursor slurry; the hydrothermal treatment temperature is 140-180 ℃; the treatment time is 12-24 hours;
(4) cooling the catalyst precursor slurry in the step (3) to carry out ammonia evaporation reaction, and obtaining precursor gel along with the reduction of pH value of ammonia evaporation; the ammonia evaporation temperature is 60-130 ℃; ammonia evaporation time is 2-6h, and the end point is that the pH value of the slurry is reduced to 7;
(5) filtering, washing, drying and roasting the gel obtained in the step (4), and forming to obtain a catalyst precursor; drying at 120 deg.C to obtain blue solid; the roasting temperature is 300-800 ℃, and the time is 3-6 h; tabletting and forming into phi 5 x 5 cylinder; the specific surface area of the obtained catalyst precursor is 400-800m2The pore volume is 0.5-1.5ml/g, and the pore diameter is 1.0-20.0 nm.
A nano-catalyst for preparing ethanediol from dimethyl oxalate through gas-phase hydrogenation is composed of carrier and the active component carried by carrier, which is CuO or the oxide of metal assistant chosen from Ni, Zr, Mg and Ag, and SiO as carrier2. The copper silicate nanotube catalyst comprises CuO accounting for 10-50% of the total catalyst, metal auxiliary accounting for 0-10%, and the rest for removing active components is SiO2The content of (a).
Preferably, the active component CuO accounts for 20-45% of the total catalyst, and the metal auxiliary agent accounts for 0-5% of the total catalyst.
The preferred carrier silica silicon source of the invention is silica sol or sodium silicate, and more preferably silica sol.
The specific surface area of the catalyst is 300-800m2The pore volume is 0.5-1.5ml/g,
the pore diameter is 1.0-20.0 nm.
The preparation method of the nanometer catalyst for preparing the ethylene glycol by hydrogenating the oxalate comprises the following steps of:
(1) dissolving copper or metal additive soluble salt in deionized water at normal temperature (25 ℃) to obtain mixed solution, adding ammonia water into the mixed solution under stirring to prepare blue transparent metal ammonia complex solution, and uniformly stirring;
(2) slowly adding a certain amount of carrier into the complexing liquid in the step (1), and stirring and mixing uniformly;
(3) transferring the mixture obtained in the step (2) into a hydrothermal kettle, sealing, and carrying out hydrothermal aging treatment for a certain period of time to obtain catalyst precursor slurry;
(4) cooling the slurry obtained in the step (3) to carry out ammonia evaporation reaction, and obtaining precursor gel along with the reduction of PH due to ammonia evaporation;
(5) and (4) filtering, washing, drying, roasting and molding the gel obtained in the step (4) to obtain a catalyst precursor.
In step (1) of the present invention, copper and metal soluble salt can be selected from one or more of nitrate, sulfate or acetate, preferably nitrate. Metal ammonia complex solution, ion concentration =0.1-1.0mol/l, preferably 0.1-0.5 mol/l;
the pH value of the ammonia complex solution in the step (1) of the method is preferably 10-11, and the pH value can influence the metal ion dispersibility and the specific surface area of the catalyst;
the carrier of the step (2) of the invention is preferably silica sol, which is cheap and easy to obtain. The content of silicon dioxide in the silica sol is 5-15wt%, and the particle size is less than 20 nm;
the temperature of the hydrothermal treatment in step (3) of the present invention is preferably 70-180 ℃, more preferably 120-160 ℃; the treatment time is preferably 12-24 hours, and a small part of metal ions are still in a free state after the hydrothermal treatment;
the ammonia distillation temperature in the step (4) of the invention is preferably 60-100 ℃, more preferably 80-90 ℃; the ammonia evaporation time is 2-6h, the end point is that the pH of the slurry is reduced to 7, the active component copper and the metal additive are completely precipitated on the carrier, and the evaporated ammonia can be recycled, so that the ammonia water concentration in the step (1) is not more than 10%;
the catalyst precursor in the step (5) is easy to wash, and the wastewater discharge and treatment difficulty is reduced; drying at 90-120 deg.C to obtain blue solid; the roasting temperature is preferably 300-800 ℃, more preferably 300-500 ℃, and the time is 3-6 h; the tablets were formed into a phi 5 x 5 cylindrical shape. The specific surface area of the obtained catalyst precursor is 300-700m2/g, the pore volume is 0.5-1.5ml/g, and the pore diameter is 1.0-20.0 nm.
The catalyst prepared by the hydrothermal-evaporation ammonia precipitation method is subjected to high-temperature aging treatment, and the layered silicate is curled due to stress generated by structural asymmetry to form a metal silicate tubular structure. The silicate nanotube has the characteristics of large specific surface area, abundant pore structures, uniform metal distribution and high thermal stability. Due to the unique structures and properties, the silicate nanotube material has strong hydrogen adsorption capacity and can enrich hydrogen; better thermal stability. The hydrothermal treatment temperature and time affect nanotube formation and growth, and there is also a sufficient amount of Cu to support nanotube growth and length. The structure has good stability, and the roasting and reduction are not damaged in the preparation process of the catalyst. The reduced metal particles are uniformly distributed on the inner and outer surfaces of the nanotube. Nanotubes have steric effects, which give good catalytic activity and selectivity to the catalyst.
Drawings
FIG. 1 is an electron micrograph of the catalyst of example 1.
Detailed Description
The details of the present invention are illustrated by the following examples. The purpose of the present invention is to further illustrate the technical features of the present invention, but not to limit the present invention.
The performance test method of the catalyst for preparing the ethylene glycol by gas phase hydrogenation of dimethyl oxalate (DMO) obtained by the preparation method of the invention comprises the following steps: in a stainless steel fixed bed reactor with the inner diameter of 5.3mm, 5ml of catalyst (20-40 meshes) is fixed in a constant temperature section of the reactor by quartz sand, methanol solution of 20 percent DMO of reaction raw material and hydrogen are mixed, enter a vaporizer for vaporization and then are introduced into the reactor, the reaction temperature is 185 ℃, the reaction pressure is 3.0MPa, the molar ratio of the hydrogen to the dimethyl oxalate is 120, and the mass airspeed of the DMO is 1.0h-1The cooled liquid product was then removed at intervals and analyzed for composition by gas chromatography, and the DMO conversion and EG (ethylene glycol) selectivity were then calculated.
Example 1
Catalyst Cu/SiO for preparing glycol by dimethyl oxalate hydrogenation2Active components CuO and SiO2Is a carrier. Wherein CuO accounts for 25% of the total amount of the carrier, and the balance is the carrier. The preparation method comprises the following steps:
taking Cu (NO)3)2•3H269.4g of copper O-nitrate is dissolved in 550ml of deionized water, 10% ammonia water is added dropwise to prepare a copper ammonia complex solution, and the pH of the solution is controlled to be = 10.5. After stirring for 1h, 5% SiO in the solution was slowly added2A silica sol solution of (2), mixingTransferring the mixture into a high-pressure hydrothermal kettle, heating to 140 ℃, stirring and aging for 14 h. And after the hydrothermal treatment, cooling to 85 ℃ for ammonia distillation, wherein the ammonia distillation is carried out for 4 hours until the pH value is reduced to 7.0, and the ammonia distillation is stopped. Filtering, washing and drying the gel at 120 ℃ to obtain light blue solid, and roasting at 400 ℃ for 4h to obtain a catalyst precursor Cu25/SiO2: "25" means a CuO content of 25%. The BET test results and the performance evaluation are shown in the table.
Example 2
Catalyst Cu-Zr/SiO for preparing glycol by dimethyl oxalate hydrogenation2The active components are CuO and auxiliary agent ZrO2，SiO2Is a carrier. Wherein CuO accounts for 25% of the total amount of the support, and ZrO23.0% of the total amount of the composition, and the balance of the composition. The preparation method comprises the following steps:
taking Cu (NO)3)2•3H267.4g of copper O-nitrate is dissolved in 500ml of deionized water, 10% ammonia water is added dropwise to prepare a copper ammonia complex solution, and the pH of the solution is controlled to be = 10.5. Stirring for 1 h. Another 9.3g of Zr (NO3) 4.5H 2O was dissolved in 650ml of deionized water and slowly added to 426.4g of silica sol (containing 15% SiO)2) Uniformly stirring and then adding the mixture into the copper ammonia complexing liquid for mixing; transferring the mixture into a high-pressure hydrothermal kettle, heating to 140 ℃, stirring and aging for 14 h. And after the hydrothermal treatment, cooling to 85 ℃ for ammonia distillation, wherein the ammonia distillation is carried out for 4 hours until the pH value is reduced to 7.0, and the ammonia distillation is stopped. Filtering, washing and drying the gel at 120 ℃ to obtain a blue solid, and roasting at 400 ℃ for 4h to obtain a catalyst precursor Cu25-3.0Zr/SiO2: "25" means that the CuO content is 25% CuO, and "3.0" means that ZrO2 is 3.0%2And (4) content. The BET test results and the performance evaluation are shown in the table.
Example 3
Catalyst Cu-Ni/SiO for preparing glycol by dimethyl oxalate hydrogenation2The active components are CuO and the auxiliary agents NiO and SiO2Is a carrier. Wherein CuO accounts for 25 percent of the total amount of the carrier, NiO accounts for 3 percent, and the rest is the carrier. The preparation method comprises the following steps:
taking Cu (NO)3)2•3H2Copper O nitrate 61.7g and Ni (NO)3)2•6H29.5g of nickel O nitrate is dissolved in 550ml of deionized water, 10% ammonia water is added dropwise to prepare a metal ammonia complex solution, and the pH of the solution is controlled to be = 10.5. After stirring for 1h, 5 was slowly added%SiO2The mixture is transferred into a high-pressure hydrothermal kettle, and the temperature is raised to 140 ℃, and the mixture is stirred and aged for 14 hours. And after the hydrothermal treatment, cooling to 85 ℃ for ammonia distillation, wherein the ammonia distillation is carried out for 4 hours until the pH value is reduced to 7.0, and the ammonia distillation is stopped. Filtering, washing and drying the gel at 120 ℃ to obtain a light blue-green solid, and roasting at 400 ℃ for 4h to obtain a catalyst precursor Cu25-3Ni/SiO2: "25" indicates a CuO content of 25% and "3" indicates a NiO content of 3%. The BET test results and the performance evaluation are shown in the table.
Example 4
Catalyst Cu-Ag/SiO for preparing glycol by dimethyl oxalate hydrogenation2Active component CuO and auxiliary agent Ag2O，SiO2Is a carrier. Wherein CuO accounts for 25% of the total amount of the carrier, and Ag2O5%, the balance being support. The preparation method comprises the following steps:
taking Cu (NO)3)2•3H262.1g of copper O nitrate and 6.0g of AgNO3 silver nitrate are dissolved in 600ml of deionized water, 10% ammonia water is added dropwise to prepare a metal ammonia complex solution, and the pH of the solution is controlled to be = 10.5. After stirring for 1h, 5% SiO in the solution was slowly added2The mixture is transferred into a high-pressure hydrothermal kettle, and the temperature is raised to 140 ℃, and the mixture is stirred and aged for 14 hours. And after the hydrothermal treatment, cooling to 85 ℃ for ammonia distillation, wherein the ammonia distillation is carried out for 4 hours until the pH value is reduced to 7.0, and the ammonia distillation is stopped. Filtering, washing and drying the gel at 120 ℃ to obtain a blue solid, and roasting at 400 ℃ for 4h to obtain a catalyst precursor Cu25-5Ag/SiO2: "25" means 25% of CuO content, and "5" means 5% of Ag2And (4) the content of O. The BET test results and the performance evaluation are shown in the table.
Example 5
Catalyst Cu-Zr/SiO for preparing glycol by dimethyl oxalate hydrogenation2The active components are CuO and auxiliary agent ZrO2，SiO2Is a carrier. Wherein CuO accounts for 25% of the total amount of the support, and ZrO21% of the total amount of the carrier. The preparation method comprises the following steps:
taking Cu (NO)3)2•3H267.4g of copper O-nitrate is dissolved in 500ml of deionized water, 10% ammonia water is added dropwise to prepare a copper ammonia complex solution, and the pH of the solution is controlled to be = 10.5. Stirring for 1 h. Another 3.1g of Zr (NO3) 4.5H 2O was dissolved in 650ml of deionized water and slowly added to 438.3g of silica sol(containing 15% SiO)2) Uniformly stirring and then adding the mixture into the copper ammonia complexing liquid for mixing; transferring the mixture into a high-pressure hydrothermal kettle, heating to 140 ℃, stirring and aging for 14 h. And after the hydrothermal treatment, cooling to 85 ℃ for ammonia distillation, wherein the ammonia distillation is carried out for 4 hours until the pH value is reduced to 7.0, and the ammonia distillation is stopped. Filtering, washing and drying the gel at 120 ℃ to obtain a blue solid, and roasting at 400 ℃ for 4h to obtain a catalyst precursor Cu25-1Zr/SiO2: "25" means a CuO content of 25% CuO, and "1" means 1% ZrO2And (4) content. The BET test results and the performance evaluation are shown in the table.
Example 6
Catalyst Cu-Zr/SiO for preparing glycol by dimethyl oxalate hydrogenation2The active components are CuO and auxiliary agent ZrO2，SiO2Is a carrier. Wherein CuO accounts for 25% of the total amount of the support, and ZrO25% of the total amount of the carrier. The preparation method comprises the following steps:
taking Cu (NO)3)2•3H267.4g of copper O-nitrate is dissolved in 500ml of deionized water, 10% ammonia water is added dropwise to prepare a copper ammonia complex solution, and the pH of the solution is controlled to be = 10.5. Stirring for 1 h. Another 15.5g of Zr (NO3) 4.5H 2O was dissolved in 650ml of deionized water and slowly added to 414.6g of silica sol (containing 15% SiO)2) Uniformly stirring and then adding the mixture into the copper ammonia complexing liquid for mixing; transferring the mixture into a high-pressure hydrothermal kettle, heating to 140 ℃, stirring and aging for 14 h. And after the hydrothermal treatment, cooling to 85 ℃ for ammonia distillation, wherein the ammonia distillation is carried out for 4 hours until the pH value is reduced to 7.0, and the ammonia distillation is stopped. Filtering, washing and drying the gel at 120 ℃ to obtain a blue solid, and roasting at 400 ℃ for 4h to obtain a catalyst precursor Cu25-5Zr/SiO2: "25" means a CuO content of 25% CuO, and "5" means 5% ZrO2And (4) content. The BET test results and the performance evaluation are shown in the table.
Example 7
Catalyst Cu-Zr/SiO for preparing glycol by dimethyl oxalate hydrogenation2The active components are CuO and auxiliary agent ZrO2，SiO2Is a carrier. Wherein CuO accounts for 35% of the total amount of the support, and ZrO23.0% of the total amount of the composition, and the balance of the composition. The preparation method comprises the following steps:
taking Cu (NO)3)2•3H294.4g of copper O-nitrate was dissolved in 700ml of deionized water and droppedAdding 10% ammonia water to prepare a copper ammonia complex solution, and controlling the pH of the solution to be = 10.5. Stirring for 1 h. Another 9.3g of Zr (NO3) 4.5H 2O was dissolved in 650ml of deionized water and slowly added to 367.2g of silica sol (containing 15% SiO)2) Uniformly stirring and then adding the mixture into the copper ammonia complexing liquid for mixing; transferring the mixture into a high-pressure hydrothermal kettle, heating to 140 ℃, stirring and aging for 14 h. And after the hydrothermal treatment, cooling to 85 ℃ for ammonia distillation, wherein the ammonia distillation is carried out for 4 hours until the pH value is reduced to 7.0, and the ammonia distillation is stopped. Filtering, washing and drying the gel at 120 ℃ to obtain a blue solid, and roasting at 400 ℃ for 4h to obtain a catalyst precursor Cu35-3Zr/SiO2: "35" means that the CuO content is 35% CuO, and "3" means 3.0% ZrO2And (4) content. The BET test results and the performance evaluation are shown in the table.
Example 8
Catalyst Cu-Zr/SiO for preparing glycol by dimethyl oxalate hydrogenation2The active components are CuO and auxiliary agent ZrO2，SiO2Is a carrier. Wherein CuO accounts for 45% of the total amount of the carrier, and ZrO23.0% of the total amount of the composition, and the balance of the composition. The preparation method comprises the following steps:
taking Cu (NO)3)2•3H2121.3g of copper O nitrate is dissolved in 900ml of deionized water, 10% ammonia water is added dropwise to prepare a copper ammonia complex solution, and the pH of the solution is controlled to be = 10.5. Stirring for 1 h. Another 9.3g of Zr (NO3) 4.5H 2O was dissolved in 650ml of deionized water and slowly added to 308.0g of silica sol (containing 15% SiO)2) Uniformly stirring and then adding the mixture into the copper ammonia complexing liquid for mixing; transferring the mixture into a high-pressure hydrothermal kettle, heating to 140 ℃, stirring and aging for 14 h. And after the hydrothermal treatment, cooling to 85 ℃ for ammonia distillation, wherein the ammonia distillation is carried out for 4 hours until the pH value is reduced to 7.0, and the ammonia distillation is stopped. Filtering, washing and drying the gel at 120 ℃ to obtain a blue solid, and roasting at 400 ℃ for 4h to obtain a catalyst precursor Cu45-3Zr/SiO2: "45" means that the CuO content is 45% CuO, and "3" means 3% ZrO2And (4) content. The BET test results and the performance evaluation are shown in the table.
Example 9
Catalyst Cu-Zr/SiO for preparing glycol by dimethyl oxalate hydrogenation2The active components are CuO and auxiliary agent ZrO2，SiO2Is a carrier. Wherein CuO accounts for 25% of the total amount of the support, and ZrO23.0% of the total amount of the composition, and the balance of the composition. Preparation ofThe method comprises the following steps:
taking Cu (NO)3)2•3H267.4g of copper O-nitrate is dissolved in 500ml of deionized water, 10% ammonia water is added dropwise to prepare a copper ammonia complex solution, and the pH of the solution is controlled to be = 10.5. Stirring for 1 h. Another 9.3g of Zr (NO3) 4.5H 2O was dissolved in 650ml of deionized water and slowly added to 426.4g of silica sol (containing 15% SiO)2) Uniformly stirring and then adding the mixture into the copper ammonia complexing liquid for mixing; transferring the mixture into a high-pressure hydrothermal kettle, heating to 140 ℃, stirring and aging for 10 hours. And after the hydrothermal treatment, cooling to 85 ℃ for ammonia distillation, wherein the ammonia distillation is carried out for 4 hours until the pH value is reduced to 7.0, and the ammonia distillation is stopped. Filtering, washing and drying the gel at 120 ℃ to obtain a blue solid, and roasting at 400 ℃ for 4h to obtain a catalyst precursor Cu25-3Zr/SiO2-10 h: "25" means that the CuO content is 25% CuO, and "3" means that ZrO2 is 3.0%2Content, "-10 h" indicates a high temperature heat treatment time of 10 h. The BET test results and the performance evaluation are shown in the table.
Example 10
Catalyst Cu/SiO for preparing glycol by dimethyl oxalate hydrogenation2The active component CuO accounts for 45% of the total amount of the carrier, and the rest is carrier SiO2. The preparation method comprises the following steps:
taking Cu (NO)3)2•3H2111.0g of copper O-nitrate is dissolved in 900ml of deionized water, 10% ammonia water is added dropwise to prepare a copper ammonia complex solution, and the pH of the solution is controlled to be = 10.5. After stirring for 1h, 5% SiO in the solution was slowly added2The mixture is transferred into a high-pressure hydrothermal kettle, and the temperature is raised to 140 ℃, and the mixture is stirred and aged for 14 hours. And after the hydrothermal treatment, cooling to 85 ℃ for ammonia distillation, wherein the ammonia distillation is carried out for 4 hours until the pH value is reduced to 7.0, and the ammonia distillation is stopped. Filtering, washing and drying the gel at 120 ℃ to obtain a blue solid, and roasting at 400 ℃ for 4h to obtain a catalyst precursor Cu45/SiO2: "45" means a CuO content of 45%. The BET test results and the performance evaluation are shown in the table.
Catalyst BET detection result and performance evaluation table
| example | catalysts | BET（m2/g） | CDMO (%) | SEG (%) | SMG (%) |
| example1 | Cu25/SiO2 | 295 | 89.3 | 90.1 | 8.9 |
| Example2 | Cu25-3Zr/SiO2 | 325 | 95.90 | 96.5 | 2.6 |
| Example3 | Cu25-3Ni/SiO2 | 446 | 97.5 | 92.3 | 7.0 |
| Example4 | Cu25-5Ag/SiO2 | 415 | 92.5 | 89.3 | 9.7 |
| Example5 | Cu25-1Zr/SiO2 | 320 | 96.3 | 95.0 | 3.3 |
| Example6 | Cu25-5Zr/SiO2 | 330 | 93.5 | 96.9 | 4.0 |
| Example7 | Cu35-3Zr/SiO2 | 473 | 99.95 | 97.8 | 0.14 |
| Example8 | Cu45-3Zr/SiO2 | 550 | 99.99 | 96.8 | 0.12 |
| Example9 | Cu25-3Zr /SiO2-10h | 310 | 91.24 | 93.3 | 6.1 |
| Example10 | Cu45/SiO2 | 525 | 99.89 | 96.1 | 0.98 |
From the above table, it can be seen that the catalyst has requirements on the types and contents of the auxiliary agents, and the types of the auxiliary agents have certain influence on the activity of the catalyst and the selectivity of the main product. From the evaluation data of examples 1 to 4, it can be seen that the addition of metal assistants Zr, Ni and Ag obviously improves the catalyst performance: the specific surface area of the catalyst is increased in different degrees, the DMO conversion rate is improved by 3.2-8.2%, the ethylene glycol selectivity is improved or reduced, the metal Zr addition agent is preferably added in consideration of the yield of EG comprehensively, the DMO conversion rate reaches 95.9%, and the EG selectivity is also improved to 96.5%; examples 2, 5, 6 catalysts with various levels of Zr metal promoter added, evaluation data combined with DMO conversion and EG selectivity, with a preferred addition of 3.0% ZrO 2; from the evaluation data of examples 2, 7 and 8, the CuO content is increased from 25% to 45%, and the catalyst activity is obviously enhanced along with the increase of the copper content under the condition of adding 3.0% of ZrO2 of the same auxiliary agent, and CDMOThe selectivity of EG is improved by 4 percent, when 45 percent of CuO is reached, the activity of the catalyst is stronger, deep hydrogenation is easy to generate ethanol, the selectivity of EG is reduced, and therefore the content of copper oxide is not easy to be too high.
FIG. 1 is an electron microscope scanning image of the catalyst in example 1, from which it can be seen that the catalyst is in a shape of a nanotube, because the layered silicate is curled due to stress generated by structural asymmetry during the preparation process due to high-temperature aging treatment, and a metal silicate tubular structure is formed. The hydrothermal treatment temperature and time can affect the formation and growth of the nanotubes, and compared with example 2, in example 9 of the application, the conversion rate of DMO and the selectivity of EG are reduced, and although the contents of CuO and Zr metal auxiliary agents are the same, the short hydrothermal treatment time does have adverse effect on the performance of the catalyst; but there is also sufficient Cu content to support nanotube growth and length, increasing CuO content from 25% to 35% from the evaluation data of examples 2, 7, and catalyst activity increases significantly with increasing copper content.
In the catalyst of example 10, only CuO is used as an active component, and when the CuO accounts for 45% of the total amount of the catalyst, the specific surface area reaches 525 m2In terms of/g, the DMO conversion was 99.85% and the EG selectivity was 95.8%. When the metal assistant oxide is introduced into the active component of the catalyst, the content of CuO can be greatly reduced, in example 7 of the present application, CuO accounts for 35% of the total amount of the catalyst, ZrO accounts for 3% of the total amount of the catalyst, and the specific surface area reaches 473 m2The conversion rate of DMO is 99.95 percent, and the selectivity of EG is 97.8 percent; compared with the catalyst in the embodiment 10, the content of CuO in the embodiment 7 is reduced by 20 percent, the content of the metal auxiliary agent oxide is only added by 3 percent, and the catalytic performance of the catalyst in the embodiment 7 is equivalent to or even better than that of the embodiment 2.
Claims (3)
1. A nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate is characterized in that: the catalyst is a copper silicate catalyst with a nanotube structure, and comprises an active component and a carrier, wherein the active component is CuO or an oxide of CuO and a metal auxiliary agent, and the metal auxiliary agent is one or more of Ni, Zr, Mg or Ag;
when only CuO is adopted as the active component, the CuO accounts for 40-50% of the total amount of the catalyst, and the balance is SiO as a carrier2；
When the active component adopts oxide of CuO and metal auxiliary agent, CuO is 20-45% of total catalyst, oxide of metal auxiliary agent is 1-5%, and the rest is carrier SiO2。
2. The nano-catalyst for preparing ethylene glycol through gas-phase hydrogenation of oxalate according to claim 1, wherein: when the active component adopts CuO and an oxide of a metal auxiliary agent, the CuO accounts for 25-35% of the total amount of the catalyst, the oxide of the metal auxiliary agent accounts for 3%, and the metal auxiliary agent is Zr.
3. The method for preparing the nano-catalyst for preparing the ethylene glycol by the gas-phase hydrogenation of the oxalate according to claim 1, comprising the following steps of:
(1) under the condition of normal temperature, dissolving copper nitrate or nitrate of copper nitrate and metal auxiliary agent in deionized water to obtain mixed solution, adding ammonia water into the mixed solution under stirring to prepare blue transparent metal ammonia complex solution, and uniformly stirring; the pH value of the metal ammonia complex solution is 10-11, and the ion concentration =0.1-1.0 mol/l;
(2) slowly adding the silica sol into the metal ammonia complex solution in the step (1), and stirring and mixing uniformly; the content of silicon dioxide in the silica sol is 5-15wt%, and the particle size is less than 20 nm;
(3) transferring the mixture obtained in the step (2) into a hydrothermal kettle, sealing, and carrying out hydrothermal aging treatment to obtain catalyst precursor slurry; the hydrothermal treatment temperature is 140-180 ℃; the treatment time is 12-24 hours;
(4) cooling the catalyst precursor slurry in the step (3) to carry out ammonia evaporation reaction, and obtaining precursor gel along with the reduction of pH value of ammonia evaporation; the ammonia evaporation temperature is 60-130 ℃; ammonia evaporation time is 2-6h, and the end point is that the pH value of the slurry is reduced to 7;
(5) filtering, washing, drying and roasting the gel obtained in the step (4), and forming to obtain a catalyst precursor; drying at 120 deg.C to obtain blue solid; the roasting temperature is 300-800 ℃, and the time is 3-6 h; tabletting and forming into phi 5 x 5 cylinder; the specific surface area of the obtained catalyst precursor is 400-800m2The pore volume is 0.5-1.5ml/g, and the pore diameter is 1.0-20.0 nm.
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| CN113117686A (en) * | 2021-04-22 | 2021-07-16 | 兰州理工大学 | Preparation method and application of supported catalyst for catalyzing dimethyl oxalate hydrogenation |
| CN113856700A (en) * | 2021-11-10 | 2021-12-31 | 太原理工大学 | Preparation method and application of copper-silver bimetallic catalyst |
| CN114054041A (en) * | 2021-09-29 | 2022-02-18 | 中触媒新材料股份有限公司 | Dimethyl oxalate hydrogenation catalyst, preparation method and application thereof |
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| CN114192164A (en) * | 2021-12-24 | 2022-03-18 | 山东氢谷新能源技术研究院 | Au @ silicate core-shell nano-structure catalyst and preparation method thereof |
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| CN115414952B (en) * | 2022-08-22 | 2023-09-12 | 中国五环工程有限公司 | Multicomponent hydrogenation catalyst for synthesizing methyl glycolate and preparation method thereof |
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