CN107790138B - A kind of copper zinc catalyst and preparation method thereof - Google Patents
A kind of copper zinc catalyst and preparation method thereof Download PDFInfo
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- CN107790138B CN107790138B CN201610773533.2A CN201610773533A CN107790138B CN 107790138 B CN107790138 B CN 107790138B CN 201610773533 A CN201610773533 A CN 201610773533A CN 107790138 B CN107790138 B CN 107790138B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000010949 copper Substances 0.000 claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000011148 porous material Substances 0.000 claims abstract description 31
- 239000011701 zinc Substances 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 230000032683 aging Effects 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000004033 plastic Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 32
- 239000012752 auxiliary agent Substances 0.000 claims description 25
- 238000009826 distribution Methods 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000004411 aluminium Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 238000001879 gelation Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 26
- 238000003786 synthesis reaction Methods 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000000748 compression moulding Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 239000012071 phase Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 13
- 125000004429 atom Chemical group 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000012224 working solution Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- -1 content are constant Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- SOYFYCJCFAHQDV-UHFFFAOYSA-J copper zinc dicarbonate Chemical compound [Cu++].[Zn++].[O-]C([O-])=O.[O-]C([O-])=O SOYFYCJCFAHQDV-UHFFFAOYSA-J 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
-
- B01J35/399—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—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
- C07C29/151—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 with hydrogen or hydrogen-containing gases
- C07C29/153—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 with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—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 with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a kind of copper zinc catalysts and preparation method thereof.Copper zinc catalyst composition includes active metal component Cu, Zn, aluminium oxide；Wherein the ratio of table phase active metal component CuO and the weight content of body phase active metal component CuO is 2.0:1 ~ 7.0:1, and the weight content of table phase active metal component ZnO is 1.2:1 ~ 4.5:1 with the ratio of the weight content of body phase active metal component ZnO.Preparation method includes: (1) by the soluble-salt of Cu, Zn, Al wiring solution-forming A soluble in water, prepares sodium carbonate liquor B；(2) plastic, aging in reactor tank is added in solution A, solution B cocurrent；(3) gained slurries are filtered, obtained material carries out hydro-thermal process；(4) material is washed, filtering, drying, roasts, compression molding, obtains catalyst.Active component oxidation copper density is big in copper zinc catalyst table phase of the present invention, and the utilization rate of active metal copper is high, and catalyst pore structure is reasonable, improves activity, selectivity and the thermal stability of catalst for synthesis of methanol and the service life of catalyst.
Description
Technical field
The present invention relates to a kind of catalst for synthesis of methanol and preparation method thereof, and in particular to one kind has high activity, Gao Xuan
Selecting property, catalst for synthesis of methanol of good heat resistance and preparation method thereof.
Background technique
Methanol is a kind of extremely important industrial chemicals, be widely used in organic synthesis, dyestuff, fuel, medicine, coating and
National defense industry, yield are only second to synthesis ammonia and ethylene, rank the third of the world, methanol demands amount and production capacity are with industry in recent years
Develop and sustainable growth.
Industrial methanol is generally with containing H2、CO、CO2Synthesis gas under certain pressure, temperature and catalyst existence condition
Production.At present generally use in the world in, low-pressure vapor phase method synthesizing methanol, used catalyst is substantially the mixing of copper, zinc, aluminium
Oxide.CuO, ZnO, Al in catalst for synthesis of methanol2O3The effect of three components is variant, CuO be main active component, ZnO and
Al2O3For auxiliary agent.The addition of ZnO can make catalyst form Cu/Zn synergic agent, and the activity and choosing of catalyst is greatly improved
Selecting property, Al2O3Skeleton function, and active component in energy dispersed catalyst are not only played in the catalyst, make CO2Absorption and turn
Rate improves, and suitable Al is added in copper-based catalysts2O3Catalyst CO can be improved2Synthesizing methanol by hydrogenating selectivity.Catalyst system
Preparation Method usually first with coprecipitation (including cocurrent, it is anti-plus, just plus coprecipitation) generate the mixing subcarbonate of copper zinc,
Then aluminium hydroxide is added in pulping process again, generated slurry is through washing, drying, roasting, compression molding.Cu/ZnO/
Al2O3Distribution and pattern of the catalyst activity with its surface component are closely related, when catalyst composition, content are constant, catalyst
The relative amount of active metal copper and its dispersibility play a crucial role catalytic activity and selectivity on surface.Catalysis
Theory thinks, H2Reaction with CO synthesizing methanol is to carry out on a series of activated centres, and this activated centre is present in
On the interface Cu-CuO being reduced.From the point of view of the whole process of synthesis, as the internal layer for going back original surface phase catalyst gos deep into, not also
Former core is smaller and smaller, and the die area as the interface Cu-CuO being reduced is also smaller and smaller, and the activity of catalyst reduces,
Synthetic reaction rate decreases, and the activity of catalyst reduces, and how to improve the chain carrier of catalyst table phase, so both
Catalyst activity is improved, and improves the service life of catalyst, it has also become the research emphasis of copper-based catalysts.
While catalst for synthesis of methanol has high activity, the selectivity of catalyst also plays a significant role, catalyst
Pore size distribution plays key effect to the selectivity of catalyst, so the pore size distribution of prepared catalyst how to be allowed to be conducive to methanol
Generation, and at present copper-based catalysts research emphasis.
CN 1329938A discloses a kind of preparation method of catalst for synthesis of methanol, using two step method preparation containing copper,
The co-precipitate of zinc, aluminium compound.The selection of dimethyl maleate disclosed in CN101502803A plus hydrogen prepare 1,4- butanediol
The metals such as auxiliary agent Mn, Mg, Cr are added on the basis of two step method to improve the dispersion of Ni metal and Zn in the preparation method of catalyst
Property.Auxiliary agent is added by change copper-based catalysts preparation process or on this basis to change copper oxide on catalyst in the above method
Dispersibility, improve the activity of catalyst, but the activated centre quantity without improving catalyst surface, activity does not obviously mention
It is high.
CN 1660490A discloses a kind of preparation method of catalst for synthesis of methanol, adds in Co-precipitation
A small amount of Surfactant OP.A kind of catalyst for synthesizing copper based methanol preparation method of CN101733109A, is added in precipitation process
Organic additive (one or more of ethylene glycol, diethylamine, glycerol, magnesium stearate, active carbon).The above method is to precipitate
Organic reagent is added in journey to improve the content of CuO in catalyst surface, but organic reagent heat is easy to decompose, and causes to be catalyzed
Agent local sintering influences catalyst thermal stability.
CN101850253A discloses a kind of copper-based catalysts and preparation method thereof containing inorganic expanding agent.It first prepares copper-based
Catalyst Precursors are simultaneously calcined, by calcined copper-based catalysts parent and molding expanding agent (basic copper carbonate zinc and aluminium hydroxide
Mixture) uniformly mixing, co-ground is to being sufficiently mixed, compression molding.This method increases molding hardly possible after expanding agent is added
Degree, it is not easily molded.
CN101327431A discloses a kind of preparation method of catalst for synthesis of methanol, prepares copper zinc co-precipitate first,
The zinc-aluminium co-precipitate with spinel structure is followed by prepared, third step prepares copper aluminium co-precipitate, then by above-mentioned three kinds
Co-precipitate mixing ageing, then washed, dry, roasting, the material after roasting are added the obtained synthesizing methanol of graphite tabletting and urge
Agent.This method main purpose is to improve active ingredient copper and auxiliary agent zinc, carrier aluminum dispersibility, but method is complicated, and three steps are heavy
It forms sediment and sediment mixing is made, cause to influence the performance of catalyst there is also the Nomenclature Composition and Structure of Complexes is uneven in product.
CN 101574649A discloses a kind of preparation method of catalst for synthesis of methanol, and step is by aluminum soluble salt
Aqueous solution is reacted with alkali metal hydroxide-carbonate mixed aqueous solution, generates a kind of transparent meta-aluminate aqueous solution, so
The transparent aqueous solution of itself and the copper containing water-soluble high-molecular compound, zinc salt is subjected to coprecipitation reaction afterwards, generate a kind of copper,
The mixing co-precipitation of zinc, aluminium, then handles by washing, dry, granulation, roasting, beats sheetmolding, and synthesizing methanol catalysis is made
Agent.The method increase the low temperature active of copper-based catalysts and heat resistances, but the active component without improving catalyst surface contains
Amount, active ingredient copper is evenly distributed with co-catalyst zinc, so without fundamentally solving copper-based catalysts activity and selectivity
Lower problem.
The catalst for synthesis of methanol method of above-mentioned patent introduction by be added new auxiliary agent (inorganic assistant and organic additive),
Change catalyst preparation process (step process is changed to two steps or three step process) or change the methods of the presoma of Al, Lai Zeng great is urged
The specific surface area of agent, grain size, the ratio of regulating catalyst component for changing CuO, improve the degree of scatter of active component,
Solve the problems, such as that copper-based catalysts activity and selectivity is lower and the service life is short with this, but all there is complex technical process, activity
Component disperses the disadvantages of table phase active metallic content in not uniform enough, catalyst is smaller and activated centre density is lower.
Al2O3Skeleton function, and active component in energy dispersed catalyst are not only played in copper-based catalysts, how to be utilized
Auxiliary agent A l2O3Skeleton function, allow main active ingredient copper and auxiliary agent zinc more to appear in the surface of catalyst, improve catalyst
The activated centre quantity on surface increases active ingredient copper and co-catalyst zinc contact probability, makes catalyst with suitable hole point
Cloth, significantly improves the activity, selectivity or service life of existing catalyst, and the above patent is all not involved with.
Summary of the invention
In view of the deficiency of the prior art, the present invention provides a kind of copper zinc catalysts and preparation method thereof.This hair
Active component oxidation copper density is big in bright copper zinc catalyst table phase, and the utilization rate of active metal copper is high, and active ingredient copper is urged with helping
Agent zinc is distributed more uniform, enhances the mating reaction of active metal copper and auxiliary agent zinc, while catalyst pore structure is reasonable,
Improve activity, selectivity and the thermal stability of catalst for synthesis of methanol and the service life of catalyst.
Copper zinc catalyst of the invention, composition include active metal component Cu, Zn, aluminium oxide；Wherein mutually activity is golden for table
The ratio of the weight content and the weight content of body phase active metal component CuO that belong to component CuO is 2.0:1 ~ 7.0:1, preferably
The ratio of the weight content and the weight content of body phase active metal component ZnO of 2.5:1 ~ 5.0:1, table phase active metal component ZnO
For 1.2:1 ~ 4.5:1, preferably 1.8 ~ 3.0:1.
In copper zinc catalyst of the invention, the weight content of table phase active metal component CuO is CuO in catalyst table phase
Weight content, the weight content of body phase active metal component CuO are the weight content of CuO in catalyst；Table phase active metal group
Divide the weight content that the weight content of ZnO is ZnO in catalyst table phase, the weight content of body phase active metal component ZnO is to urge
The weight content of ZnO in agent.
Copper zinc catalyst of the invention, on the basis of the weight of catalyst, the composition of catalyst includes, with mass fraction
Meter: CuO is 20%~65%, and preferably 25%~60%, ZnO is 15%~40%, preferably 15%~35%, Al2O3It is 5%~40%, it is excellent
It is selected as 10%~35%.
It is can according to need in catalyst of the invention containing auxiliary agent, the one of auxiliary agent Mn, Mg, Cr, Mo, W, Li or Zr etc.
Kind or it is several, can be added according to a conventional method, with overall catalyst weight meter, auxiliary agent is calculated as 1% ~ 15% with oxide, preferably 1% ~
10%, the sum of catalyst components content is 100%.
The property of copper zinc catalyst of the invention is as follows: specific surface area is 100 ~ 450m20.20 ~ 0.60ml/ of/g, Kong Rongwei
G, pore-size distribution are as follows: diameter is that Kong Rong shared by the hole below 4nm accounts for the 1% ~ 17% of total pore volume, diameter for 4 ~ 8nm hole institute
Kong Rong accounts for total pore volume 2% ~ 20% is accounted for, diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for the 45% ~ 80% of total pore volume, diameter 15nm
It is 1% ~ 20% that above Kong Rong, which accounts for total pore volume, and preferred pore-size distribution is as follows: diameter is Kong Rongzhan shared by the hole below 4nm
The 5% ~ 12% of total pore volume, diameter are that account for total pore volume be 4% ~ 15% to Kong Rong shared by the hole of 4 ~ 8nm, and diameter is shared by the hole of 8 ~ 15nm
Kong Rong account for the 50% ~ 75% of total pore volume, it is 5% ~ 15% that the Kong Rong that diameter is 15nm or more, which accounts for total pore volume,.
The preparation method of copper zinc catalyst of the invention, including following content:
(1) by the soluble-salt of Cu, Zn, Al wiring solution-forming A soluble in water, sodium carbonate liquor B is prepared；
(2) plastic, aging in reactor tank is added in solution A, solution B cocurrent；
(3) slurries obtained by step (2) are filtered, obtained material carries out hydro-thermal process with water vapour, wherein hydro-thermal process
When urea is added；
(4) material that step (3) obtains is washed, filtering, drying, roasts, compression molding, obtains catalyst.
Copper as described in step (1), zinc soluble-salt are nitrate and/or acetate, soluble-salt containing aluminium be aluminum nitrate,
One or more of aluminum sulfate, aluminium chloride or aluminium acetate etc..Copper (Cu in solution A2+) concentration be 1.0~6.0mol/L, preferably
For 2.0~4.0mol/L, zinc (Zn in solution A2+) concentration be 0.5~5.0mol/L, preferably 1.0~3.0mol/L, aluminium (Al3 +) concentration be 1.0~7.0mol/L, preferably 2.0~5.0mol/L.Copper in sodium carbonate and solution A in solution B, zinc, aluminium (copper,
Zinc and aluminium summation) molar ratio be 0.5~3.0, preferably 0.8~1.5.
In solution A as described in step (1), cu zn atomic molar ratio is 0.1~10, preferably 0.2~5, (copper+zinc)/
Aluminium atom molar ratio is 0.1~10, preferably 3~8.
Gelation Conditions described in step (2): reaction temperature be 30~90 DEG C, preferably 40~85 DEG C, pH value be 6.0 ~
11.0, preferably 7.0 ~ 9.0, gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.Aging temperature 50 after plastic~
100 DEG C, preferably 60~90 DEG C, the control of aging pH value are 6.0 ~ 11.0, preferably 7.0 ~ 10.0, and ageing time is 0.5 ~ 5.0
Hour, preferably 1 ~ 3.0 hour.
Hydrothermal conditions described in step (3) are as follows: carrying out under closed container, temperature is 200 ~ 300 DEG C, preferably
It is 210 ~ 260 DEG C, pressure is 1.0 ~ 8.0 MPa, preferably 3.0 ~ 6.0MPa, and the processing time is 0.5 ~ 10.0 hour, preferably
1.0 ~ 6.0 hours.When hydro-thermal process, in the additional amount and catalyst of urea the molar ratio of metallic atom total amount be 0.5:1 ~
10.0:1, preferably 2.0:1 ~ 8.0:1.
Step (4) washing is washed with deionized, and wash temperature is controlled at 30~90 DEG C, and preferably 40~70 DEG C.
Washing times are at 1~8 time, and preferably 2~6 times.Filter cake is dry under the conditions of 50 ~ 150 DEG C, and drying temperature is preferably 60 ~ 120
DEG C, drying time 0.5 ~ 24.0 hour, drying time was preferably 1 ~ 16 hour.The condition of the roasting is as follows: 300~360
DEG C roasting 1 ~ 16 hour, preferably 2 ~ 10 hours.
It can according to need in the method for the present invention and auxiliary agent be added during step (1) and/or (2), auxiliary agent Mn, Mg,
The one or more of Cr, Mo, W, Li or Zr etc., auxiliary agent can be added according to a conventional method, with overall catalyst weight meter, auxiliary agent with
Oxide is calculated as 1% ~ 15%, preferably 1% ~ 10%, and the sum of catalyst components content is 100%.
Copper zinc catalyst of the invention applied to synthesizing methanol react, general process conditions are as follows: reaction temperature be 210~
320 DEG C, more preferably 230~280 DEG C；Pressure is 2~10MPa, more preferably 2~7MPa；Volume space velocity is 2000~15000 h-1,
Preferably 4000~12000 h-1。
Method in compared with the prior art, copper zinc catalyst surface-active bit density of the invention is big, active metal divides
It dissipates that cooperation more evenly, between active metal and auxiliary agent is good, catalyst pore distribution concentration (being concentrated mainly on 8 ~ 15nm), has
The good feature of higher activity, selectivity, thermal stability.
In the preparation method of catalyst of the present invention, Cu, Zn, Al component mixture material precipitated is under appropriate conditions
Simultaneously urea is added in steam treatment, and urea is decomposed into NH under high temperature environment3And CO2, NH3And CO2Water vapour there are the case where
Lower generation NH4 +And HCO3 -Ion, NH4 +And HCO3 -Ion at high temperature under high pressure has a significant impact the micromorphology of material, hydro-thermal
Material phase structure is in rule body before handling, and is changed into the irregular body that irregular sheet is piled into, this structure after hydro-thermal process
Transformation obviously increase distribution of the active metal in table phase, be conducive to improve surface-active metal copper and auxiliary agent density,
Active component and auxiliary agent disperse more evenly simultaneously, increase auxiliary agent to the facilitation of Cu dispersed distribution again in this way.In addition, In
Urea is added when steam treatment, in the transition process of material form the pore size distribution of catalyst can also more concentrated, has
Conducive to being greatly improved for methanol selectivity and thermal stability.In addition, the addition of auxiliary agent facilitates active component CuO and auxiliary agent
Component ZnO is evenly dispersed in table phase in the catalyst.
Specific embodiment
The solution of the present invention and effect are further illustrated below by embodiment.In the present invention, specific surface area and Kong Rong, hole
Distribution is using low temperature liquid nitrogen determination of adsorption method.Catalyst table phase active metallic content uses x-ray photoelectron spectroscopy
(XPS) it measures, caltalyst phase active metallic content is surveyed using inductively coupled plasma atomic emission spectrum (ICP-AES)
It is fixed.Wt% is mass fraction.
Embodiment 1
Weigh Cu (NO3)2·3H2O168g, Zn (NO3)2·6H2O76g, AlCl3·6H2O95g is dissolved in 850mL deionization
Working solution A is made into water, by Na2CO3It is dissolved in wiring solution-forming B in 1000ml deionized water, sodium carbonate and solution in solution B
Copper in A, zinc, aluminium molar ratio be 1.2,450mL water is added into reactor tank, temperature rises to 60 DEG C.Under stirring conditions, will
Solution A and solution B cocurrent are added in reactor tank, and gelation time is 1 hour, and the pH value of control plastic slurries is 7.8 ± 0.2.It stirs
Starting aging in the case where mixing, pH is 7.8 ± 0.2 when aging, and temperature is 75 DEG C, aging 2 hours, by material filtering after aging,
Filter cake carries out hydro-thermal process, the condition of hydro-thermal process under the water vapour containing urea are as follows: urea and active metal atom total amount
Molar ratio be 6:1, temperature be 220 DEG C, pressure 3.5MPa, processing the time be 4 hours, temperature is washed at 50 DEG C with water purification
It washs 3 times, it is 7 hours dry at 90 DEG C after washing, then roasted 4 hours at 320 DEG C, appropriate graphite and hydraulic pressure is added in the material after roasting
In flakes, catalyst A is obtained.Composition, pore size distribution and main character are shown in Table 1.
Embodiment 2
According to the method for embodiment 1, it is matched by the constituent content of the catalyst B in table 1, nitric acid is added into dissolving tank 1
Copper, zinc nitrate, aluminum nitrate, magnesium chloride prepare working solution A, and sodium carbonate is added into NaOH solution tank NaOH 2 and is configured to working solution B, molten
Copper in sodium carbonate and solution A in liquid B, zinc, aluminium molar ratio be 1.0,500mL water is added into reactor tank, temperature rises to 65 DEG C.
Under stirring conditions, solution A and solution B cocurrent are added in reactor tank, gelation time is 0.8 hour, controls plastic slurries
PH value be 8.0 ± 0.2.Start aging in the case where stirring, pH is 8.2 ± 0.2 when aging, and temperature is 70 DEG C, and aging 3 is small
When, by material filtering after aging, filter cake carries out hydro-thermal process, the condition of hydro-thermal process under the water vapour containing urea are as follows: urine
The molar ratio of element and active metal atom total amount is 7:1, and temperature is 250 DEG C, pressure 4.0MPa, and the processing time is 3 hours, temperature
Degree is washed 5 times at 40 DEG C with water purification, 10 hours dry at 80 DEG C after washing, then is roasted 5 hours at 350 DEG C, the object after roasting
Appropriate graphite is added in material and hydraulic pressure is in blocks, obtains catalyst B.Composition, pore size distribution and main character are shown in Table 1.
Embodiment 3
According to the method for embodiment 1, it is matched by the constituent content of the catalyst C in table 1, nitric acid is added into dissolving tank 1
Copper, zinc nitrate, aluminium chloride prepare working solution A, and sodium carbonate is added into NaOH solution tank NaOH 2 and is configured to working solution B, carbon in solution B
Copper in sour sodium and solution A, zinc, aluminium molar ratio be 1.3,600mL water is added into reactor tank, temperature rises to 70 DEG C.It is stirring
Under conditions of, solution A and solution B cocurrent are added in reactor tank, gelation time is 1.5 hours, controls the pH value of plastic slurries
It is 7.4 ± 0.2.Starting aging in the case where stirring, pH is 7.8 ± 0.2 when aging, and temperature is 80 DEG C, aging 2.5 hours, always
By material filtering after change, filter cake carries out hydro-thermal process, the condition of hydro-thermal process under the water vapour containing urea are as follows: urea and work
Property metallic atom total amount molar ratio be 5:1, temperature be 220 DEG C, pressure 5.0MPa, processing the time be 6 hours, temperature is 60
DEG C when, washed 2 times with water purification, 6 hours dry at 120 DEG C after washing, then roast 6 hours at 300 DEG C, the material after roasting is added
Appropriate graphite and hydraulic pressure are in blocks, obtain catalyst C.Composition, pore size distribution and main character are shown in Table 1.
Embodiment 4
According to the method for embodiment 1, it is matched by the constituent content of the catalyst D in table 1, nitric acid is added into dissolving tank 1
Copper, zinc nitrate, aluminum sulfate prepare working solution A, and sodium carbonate is added into NaOH solution tank NaOH 2 and is configured to working solution B, carbon in solution B
Copper in sour sodium and solution A, zinc, aluminium molar ratio be 1.2,450mL water is added into reactor tank, temperature rises to 60 DEG C.It is stirring
Under conditions of, solution A and solution B cocurrent are added in reactor tank, gelation time is 1 hour, and the pH value of control plastic slurries is
7.8±0.2.Starting aging in the case where stirring, pH is 7.6 ± 0.2 when aging, and temperature is 75 DEG C, aging 2 hours, after aging
By material filtering, filter cake carries out hydro-thermal process, the condition of hydro-thermal process under the water vapour containing urea are as follows: urea and activity gold
The molar ratio for belonging to atom total amount is 4.5:1, and temperature is 260 DEG C, pressure 6.0MPa, and the processing time is 5 hours, and temperature is at 45 DEG C
When, it is washed 4 times with water purification, it is 8 hours dry at 100 DEG C after washing, then roasted 5 hours at 330 DEG C, the material after roasting is added suitable
It measures graphite and hydraulic pressure is in blocks, obtain catalyst D.Composition, pore size distribution and main character are shown in Table 1.
Comparative example 1
It is added without urea by 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, prepares reference agent E, composition,
The main characters such as pore size distribution are shown in Table 1.
Comparative example 2
By 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but NH is added3, at hydro-thermal
The condition of reason are as follows: the molar ratio of ammonia and active metal atom total amount is 6:1, and temperature is 220 DEG C, pressure 3.5MPa, processing
Time is 4 hours, prepares reference agent F, the main characters such as composition, pore size distribution are shown in Table 1.
Comparative example 3
By 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but CO is added2, at hydro-thermal
The condition of reason are as follows: CO2It is 6:1 with the molar ratio of active metal atom total amount, temperature is 220 DEG C, pressure 3.5MPa, when processing
Between be 4 hours, prepare reference agent G, the main characters such as composition, pore size distribution are shown in Table 1.
Embodiment 5
Catalst for synthesis of methanol is pulverized for 16-40 mesh, is using low-concentration hydrogen (H using preceding2/N2=3/97(volume ratio))
Hydrogen nitrogen mixed gas restore 16~20h, highest reduction temperature be 235 DEG C.Catalyst is carried out on miniature fixed-bed reactor
Activity rating.Loaded catalyst is 5ml, and unstripped gas group becomes CO/H2/CO2/N2=12/70/5/13(volume ratio), reaction
Pressure is 5.0MPa, air speed 10000h-1, reaction temperature is 250 DEG C, measures CO and CO2Conversion ratio be catalyst initial live
Property.Then by catalyst in synthesis atmosphere by 450 DEG C of heat treatment 5h, then drop to 250 DEG C of measurement CO and CO2Conversion ratio be heat
Activity, i.e. heat resistance after processing.Product chromatographic generates the space-time yield gmL of methanol-1·h-1I.e. per small
When every milliliter of catalyst produce the grams of methanol, the results are shown in Table 1.
As can be seen from Table 1 and Table 2, catalyst of the present invention is not in the case where active metal amount changes, catalyst table
Face active metal atom concentration increases, and hydrogenation sites density increases, and pore size distribution$ more concentrates, be concentrated mainly on 8nm ~
15nm has high activity and selectivity with catalyst within the scope of this pore size distribution, finds out from test result, and methanol of the present invention closes
There is high activity, heat resistance and excellent selectivity at catalyst.
1 catalyst of table composition and property.
The weight ratio of table 2 catalyst table phase reactive metal oxides and body phase reactive metal oxides.
The evaluation of 3 catalyst activity of table and heat resistance experimental result.
Claims (12)
1. a kind of copper zinc catalyst, composition includes active metal component Cu, Zn, aluminium oxide；It is characterized by: wherein table is mutually lived
Property metal component CuO weight content and the ratio of the weight content of body phase active metal component CuO be 2.0:1 ~ 7.0:1, table phase
The ratio of the weight content of active metal component ZnO and the weight content of body phase active metal component ZnO is 2.54:1 ~ 4.5:1；Copper
The property of zinc catalyst is as follows: specific surface area is 100 ~ 450m20.20 ~ 0.60mL/g of/g, Kong Rongwei, pore-size distribution are as follows: straight
Diameter is that Kong Rong shared by the hole below 4nm accounts for the 1% ~ 17% of total pore volume, and diameter is that Kong Rong shared by the hole of 4 ~ 8nm accounts for the 2% of total pore volume
~ 20%, diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for the 45% ~ 80% of total pore volume, and diameter is that the Kong Rong of 15nm or more accounts for total pore volume
It is 1% ~ 20%.
2. copper zinc catalyst described in accordance with the claim 1, it is characterised in that: on the basis of the weight of catalyst, catalyst
Composition includes that based on mass fraction: CuO is that 20%~65%, ZnO is 15%~40%, Al2O3It is 5%~40%.
3. copper zinc catalyst described in accordance with the claim 1, it is characterised in that: contain auxiliary agent in catalyst, auxiliary agent Mn, Mg,
The one or more of Cr, Mo, W, Li or Zr, with overall catalyst weight meter, auxiliary agent is calculated as 1% ~ 15% with oxide, catalyst each group
Dividing the sum of content is 100%.
4. copper zinc catalyst described in accordance with the claim 1, it is characterised in that: the pore-size distribution of copper zinc catalyst is as follows: diameter
The 5% ~ 12% of total pore volume is accounted for for Kong Rong shared by the hole below 4nm, it is 4% that Kong Rong shared by hole of the diameter for 4 ~ 8nm, which accounts for total pore volume,
~ 15%, diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for the 50% ~ 75% of total pore volume, and diameter is that the Kong Rong of 15nm or more accounts for total pore volume
It is 5% ~ 15%.
5. a kind of preparation method of copper zinc catalyst described in claim 1 ~ 4 any claim, it is characterised in that including such as
Lower content: (1) by the soluble-salt of Cu, Zn, Al soluble in water wiring solution-forming A, sodium carbonate liquor B is prepared；(2) by solution A, molten
Plastic, aging in reactor tank is added in liquid B cocurrent；(3) slurries obtained by step (2) are filtered, obtained material is carried out with water vapour
Urea is wherein added in hydro-thermal process when hydro-thermal process；(4) material that step (3) obtains is washed, filtering, dry, roasting, presses
Sheetmolding obtains catalyst.
6. according to the method for claim 5, it is characterised in that: in step (1) in solution A copper ion concentration be 1.0~
6.0mol/L, zinc ion concentration is 0.5~5.0mol/L in solution A, and aluminium ion concentration is 1.0~7.0mol/L；Carbon in solution B
Copper in sour sodium and solution A, zinc, aluminium molar ratio be 0.5~3.0.
7. according to method described in claim 5 or 6, it is characterised in that: in solution A as described in step (1), cu zn atom
Molar ratio is 0.1~10, and (copper+zinc)/aluminium atom molar ratio is 0.1~10.
8. according to the method for claim 5, it is characterised in that: Gelation Conditions described in step (2): reaction temperature be 30~
90 DEG C, pH value is 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour；50~100 DEG C of aging temperature after plastic, aging pH value control
6.0 ~ 11.0 are made as, ageing time is 0.5 ~ 5.0 hour.
9. according to the method for claim 5, it is characterised in that: hydrothermal conditions described in step (3) are as follows: closed
Container under carry out, temperature be 200 ~ 300 DEG C, pressure be 1.0 ~ 8.0MPa, processing the time be 0.5 ~ 10.0 hour；Hydro-thermal process
When, the molar ratio of metallic atom total amount is 0.5:1 ~ 10.0:1 in the additional amount and catalyst of urea.
10. according to the method for claim 5, it is characterised in that: step (4) washing is washed with deionized, and washs
Temperature is controlled at 30~90 DEG C；Filter cake is dry under the conditions of 50 ~ 150 DEG C, and drying temperature is 60 ~ 120 DEG C, and drying time 0.5 ~
24.0 hours；The roasting condition is as follows: roasting 1 ~ 16 hour at 300~360 DEG C.
11. according to the method for claim 5, it is characterised in that: auxiliary agent is added during step (1) and/or (2), helps
Agent is the one or more of Mn, Mg, Cr, Mo, W, Li or Zr, and with overall catalyst weight meter, promoter addition is calculated as with oxide
1% ~ 15%, the sum of catalyst components content is 100%.
12. a kind of application of the copper zinc catalyst described in claim 1 ~ 4 any claim in synthesizing methanol reaction, special
Sign is: process conditions are as follows: reaction temperature is 210~320 DEG C, and pressure is 2~10MPa, and volume space velocity is 2000~15000h-1。
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