CN105582935B - A kind of copper zinc composite oxide, preparation method and the usage - Google Patents
A kind of copper zinc composite oxide, preparation method and the usage Download PDFInfo
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- CN105582935B CN105582935B CN201610128052.6A CN201610128052A CN105582935B CN 105582935 B CN105582935 B CN 105582935B CN 201610128052 A CN201610128052 A CN 201610128052A CN 105582935 B CN105582935 B CN 105582935B
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- 239000002131 composite material Substances 0.000 title claims abstract description 122
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 60
- 229910001431 copper ion Inorganic materials 0.000 claims description 60
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 58
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000010949 copper Substances 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 15
- 239000012670 alkaline solution Substances 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 9
- 239000002135 nanosheet Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 6
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000004005 microsphere Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 74
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 65
- 239000000047 product Substances 0.000 description 55
- 238000009616 inductively coupled plasma Methods 0.000 description 38
- 238000012360 testing method Methods 0.000 description 37
- 239000011787 zinc oxide Substances 0.000 description 33
- 239000000725 suspension Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000001913 cellulose Substances 0.000 description 16
- 229920002678 cellulose Polymers 0.000 description 16
- 239000000320 mechanical mixture Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 10
- 229960004643 cupric oxide Drugs 0.000 description 10
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 235000013312 flour Nutrition 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000004246 zinc acetate Substances 0.000 description 7
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000011863 silicon-based powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 239000011807 nanoball Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910018067 Cu3Si Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 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
-
- B01J35/40—
-
- B01J35/51—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
Abstract
The invention provides a kind of copper zinc composite oxide, preparation method and the usage, the pattern of the copper zinc composite oxide is the microballoon that nanometer sheet assembles, the component of nanometer sheet includes ZnO and CuO, ZnO is dispersed in CuO, wherein, the weight/mass percentage composition that ZnO weight/mass percentage composition is 1%~20%, CuO is 80%~99%.Copper zinc composite oxide provided by the invention is directly synthesized using a step; it is simple to operate; avoid needed in template first synthesize microsphere template the shortcomings that; without any organic surface active agent or supplementary energy; so as to reduce reaction cost and energy consumption, and environmentally friendly, easy control of reaction conditions; favorable reproducibility, it is adapted to industrial scale production；The catalyst that the copper zinc composite oxide is used in " direct method " synthesis M2 monomer reactions, enables to M2 selectivity >=89.0%, silicon power raw material conversion ratio >=30.0%.
Description
Technical field
The invention belongs to technical field of inorganic material, is related to a kind of copper zinc composite oxide, preparation method and the usage, especially
It is related to a kind of copper zinc composite oxide microspherical catalyst with special loose structure, its preparation method and its as synthesis two
The catalyst of dimethyl dichlorosilane (DMCS).
Background technology
Metal composite oxide has broad application prospects as a kind of novel and multifunctional property inorganic fine material.Its
In, answered as the CuO of the p-type metal oxide semiconductor of low energy gap and the n-type metal oxide semiconductor ZnO of broad stopband
Conjunction can effectively improve sample Electron band structure, and then improve the physical and chemical performance of sample, make it in catalysis, photocatalysis and photoelectricity
There is potential application value in terms of device.
At present, the main production process of CuO/ZnO composite oxides has coprecipitation, high-temperature solid-phase sintering method and ultraviolet light
Auxiliary law etc..Although coprecipitation technique is simple, easy to operate, the easily independent split-phase of two components, composite effect is had a strong impact on.High temperature
Solid sintering technology high energy consumption, three-waste pollution is serious, is close to superseded method.CN 102513112A disclose one kind ultraviolet
Under light auxiliary, using soluble copper salt and ZnOw as raw material, polyethylene glycol is solvent to prepare CuO/ZnO composite oxides
Method, but its raw material sources is single, and production cost is higher, and equipment requirement is strict, has had a strong impact on process of industrialization.CN
102817078A discloses one kind using PEG-4000 as surfactant, and soluble copper salt is copper source, Zn (OH)4 2-Make
The method that flowers shape CuO/ZnO composite oxides are prepared for precipitating reagent, but it faces cost of material height, and high aqueous slkali easily makes to set
Standby the problems such as scabbing, seriously limit its application.CN 104726094A disclose one kind and prepare ZnO- using colloidal sol-gel
The method of CuO nuclear shell structure quantum points/nanocrystalline, but this method process is cumbersome, and product post processing is difficult and efficiency of pcr product is low.Cause
This, the production technology for developing the CuO/ZnO composite oxides of efficient, low consumption, high yield and high quality is that industry urgently to be resolved hurrily is asked
Topic.
Dimethyldichlorosilane [(CH3) 2SiCl2, abbreviation M2] is list most important in organosilicon industry and maximum dosage
Body.Industrially mainly synthesized at present using " direct method " (Rochow reactions), i.e., under copper-based catalysts effect, by silica flour
(Si) and direct substitution reaction occurs for chloromethanes (MeCl).But because this reaction can be with generation disproportionation, thermal decomposition and hydrolysis
Etc. numerous complicated side reaction, cause accessory substance more, therefore, it is always grinding for organosilicon industry to improve M2 yield and selectivity
Study carefully emphasis.Cu base catalyst is the most effective catalyst of current Rochow reaction, including Cu simple substance, Cu2O and CuO etc..In addition,
Research finds that Zn or Zn compound is added in Cu base major catalysts as auxiliary agent, can further improve its catalytic performance
(J.Catal.,1991,128,468；US 4500724；CN 101811057A；CN 1812834A).But due to Industrial Catalysis
The usual structure of agent is irregular, surface compact, and co-catalyst addition manner typically belongs to additional blending, causes main co-catalyst point
Heterogeneity is dissipated, interaction force is weaker, have impact on both synergisticing performances, and then have impact on the lifting of catalytic performance.Therefore, open
It is still Rochow to send out high activity, high selectivity, compound with regular structure, loose porous and complex catalyst system homogeneous Elemental redistribution
One of technological difficulties of reaction.
The content of the invention
For technological process present in existing CuO/ZnO composite oxides industrial production technology is cumbersome, product yield is low
And major catalyst CuO compact structures in the shortcomings of of poor quality, and Rochow reactions, and mixed between auxiliary agent Zn or ZnO component
The shortcomings of closing heterogeneity, it is an object of the invention to provide a kind of copper zinc composite oxide, preparation method and the usage, the copper
Zinc composite oxide pattern and homogeneous grain diameter, CuO and ZnO dispersivenesses preferably, have synergy, and it is used for " direct method " synthesis
Catalyst in M2 monomer reactions, there is excellent M2 selectivity and silicon power raw material conversion ratio, M2 selectivity >=89.0%, silica flour
Feed stock conversion >=30.0%.
To use following technical scheme up to this purpose, the present invention：
An object of the present invention is to provide a kind of copper zinc composite oxide, and the pattern of the copper zinc composite oxide is
The microballoon that porous nano-sheet assembles, the component of the nanometer sheet includes ZnO and CuO, ZnO are dispersed in CuO, its
In, the weight/mass percentage composition that ZnO weight/mass percentage composition is 1%~20%, CuO is 80%~99%.
Described copper zinc composite oxide microballoon is assembled by multiple porous nano-sheets.The porous nano-sheet is ZnO
With CuO compound, wherein ZnO is dispersed in CuO.The weight/mass percentage composition of the ZnO and CuO are that ZnO and CuO distinguishes
Account for the weight/mass percentage composition of the copper zinc composite oxide.ZnO weight/mass percentage compositions be 1%~20%, such as 2%, 3%, 5%,
8%th, 10%, 12%, 15%, 18% or 19% etc., CuO weight/mass percentage composition be 80%~99%, such as 82%, 85%,
88%th, 90%, 92%, 95% or 98% etc..
The particle size of the microballoon is 1~20 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μ
M, 12 μm, 15 μm, 18 μm or 19 μm etc..
Preferably, the thickness of the nanometer sheet is 20~80nm, such as 20nm, 30nm, 40nm, 50nm, 60nm, 70nm or
80nm etc..
Preferably, the microballoon is loose structure.The Porous Cu zinc composite oxide is stacked by nanometer sheet and formed more
Pore structure.
Described copper zinc composite oxide is loose structure, pattern and homogeneous grain diameter, and CuO and ZnO dispersivenesses are preferably.
The second object of the present invention is to provide a kind of preparation method of described copper zinc composite oxide, methods described bag
Include following steps：
(1) solution containing copper ion and zinc ion is mixed with alkaline solution, obtains mixed liquor；
(2) mixed liquor is subjected to hydro-thermal reaction, afterwards, by the product separation of solid and liquid of hydro-thermal reaction, obtains solid formation；
(3) solid formation is washed, dried, calcining, obtain the copper zinc composite oxide.
The copper zinc composite oxide is directly synthesized using a step, simple to operate, and avoid needs to synthesize first in template
The shortcomings that microsphere template；Any organic surface active agent need not be added, cost is relatively low, environmentally friendly.
In the solution containing copper ion and zinc ion described in step (1) mol ratio of copper ion and zinc ion for (5~
20):1, such as 5:1、6:1、8:1、10:1、12:1、14:1、15:1、16:1、18:1 or 20:1 etc..
Preferably, in the solution containing copper ion and zinc ion described in step (1) concentration of copper ion for 0.08~
0.25mol/L, as 0.08mol/L, 0.09mol/L, 0.10mol/L, 0.12mol/L, 0.15mol/L, 0.18mol/L,
0.20mol/L or 0.25mol/L etc..
Preferably, in the step (1) content of copper ion and zinc ion by inductively coupled plasma spectrum generator
(ICP) test obtains.
Preferably, the solution containing copper ion and zinc ion described in step (1) is by by soluble copper salt and solubility
Zinc salt is dissolved in solvent and obtained.The soluble copper salt and soluble zinc salt are the mantoquita and zinc salt for referring to be dissolved in solvent for use.
Preferably, the soluble copper salt is any of copper nitrate, copper chloride or copper acetate or at least two group
Close.Typical but non-limiting combination is such as：Copper nitrate and copper chloride, copper nitrate and copper acetate, copper chloride and copper acetate, nitric acid
Copper, copper chloride and copper acetate.
Preferably, the soluble zinc salt is any of zinc nitrate, zinc chloride or zinc acetate or at least two group
Close.Typical but non-limiting combination is such as：Zinc nitrate and zinc chloride, zinc nitrate and zinc acetate, zinc chloride and zinc acetate, nitric acid
Zinc, zinc chloride and zinc acetate.
Preferably, the solvent is water and/or ethanol, and preferably volume ratio is 0:1~1:1 second alcohol and water, such as 0:1、
0.1:1、0.3:1、0.5:1、0.7:1、0.9:1 or 1:1 etc., preferably 0.1:1~0.5:1, most preferably 0.2:1.
Alkaline solution described in step (1) is sodium bicarbonate solution, sal volatile, sodium carbonate liquor or solution of potassium carbonate
In it is any or at least two mixed liquor.Typical but non-limiting alkaline solution mixed liquor is such as：Sodium bicarbonate solution and carbon
Acid ammonium solution, sodium carbonate liquor and solution of potassium carbonate, sal volatile and sodium carbonate liquor, sodium bicarbonate solution, ammonium carbonate are molten
Liquid, sodium carbonate liquor and solution of potassium carbonate.
Preferably, the concentration of step (1) described alkaline solution is 0.1~2mol/L, as 0.2mol/L, 0.3mol/L,
0.5mol/L, 0.6mol/L, 0.8mol/L, 1.0mol/L, 1.2mol/L, 1.5mol/L, 1.7mol/L or 1.9mol/L etc..Institute
State alkaline solution concentration refer to alkali lye mixed with the solution containing copper ion and zinc ion before concentration.
Preferably, the volume ratio of the alkaline solution described in step (1) and the solution containing copper ion and zinc ion is
1:6~2:1, such as 1:6、1:5、1:4、1:3、1:2、1:1 or 2:3 etc..
Described in step (1) be blended in 10~35 DEG C under the conditions of carry out, such as 12 DEG C, 15 DEG C, 18 DEG C, 20 DEG C, 25 DEG C, 28
DEG C, 30 DEG C or 32 DEG C etc..
Preferably, the mode of step (1) described mixing is stirring.
Preferably, the time of the stirring is 0.5~4h, such as 0.5h, 1h, 2h, 2.5h, 3h or 4h.
The reaction temperature of step (2) described hydro-thermal reaction be 100~180 DEG C, such as 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C,
150 DEG C, 160 DEG C, 165 DEG C or 175 DEG C etc..
Preferably, the reaction time of step (2) described hydro-thermal reaction is 12~24h, as 12h, 13h, 15h, 18h, 20h,
22h, 23h or 24h etc..
Preferably, step (2) described hydro-thermal reaction is carried out in autoclave.
Preferably, the volume of the autoclave is 100~1000mL, as 100mL, 300mL, 500mL, 600mL,
800mL or 900mL etc..
Preferably, the liner of the autoclave is polytetrafluoroethylene (PTFE).
Preferably, the product of the hydro-thermal reaction described in step (2) first cools down carries out separation of solid and liquid again.The temperature of the cooling
Degree, those skilled in the art can select as needed, typically be cooled to 15-30 DEG C.It is cold that nature may be selected in the mode of the cooling
But etc..
The mode of separation of solid and liquid described in step (2) is without specifically limited, as long as can reach solid and liquid separation
Purpose, typical but non-limiting solid-liquid separation method is such as：Centrifugation or filtering etc..
The temperature of step (3) described drying be 60~200 DEG C, such as 65 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 120 DEG C,
150 DEG C, 170 DEG C, 180 DEG C or 190 DEG C etc..
Preferably, the time of step (3) described drying is 6~20h, as 6h, 7h, 8h, 10h, 12h, 15h, 17h, 20h,
22h or 23h etc..
Preferably, the temperature of step (3) described calcining be 400~1000 DEG C, such as 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C,
800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or 1000 DEG C etc..
Preferably, the time of step (3) described calcining is 2~12h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or
12h。
Preferably, step (3) calcining is carried out in air atmosphere or inert atmosphere.The purpose of the calcining is point
Solid formation is solved, the atmosphere of calcining influences less on the product that calcining obtains.
As preferable technical scheme, the preparation method of the copper zinc composite oxide comprises the following steps：
(1) soluble copper salt and soluble zinc salt are dissolved in volume ratio for (0:1~1):In 1 second alcohol and water, contained
There is the solution of copper ion and zinc ion, wherein, the concentration of copper ion is 0.08~0.25mol/L, and copper ion and zinc ion rub
Your ratio is (5~20):1；
(2) it is 1 by volume ratio:6~2:1 alkaline solution and solution containing copper ion and zinc ion are in 10~35 DEG C of bars
It is stirred under part, mixing time is 0.5~4h, obtains mixed liquor, wherein, the concentration of alkaline solution is 0.1~2mol/L；
(3) mixed liquor is subjected to hydro-thermal reaction in autoclave, the temperature of hydro-thermal reaction is 100~180 DEG C, the time
For 12~24h, hydrothermal product is obtained；By hydrothermal product separation of solid and liquid, solid formation is obtained；
(4) solid formation is washed, afterwards in 60~200 DEG C of dry 6~20h, then 400~1000 DEG C calcine 2~12h,
Obtain the copper zinc composite oxide.
The preparation method easy control of reaction conditions of copper zinc combined oxidation provided by the invention, favorable reproducibility, it is adapted to industry
Large-scale production.
The third object of the present invention is to provide a kind of purposes of described copper zinc composite oxide, and it is used as organosilicon list
Catalyst in body synthetic reaction, promote the selectivity synthesis of dimethyldichlorosilane.
Micro-nano spherical catalyst pattern provided by the invention, particle diameter distribution are homogeneous；The copper zinc composite oxide microballoon
Assembled by porous nano-sheet, its surface porosity is porous, is advantageous to the diffusion of reactant chloromethanes, the desorption of gaseous product；
Cupric oxide and zinc oxide are uniformly dispersed, and enhance the synergy between two kinds of components so that effective between each component and silica flour
Contact probability is significantly greatly increased, and results in more Cu3Si activity phases, so as to improve M2 selectivity and silica flour conversion ratio, its M2
Selectivity >=89.0%, silicon power raw material conversion ratio >=30.0%.
Compared with prior art, beneficial effects of the present invention are：
1st, copper zinc composite oxide provided by the invention is loose structure, pattern and homogeneous grain diameter, and CuO and ZnO are dispersed
Preferably；
2nd, the preparation method of copper zinc composite oxide provided by the invention is a step direct synthesis technique, simple to operate, is avoided
The shortcomings that needing to synthesize microsphere template first in template；Without any organic surface in the preparation process of copper zinc composite oxide
Activating agent or supplementary energy, so as to reduce reaction cost and energy consumption, and environmentally friendly, easy control of reaction conditions, reappear
Property it is good, be adapted to industrial scale production；
3rd, copper zinc composite oxide catalyst provided by the invention is used in " direct method " synthesis M2 monomer reactions, with industry
CuO, ZnO, CuO compare with ZnO mechanical mixture sample, the single CuO of preparation with ZnO and commercial catalysts, have higher
M2 selectivity and silicon power raw material conversion ratio, M2 selectivity >=89.0%, silicon power raw material conversion ratio >=30.0%.
Brief description of the drawings
Fig. 1 is the XRD of copper zinc composite oxide made from embodiment 1.
Fig. 2 is the low range SEM figures of copper zinc composite oxide made from embodiment 1.
Fig. 3 is the high magnification SEM figures of copper zinc composite oxide made from embodiment 1, wherein, Fig. 3 a are that single copper zinc is compound
The high magnification SEM figures of oxidate microspheres；Fig. 3 b are the high magnification SEM figures of the nanometer sheet of composition copper zinc composite oxide microballoon.
Fig. 4 is the FBI-SEM figures of copper zinc composite oxide made from embodiment 1.
Fig. 5 is the distribution diagram of element of copper zinc composite oxide made from embodiment 1.
Fig. 6 is the grain size distribution of copper zinc composite oxide made from embodiment 1.
Fig. 7 is waste catalyst XRD after embodiment 1, comparative example 3 and commercial catalysts fixed bed catalyst, and built-in figure is
The enlarged drawing of rectangular area, tri- curves of A, B and C therein are respectively the waste catalyst of comparative example 3, the waste catalyst of embodiment 1 and business
The XRD curves of cupric oxide waste catalyst.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Raw material described in following examples and experimental facilities those skilled in the art are commercially available.Wherein, high pressure
Reactor is provided by the crack Ze Xiang laboratory apparatus Co., Ltd in Beijing.
N in following examplesCu2+ and nZn2+The amount of the material of copper ion and zinc ion is represented respectively, and C represents the amount of material
Concentration, wt% represent weight/mass percentage composition.
Embodiment 1：
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 20 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 4mmol and nCu2+:nZn2+=10:1)
50mL, solvent are pure water solution, and copper ion source is in copper nitrate, and zinc ion source is in zinc nitrate；
(2) sodium carbonate liquor (C is preparedNa2CO3For 0.8mol/L) 50mL, add it to and contain copper ion described in (1)
In the solution of zinc ion, 0.5h is stirred, obtains suspension；
(3) suspension is transferred in the 100mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 18h at 130 DEG C
Afterwards, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) filter hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after at 60 DEG C
Dry 12h；
(5) dried product is calcined into 12h for 400 DEG C in air atmosphere, obtains product.
Obtained product is multi-functional in the X ' Pert PRO MPD types that Dutch Panalytical companies (PANalytical) produce
XRD tests are carried out on X-ray diffractometer；Observed in the JSM-7001F type SEM of Japanese JEOL companies production
Its microscopic appearance；The NanoLab type SEM focused ion beam two-beams of Nova 200 that FEI Co. produces in the U.S.
Its cross section is observed in system；Its granularity point is analyzed on the BT-9300Z laser particle analyzers of Dandong particle size analyzer Co., Ltd production
Cloth；ICP tests are carried out on U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers.
Test result：
Fig. 1 is the XRD of obtained product, wherein, " ▼ " represents CuO characteristic diffraction peak, and " ◆ " spreads out for ZnO feature
Peak is penetrated, it will be seen from figure 1 that products obtained therefrom is CuO and ZnO compound, as copper zinc composite oxide；Fig. 2 is obtained
The low range SEM figures of copper zinc composite oxide, it can be seen that prepared sample topography and size uniformity degree are high, monodispersity
It is good；Fig. 3 is the high magnification SEM figures of obtained copper zinc composite oxide, it can be seen that obtained copper zinc composite oxide
In nanoparticle shape (such as Fig. 3 a), a footpath is about 6.0 μm, and surface is formed by being distributed homogeneous porous nano-sheet (such as Fig. 3 b), is received
The thickness about 50nm of rice piece；Fig. 4 is the FBI-SEM figures of obtained copper zinc composite oxide, and system is can be clearly seen that from figure
The copper zinc composite oxide obtained is in loose structure；Fig. 5 is the elemental map of obtained copper zinc composite oxide microspherical catalyst
Scheme, show that Cu (Fig. 5 c) and Zn (Fig. 5 d) Elemental redistribution are uniform in figure；Fig. 6 is the particle diameter of obtained copper zinc composite oxide microballoon
Distribution map, it can be seen that the particle diameter of obtained copper zinc composite oxide, all less than 15 μm, most of particle diameter is 6.04
μm；ICP test results show that copper coin cellulose content is 72.5wt%, and Zn-ef ficiency content is 7.2wt%.
Embodiment 2：
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 25 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 10mmol and nCu2+:nZn2+=5:1)
300mL, solvent are pure water solution, and copper ion source is in copper acetate, and zinc ion source is in zinc acetate；
(2) solution of potassium carbonate (C is preparedK2CO3For 2mol/L) 50mL, add it to and contain copper ion and zinc described in (1)
In the solution of ion, 1.5h is stirred, obtains suspension；
(3) suspension is transferred in the 600mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 24h at 100 DEG C
Afterwards, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) centrifuge hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after at 80 DEG C
Dry 10h；
(5) dried product is calcined into 10h for 500 DEG C in air atmosphere, obtains copper zinc composite oxide.
By obtained copper zinc composite oxide in the JSM-7001F type SEM that Japanese JEOL companies produce
Observe microscopic appearance；Sample granularity distribution is analyzed on the BT-9300Z laser particle analyzers of Dandong particle size analyzer Co., Ltd production；
ICP tests are carried out on U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers.
Test result shows that obtained copper zinc composite oxide is in porous micro-nano ball, and particle diameter is about 6.5 μm；Table
Face is formed by being distributed homogeneous porous nano-sheet, the thickness about 60nm of nanometer sheet；The particle diameter of obtained copper zinc composite oxide is complete
Portion is less than 15 μm, and most of particle diameter is 6.20 μm；ICP test results show, copper coin cellulose content is 66.5wt%, Zn-ef ficiency content
For 13.2wt%.
Embodiment 3：
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 30 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 50mmol and nCu2+:nZn2+=6:1)
200mL, solvent are that (alcohol water ratio is 0.4 to ethanol water:1), copper ion source is in copper chloride, and zinc ion source is in zinc chloride；
(2) sodium bicarbonate solution (C is preparedNaHCO3For 1mol/L) 100mL, add it to and contain copper ion described in (1)
In the solution of zinc ion, 2.5h is stirred, obtains suspension；
(3) suspension is transferred in the 500mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 18h at 150 DEG C
Afterwards, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) filter hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after 100 DEG C
Lower dry 8h；
(5) dried product is calcined into 9h for 600 DEG C in air atmosphere, obtains copper zinc composite oxide.
By obtained copper zinc composite oxide on the BT-9300Z laser particle analyzers that Dandong particle size analyzer Co., Ltd produces
Analyze sample granularity distribution；ICP surveys are carried out on U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Examination.
Test result shows that for the particle diameter of obtained copper zinc composite oxide all less than 20 μm, most of particle diameter is 6.11 μ
m；ICP test results show that copper coin cellulose content is 68.2wt%, and Zn-ef ficiency content is 11.8wt%
Embodiment 4：
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 35 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 6mmol and nCu2+:nZn2+=8:1)
80mL, solvent are that (alcohol water ratio is 1 to ethanol water:1), copper ion source is in copper acetate, and zinc ion source is in zinc chloride；
(2) sal volatile (C is prepared(NH4)2CO3For 0.5mol/L) 50mL, add it to described in (1) containing copper from
In the solution of son and zinc ion, 3h is stirred, obtains suspension；
(3) suspension is transferred in the 200mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 16h at 150 DEG C
Afterwards, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) centrifuge hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after 120 DEG C
Lower dry 6h；
(5) dried product is calcined into 8h for 700 DEG C in air atmosphere, obtains copper zinc composite oxide.
By obtained copper zinc composite oxide on the BT-9300Z laser particle analyzers that Dandong particle size analyzer Co., Ltd produces
Analyze sample granularity distribution；ICP surveys are carried out on U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Examination.
Test result shows that for the particle diameter of obtained copper zinc composite oxide all less than 15 μm, most of particle diameter is 6.00 μ
m；Copper coin cellulose content is 71.9wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is 7.9wt%.
Embodiment 5：
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 40 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 20mmol and nCu2+:nZn2+=10:
1) 300mL, solvent are that (alcohol water ratio is 1 to ethanol water:1), in copper nitrate and copper acetate, (the former with the latter rubs copper ion source
You are than being 1:1), zinc ion source is in zinc nitrate；
(2) (the former with the latter mol ratio is 1 to the solution containing copper ion and zinc ion of preparation sodium carbonate and potassium carbonate:2
And CK2CO3+Na2CO3For 1.0mol/L) 50mL, add it in the solution containing copper ion and zinc ion described in (1), stir
3.5h, obtain suspension；
(3) suspension is transferred in the 1000mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction at 160 DEG C
After 16h, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) filter hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after 140 DEG C
Lower dry 4h；
(5) dried product is calcined into 6h for 800 DEG C in air atmosphere, obtains copper zinc composite oxide.
By obtained copper zinc composite oxide on the BT-9300Z laser particle analyzers that Dandong particle size analyzer Co., Ltd produces
Analyze sample granularity distribution；ICP surveys are carried out on U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Examination.
Test result shows that for the particle diameter of obtained copper zinc composite oxide all less than 20 μm, most of particle diameter is 6.80 μ
m；Copper coin cellulose content is 72.1wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is 7.8wt%.
Embodiment 6：
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 20 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 12mmol and nCu2+:nZn2+=5:1)
200mL, solvent are that (alcohol water ratio is 0.8 to ethanol water:1), copper ion source is in copper acetate, and zinc ion source is in zinc chloride；
(2) (the former with the latter mol ratio is 2 to the mixed solution of preparation sodium carbonate and ammonium carbonate:1 and CNa2CO3+(NH4)2CO3For
2mol/L) 50mL, add it in the solution containing copper ion and zinc ion described in (1), stir 4h, obtain suspension；
(3) suspension is transferred in the 400mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 12h at 180 DEG C
Afterwards, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) centrifuge hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after 160 DEG C
Lower dry 2h；
(5) dried product is calcined into 4h for 900 DEG C in air atmosphere, obtains copper zinc composite oxide.
By obtained copper zinc composite oxide in U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Upper progress ICP tests.
Test result shows that copper coin cellulose content is 65.1wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is
14.9wt%.
Embodiment 7：
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 20 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 15mmol and nCu2+:nZn2+=5:1)
500mL, solvent are pure water solution, and copper ion source is in copper acetate, and zinc ion source is in zinc acetate；
(2) sodium carbonate liquor (C is preparedNa2CO3For 1.2mol/L) 150mL, add it to and contain copper ion described in (1)
In the solution of zinc ion, 1.5h is stirred, obtains suspension；
(3) suspension is transferred in the 900mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 24h at 140 DEG C
Afterwards, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) centrifuge hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after 180 DEG C
Lower dry 10h；
(5) dried product is calcined into 2h for 1000 DEG C in air atmosphere, obtains copper zinc composite oxide.
By obtained copper zinc composite oxide in U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Upper progress ICP tests.
Test result shows that copper coin cellulose content is 66.7wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is
13.3wt%.
Embodiment 8：
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 20 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 4mmol and nCu2+:nZn2+=10:1)
50mL, solvent are pure water solution, and in copper nitrate and copper chloride, (the former with the latter mol ratio is 1 to copper ion source:3), zinc ion
From zinc nitrate and zinc acetate, (the former with the latter mol ratio is 2:1)；
(2) sodium carbonate liquor (C is preparedNa2CO3For 0.8mol/L) 50mL, add it to and contain copper ion described in (1)
In the solution of zinc ion, 1.5h is stirred, obtains suspension；
(3) suspension after stirring is transferred in the 100mL autoclave of polytetrafluoroethyllining lining, the water at 130 DEG C
After thermal response 18h, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) filter hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after 120 DEG C
Lower dry 12h；
(5) dried product is calcined into 6h for 400 DEG C in air atmosphere, obtains copper zinc composite oxide.
By obtained copper zinc composite oxide in U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Upper progress ICP tests.
Test result shows that copper coin cellulose content is 71.5wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is
8.1wt%.
Embodiment 9：
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 20 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 4mmol and nCu2+:nZn2+=10:1)
50mL, solvent are pure water solution, and copper ion source is in copper nitrate, and zinc ion source is in zinc nitrate；
(2) (the former with the latter mol ratio is 1 to the mixed solution of preparation sodium acid carbonate and sodium carbonate:2 and CNaHCO3+(NH4)2CO3
For 0.8mol/L) 50mL, add it in the solution containing copper ion and zinc ion described in (1), stir 1.5h, hanged
Turbid；
(3) suspension is transferred in the 100mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 18h at 130 DEG C
Afterwards, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) filter hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after at 60 DEG C
Dry 12h；
(5) dried product is calcined into 6h for 400 DEG C in a nitrogen atmosphere, obtains copper zinc composite oxide.
By obtained copper zinc composite oxide in U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Upper progress ICP tests.
Test result shows that copper coin cellulose content is 71.9wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is
8.2wt%.
Embodiment 10：
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 10 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 4mmol and nCu2+:nZn2+=20:1)
50mL, solvent are pure water solution, and copper ion source is in copper nitrate, and zinc ion source is in zinc nitrate；
(2) (the former with the latter mol ratio is 1 to the mixed solution of preparation sodium acid carbonate and sodium carbonate:2 and CNaHCO3+(NH4)2CO3
For 0.1mol/L) 50mL, add it in the solution containing copper ion and zinc ion described in (1), stir 2h, obtain suspended
Liquid；
(3) suspension is transferred in the 500mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 20h at 120 DEG C
Afterwards, 15 DEG C are naturally cooled to, obtains hydrothermal product；
(4) filter hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after 200 DEG C
Lower dry 20h；
(5) dried product is calcined into 8h for 600 DEG C in a nitrogen atmosphere, obtains copper zinc composite oxide.
Obtained copper zinc composite oxide is subjected to surface sweeping Electronic Speculum sign, characterization result shows obtained copper zinc combined oxidation
Thing is in nanoparticle shape, and a footpath is about 10.0 μm, and surface is formed by being distributed homogeneous porous nano-sheet, and the thickness of nanometer sheet is about
80nm。
By obtained copper zinc composite oxide in U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Upper progress ICP tests.
Test result shows that copper coin cellulose content is 79.2wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is
0.8wt%.
Embodiment 11
A kind of preparation method of copper zinc composite oxide, comprises the following steps：
(1) at 20 DEG C, the solution (n containing copper ion and zinc ion is configuredCu2+For 4mmol and nCu2+:nZn2+=15:1)
50mL, solvent are pure water solution, and copper ion source is in copper nitrate, and zinc ion source is in zinc nitrate；
(2) (the former with the latter mol ratio is 1 to the mixed solution of preparation sodium acid carbonate and sodium carbonate:2 and CNaHCO3+(NH4)2CO3
For 1mol/L) 50mL, add it in the solution containing copper ion and zinc ion described in (1), stir 3h, obtain suspended
Liquid；
(3) suspension is transferred in the 500mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 20h at 120 DEG C
Afterwards, 25 DEG C are naturally cooled to, obtains hydrothermal product；
(4) filter hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after 180 DEG C
Lower dry 20h；
(5) dried product is calcined into 6h for 800 DEG C in a nitrogen atmosphere, obtains copper zinc composite oxide.
Obtained copper zinc composite oxide is subjected to surface sweeping Electronic Speculum sign, characterization result shows obtained copper zinc combined oxidation
Thing is in nanoparticle shape, and a footpath is about 12.0 μm, and surface is formed by being distributed homogeneous porous nano-sheet, and the thickness of nanometer sheet is about
20nm。
By obtained copper zinc composite oxide in U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Upper progress ICP tests.
Test result shows that copper coin cellulose content is 64wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is
15.8wt%.
Comparative example 1：
The preparation method of porous copper oxide is to comprise the following steps：
(1) at 20 DEG C, copper ion solution (n is configuredCu2+For 4mmol) 50mL, solvent is pure water solution, copper ion source
In copper nitrate；
(2) sodium carbonate liquor (C is preparedNa2CO3For 0.8mol/L) 50mL, add it to and contain copper ion described in (1)
In the solution of zinc ion, 0.5h is stirred, obtains suspension；
(3) suspension is transferred in the 100mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 18h at 130 DEG C
Afterwards, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) filter hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after at 60 DEG C
Dry 12h；
(5) dried product is calcined into 6h for 400 DEG C in air atmosphere, obtains copper oxide catalyst.
Obtained CuO is subjected to ICP surveys on U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Examination.
Test result shows that copper coin cellulose content is 79.8wt% in obtained CuO.
Comparative example 2：
The preparation method of porous zinc bloom comprises the following steps：
(1) at 20 DEG C, zinc ion solution (n is configuredZn2+For 4mmol) 50mL, solvent is pure water solution, zinc ion source
In zinc nitrate；
(2) sodium carbonate liquor (C is preparedNa2CO3For 0.8mol/L) 50mL, add it to and contain copper ion described in (1)
In the solution of zinc ion, 0.5h is stirred, obtains suspension；
(3) suspension is transferred in the 100mL autoclave of polytetrafluoroethyllining lining, the hydro-thermal reaction 18h at 130 DEG C
Afterwards, 20 DEG C are naturally cooled to, obtains hydrothermal product；
(4) filter hydrothermal product, gained solid washs for several times repeatedly with deionized water and absolute ethyl alcohol, after at 60 DEG C
Dry 12h；
(5) dried product is calcined into 6h for 400 DEG C in air atmosphere, obtains copper zinc composite oxide catalyst.
Obtained composite oxides are enterprising in U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrometers
Row ICP is tested.
Test result shows that Zn-ef ficiency content is 81.8wt% in obtained ZnO
Comparative example 3：
The preparation method of mechanical mixture type Porous Cu zinc composite oxide is：
The preparation method of cupric oxide is identical with comparative example 1, and the preparation method of zinc oxide is identical with comparative example 2, and both are pressed
According to the ratio (n of embodiment 1Cu2+:nZn2+=10:1) mechanical mixture is carried out.
By obtained copper zinc mechanical mixture type composite oxides in U.S. Pekin-Elmer inductively coupled plasma atoms
ICP tests are carried out on emission spectrometer.
Test result shows that copper coin cellulose content is 71.9wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is
8.2wt%.
Comparative example 4：
The preparation method of mechanical mixture type copper zinc composite oxide is：
The preparation method of cupric oxide is identical with comparative example 1, and zinc oxide uses certain commercial oxidation zinc, by both according to embodiment
1 ratio (nCu2+:nZn2+=10:1) mechanical mixture is carried out.
By obtained copper zinc mechanical mixture type composite oxides in U.S. Pekin-Elmer inductively coupled plasma atoms
ICP tests are carried out on emission spectrometer.
Test result shows that copper coin cellulose content is 71.8wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is
7.7wt%.
Comparative example 5：
The preparation method of mechanical mixture type copper zinc composite oxide is：
Cupric oxide uses certain commercial oxidation copper, and the preparation method of zinc oxide is identical with comparative example 2, by both according to embodiment
1 ratio (nCu2+:nZn2+=10:1) mechanical mixture is carried out.
By obtained copper zinc mechanical mixture type composite oxides in U.S. Pekin-Elmer inductively coupled plasma atoms
ICP tests are carried out on emission spectrometer.
Test result shows that copper coin cellulose content is 72.0wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is
8.0wt%.
Comparison example 6：
The preparation method of mechanical mixture type business copper zinc composite oxide is：
Cupric oxide uses certain commercial oxidation copper, and zinc oxide uses certain commercial oxidation zinc, the ratio by both according to embodiment 1
(nCu2+:nZn2+=10:1) mechanical mixture is carried out.
By obtained copper zinc mechanical mixture type composite oxides in U.S. Pekin-Elmer inductively coupled plasma atoms
ICP tests are carried out on emission spectrometer.
Test result shows that copper coin cellulose content is 72.1wt% in obtained copper zinc composite oxide, and Zn-ef ficiency content is
7.6wt%.
Evaluating catalyst：
Catalyst performance evaluation is carried out using miniature fixed bed device, reactor inside diameter 20cm, length 50cm, evaluation
Process is as follows：Copper zinc composite oxide catalyst made from 10g Si powder and 0.5g and 0.05g business zinc powder are uniformly mixed
Afterwards, ground and mixed forms contact；During reaction, first using N2Reaction system is purged, then, MeCl gases are switched to, by pre-
Reaction is in contact after heat with contact, reacted product flows out from reactor lower end, is received after condensed pipework condensation using toluene
Collection, unnecessary tail gas after alkali liquor absorption with emptying；Pass through capillary gas chromatography (Agilent after the mixed liquor constant volume of collection
7890A, KB-210 chromatographic column, TCD detectors) carry out quantitative analysis.This example is used to illustrate in " direct method " synthesis M2 reactions
In, the activity of catalyst and business copper catalyst made from embodiment 1~9 and comparative example 1~6, the test result such as institute of table 1
Show.
The catalyst activity test result table of table 1(1)
Note：(1) reaction condition：Preheating temperature is 350 DEG C, and reaction temperature is 325 DEG C, and reaction pressure is normal pressure, chloromethanes
Flow velocity is 25mL/min, reaction time 24h.
(2)M1：MeSiCl3(Trichloromethyl silane)；M2：Me2SiCl2(dimethyldichlorosilane), M3：Me3SiCl
(tri-methyl-chlorosilane)；M1H：MeHSiCl2(monomethyl silane containing hydrogen)；M2H：Me2HSiCl (dimethyl silane containing hydrogen)；
LBR：Low-boiling-point substance；HBR：High-boiling components；Product distribution is calculated by the percentage of reaction product corresponding area, and silicon conversion calculates public
Formula is as follows：
Wherein, W is the weight of contact.
As it can be seen from table 1 single copper oxide catalyst M2 prepared by comparative example 1 selectively converts for 81.2%, Si powder
Rate is 28.2%；Single Zinc oxide catalytic catalytically inactive prepared by comparative example 2；And mechanical mixture type prepared by comparative example 3
Copper zinc composite oxide catalyst, catalytic activity are obviously improved, and M2 selectively rises to 85.1%, Si powder conversion ratios and risen to
32.5%, and this catalytic activity, compared with adulterating industrial catalyst in comparative example 4, comparative example 5 and comparative example 6, catalytic performance is big
Width improves, and not only shows to be implicitly present in mutual synergy between CuO and ZnO, while confirm that method provided by the invention has
Obvious advantage.When micro-nano ball catalysis porous using copper zinc composite oxide made from embodiment 1~9, although copper zinc is compound
The constituent content of oxide micro-nano rice ball is different, and catalytic performance slightly has difference, but catalytic activity and selectivity and comparative example 1 and
Business copper catalyst is compared to significantly improving, and M2 selectively up to 89.5%, silica flour conversion ratio is up to 43.2%；And adopt
During 5% commercial oxidation zinc catalysis monomer synthetic reaction additional with the commercial oxidation copper of comparative example 6, most important index M2 selectivity
Only 69.5%, Si powder conversion ratios are also only 22.8%, and business copper catalyst M2 selectivity is 75.6%, silica flour conversion ratio
For 29.5%.This fully confirms that copper zinc composite oxide micro-nano ball provided by the invention has excellent catalytic performance.
It is above-mentioned test result indicates that, for M2 monomer synthetic reactions, with industrial catalyst, comparative example 1 and 2 prepare list
One CuO compares with ZnO and commercial catalysts, and the catalyst that method provided by the invention is prepared has in terms of catalytic performance
There is significant advantage.This mainly has the reason for following three aspect, one, micro-nano spherical catalyst pattern provided by the invention, particle diameter
It is distributed homogeneous；2nd, its module units nanometer sheet surface porosity of micro-nano spherical catalyst provided by the invention is porous, is advantageous to anti-
Answer the diffusion of thing chloromethanes, the desorption of gaseous product；3rd, cupric oxide and zinc oxide are uniformly dispersed, and enhance between two kinds of components
Synergy so that effective contact probability between each component and silica flour is significantly greatly increased, and results in more Cu3Si activity phases
(as shown in Figure 7), so as to improve M2 selectivity and silica flour conversion ratio.
Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention
In the technical scope of dew, the change or replacement that can readily occur in, all fall within protection scope of the present invention and it is open within the scope of.
Claims (32)
1. a kind of copper zinc composite oxide, it is characterised in that the pattern of the copper zinc composite oxide assembles for porous nano-sheet
The microballoon formed, the component of the nanometer sheet includes ZnO and CuO, ZnO are dispersed in CuO, wherein, ZnO mass percentages contain
The weight/mass percentage composition measured as 1%~20%, CuO is 80%~99%.
2. copper zinc composite oxide according to claim 1, it is characterised in that the particle size of the microballoon is 1~20 μ
m。
3. copper zinc composite oxide according to claim 1, it is characterised in that the thickness of the nanometer sheet be 20~
80nm。
4. copper zinc composite oxide according to claim 1, it is characterised in that the microballoon is loose structure.
5. the preparation method of the copper zinc composite oxide according to claim any one of 1-4, it is characterised in that methods described
Comprise the following steps：
(1) solution containing copper ion and zinc ion is mixed with alkaline solution, obtains mixed liquor；
(2) mixed liquor is subjected to hydro-thermal reaction, afterwards, by the product separation of solid and liquid of hydro-thermal reaction, obtains solid formation；
(3) solid formation is washed, dried, calcining, obtain the copper zinc composite oxide；
Wherein, the alkaline solution described in step (1) is that sodium bicarbonate solution, sal volatile, sodium carbonate liquor or potassium carbonate are molten
In liquid it is any or at least two mixed liquor.
6. according to the method for claim 5, it is characterised in that molten containing copper ion and zinc ion described in step (1)
The mol ratio of copper ion and zinc ion is (5~20) in liquid:1.
7. according to the method for claim 5, it is characterised in that molten containing copper ion and zinc ion described in step (1)
The concentration of copper ion is 0.08~0.25mol/L in liquid.
8. according to the method for claim 5, it is characterised in that molten containing copper ion and zinc ion described in step (1)
Liquid is obtained by the way that soluble copper salt and soluble zinc salt are dissolved in into solvent.
9. according to the method for claim 8, it is characterised in that the soluble copper salt is copper nitrate, copper chloride or acetic acid
Any of copper or at least two combination.
10. according to the method for claim 8, it is characterised in that the soluble zinc salt is zinc nitrate, zinc chloride or acetic acid
Any of zinc or at least two combination.
11. according to the method for claim 8, it is characterised in that the solvent is water and/or ethanol.
12. according to the method for claim 11, it is characterised in that the solvent is that volume ratio is 0:1~1:1 ethanol and
Water.
13. according to the method for claim 12, it is characterised in that the solvent is that volume ratio is 0.1:1~0.5:1 second
Alcohol and water.
14. according to the method for claim 13, it is characterised in that the solvent is that volume ratio is 0.2:1 second alcohol and water.
15. according to the method for claim 5, it is characterised in that the concentration of step (1) described alkaline solution be 0.1~
2mol/L。
16. according to the method for claim 5, it is characterised in that alkaline solution described in step (1) with it is described containing copper from
The volume ratio of the solution of son and zinc ion is 1:6~2:1.
17. according to the method for claim 5, it is characterised in that described in step (1) be blended in 10~35 DEG C under the conditions of enter
OK.
18. according to the method for claim 5, it is characterised in that the mode of step (1) described mixing is stirring.
19. according to the method for claim 18, it is characterised in that the time of the stirring is 0.5~4h.
20. according to the method for claim 5, it is characterised in that the reaction temperature of step (2) described hydro-thermal reaction is 100
~180 DEG C.
21. according to the method for claim 5, it is characterised in that the reaction time of step (2) described hydro-thermal reaction be 12~
24h。
22. according to the method for claim 5, it is characterised in that step (2) described hydro-thermal reaction is entered in autoclave
OK.
23. according to the method for claim 22, it is characterised in that the volume of the autoclave is 100~1000mL.
24. according to the method for claim 22, it is characterised in that the liner of the autoclave is polytetrafluoroethylene (PTFE).
25. according to the method for claim 5, it is characterised in that the product of the hydro-thermal reaction described in step (2) first cools down again
Carry out separation of solid and liquid.
26. according to the method for claim 5, it is characterised in that the temperature of step (3) described drying is 60~200 DEG C.
27. according to the method for claim 5, it is characterised in that the time of step (3) described drying is 6~20h.
28. according to the method for claim 5, it is characterised in that the temperature of step (3) described calcining is 400~1000 DEG C.
29. according to the method for claim 5, it is characterised in that the time of step (3) described calcining is 2~12h.
30. according to the method for claim 5, it is characterised in that step (3) calcining is in air atmosphere or inert atmosphere
Middle progress.
31. according to the method described in one of claim 5-30, it is characterised in that methods described comprises the following steps：
(1) soluble copper salt and soluble zinc salt are dissolved in volume ratio for (0:1~1):In 1 second alcohol and water, obtain containing copper
The solution of ion and zinc ion, wherein, the concentration of copper ion is 0.08~0.25mol/L, copper ion and zinc ion mol ratio
For (5~20):1；
(2) it is 1 by volume ratio:6~2:1 alkaline solution and solution containing copper ion and zinc ion are under the conditions of 10~35 DEG C
It is stirred, mixing time is 0.5~4h, obtains mixed liquor, wherein, the concentration of alkaline solution is 0.1~2mol/L；
(3) mixed liquor is subjected to hydro-thermal reaction in autoclave, the temperature of hydro-thermal reaction is 100~180 DEG C, the time 12
~24h, obtains hydrothermal product；By hydrothermal product separation of solid and liquid, solid formation is obtained；
(4) solid formation is washed, afterwards in 60~200 DEG C of dry 6~20h, then 400~1000 DEG C calcine 2~12h, obtain
The copper zinc composite oxide.
32. the purposes of the copper zinc composite oxide according to one of claim 1-4, it is used as organic silicon monomer synthetic reaction
In catalyst, promote the selectivity synthesis of dimethyldichlorosilane.
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| CN106861693B (en) * | 2017-04-07 | 2019-07-05 | 中国科学院过程工程研究所 | A kind of copper based composite metal oxidate mesomorphic material and its preparation method and application |
| CN107039649A (en) * | 2017-06-06 | 2017-08-11 | 中国科学院过程工程研究所 | A kind of multistage hollow microsphere of copper based composite metal oxidate, preparation method and the usage |
| CN108346782B (en) * | 2017-12-28 | 2020-08-04 | 杭州电子科技大学 | Porous copper oxide microsphere/multilayer graphene composite material and preparation method thereof |
| CN109663595A (en) * | 2018-12-11 | 2019-04-23 | 中科廊坊过程工程研究院 | A kind of copper based composite metal oxidate hollow microsphere, preparation method and the usage |
| CN109663596B (en) * | 2018-12-11 | 2021-11-16 | 廊坊绿色工业技术服务中心 | Double-monoatomic auxiliary agent supported copper oxide catalyst, and preparation method and application thereof |
| CN111326347B (en) * | 2020-02-28 | 2021-12-07 | 上海应用技术大学 | Zn-Cu-Se composite material and preparation method and application thereof |
| CN111871417B (en) * | 2020-08-24 | 2022-11-01 | 广州大学 | Mesoporous nanorod catalyst and preparation method and application thereof |
| CN113058609B (en) * | 2021-03-29 | 2022-03-04 | 蚌埠学院 | Preparation method of copper oxide-cuprous oxide-zinc oxide ternary compound |
| CN113828319B (en) * | 2021-10-13 | 2024-03-26 | 江苏扬农化工集团有限公司 | Cu-Zn-M composite oxide catalyst and preparation method and application thereof |
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