CN103495420B - Method for preparing ZnO-CuO composite metal oxide powder - Google Patents
Method for preparing ZnO-CuO composite metal oxide powder Download PDFInfo
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- CN103495420B CN103495420B CN201310443751.6A CN201310443751A CN103495420B CN 103495420 B CN103495420 B CN 103495420B CN 201310443751 A CN201310443751 A CN 201310443751A CN 103495420 B CN103495420 B CN 103495420B
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- 239000000843 powder Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 19
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910007565 Zn—Cu Inorganic materials 0.000 claims abstract description 21
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011265 semifinished product Substances 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The invention relates to a method for preparing ZnO-CuO composite metal oxide powder, which belongs to the technical field of preparation of composite metal oxide powders. The method comprises the following steps: firstly, uniformly mixing zinc powder with copper powder to obtain a zinc-copper powder mixture, and then, grinding the zinc-copper powder mixture for 30-240 minutes in an inert gas environment to obtain Zn-Cu alloy powder with a flaky surface; then, adding a mineralizer into the Zn-Cu alloy powder, reacting for 4-48 hours under conditions of pressure of 1-3 Mpa and temperature of 100-200 DEG C, and finally, naturally cooling the reaction product to room temperature to obtain a semi-finished product of ZnO-CuO composite metal oxide powder; and finally, washing and drying the semi-finished product of ZnO-CuO composite metal oxide powder to prepare the ZnO-CuO composite metal oxide powder. The preparation method has the advantages that the raw materials are easily obtained, reaction equipment and process are simple and the cost is low.
Description
Technical field
The present invention relates to a kind of method of making ZnO-CuO composite metal oxide powder, belong to composite metal oxide powder preparing technical field.
Background technology
Because ZnO-CuO composite granule has very wide application in the field such as Water warfare, catalysis, be applicable to multiple different reaction system.Modal is for CO, CO
2synthesizing methanol by hydrogenating or use its synthesizing dimethyl ether by synthetic gas, also may be used for methyl alcohol and ethanol or normal propyl alcohol one-step synthesis isobutylaldehyde and methanol dehydrogenation dimethoxym ethane etc.CO
2be the abundantest carbon resource that nature exists, be the important source material of following organic synthesis, utilize CO
2catalytic hydrogenation dimethyl ether synthesis etc. is CO
2the effective way transformed.
The preparation method that such powder adopts at present mostly is chemical method, and the general nitrate that adopts is prepared by the method for co-precipitation or hydro-thermal.Fan Huitao, Zeng Yi, the document " preparation of ZnO-CuO nano composite oxide and air-sensitive performance thereof " that Yang Haibin etc. deliver discloses a kind of preparation method of ZnO-CuO nano composite oxide: in the environment of high temperature, high pressure, become by Zn-Cu reasonable offer average grain diameter to be the Zn-Cu composite nanometer particle of 60 ~ 90nm, obtain pure ZnO-CuO nano composite oxide at 500 DEG C of roasting 2h.The process employs the complex device that HTHP can be provided, first raw material Zn-Cu alloy need be prepared into the Zn-Cu composite nanometer particle of 60 ~ 90nm and need at high temperature roasting just can make ZnO-CuO nano composite oxide, technique is more complicated in this way in institute, and higher to the requirement of equipment.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides a kind of method of making ZnO-CuO composite metal oxide powder.Not only raw material is easy to get this preparation method, consersion unit technique simple, with low cost, and the reunion preventing product that can be controlled, and product good dispersion, the present invention is achieved through the following technical solutions.
A method for making ZnO-CuO composite metal oxide powder, its concrete steps are as follows:
(1) be first that the zinc powder of 1 ~ 10:1 mixes with copper powder and obtains zinc-copper powder compound by mass ratio, then in inert-gas environment, by zinc-copper powder compound mill 30 ~ 240min, surface Zn-Cu alloy powder in the form of sheets can be obtained;
(2) add mineralizer in the Zn-Cu alloy powder obtained to step (1), pressure be 1 ~ 3Mpa, temperature be 100 ~ 200 DEG C of conditions under reaction 4 ~ 48h, obtain ZnO-CuO composite metal oxide powder semi-finished product after finally being naturally cooled to room temperature;
(3) under agitation, the pH value ZnO-CuO composite metal oxide powder semi-finished product that step (2) obtains being washed with water to filtrate is 7, absolute ethanol washing 20 ~ 120min is added again after filtration, filtered filtration residue dry 3 ~ 10h under temperature is 60 ~ 100 DEG C of conditions, namely obtains ZnO-CuO composite metal oxide powder again.
The granularity of described zinc powder, copper powder is 40 ~ 100 orders, and purity is more than 99%.
The quality of described Zn-Cu alloy powder and the volume ratio of mineralizer are 1:10 ~ 40g/ml.
Described mineralizer is the mixed solution of one or both arbitrary proportions in NaOH, potassium hydroxide, and concentration is 0.5 ~ 5mol/L.
Be high energy ball mill by levigate for zinc-copper powder compound adopted device in above-mentioned steps (1), in zinc-copper powder compound and high energy ball mill, the mass ratio of steel ball is 1:5 ~ 20.
Under stirring condition in above-mentioned steps (3), stir speed (S.S.) is 100 ~ 300r/min.
The invention has the beneficial effects as follows: the raw material of (1) this method directly chooses copper, zinc powder, directly by levigate rear acquisition ZnO-CuO composite granule, in preparation process, by the hydro-thermal reaction with mineralizer, copper obtains more highly active surface, and the zinc in alloy can be dispersed in copper surface after being oxidized to zinc oxide uniformly; (2) not only raw material is easy to get this preparation method, consersion unit technique is simple, with low cost, and the reunion preventing product that can be controlled, product good dispersion; (3) can realize ZnO and CuO with ZnO-CuO composite catalyst prepared by the present invention to combine closely, have well dispersed and excellent photocatalysis performance, in 90min, catalytic efficiency can reach 93.5%.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.
Embodiment 1
The method of this making ZnO-CuO composite metal oxide powder, its concrete steps are as follows:
(1) be first that the zinc powder of 1:1 mixes with copper powder and obtains zinc-copper powder compound by mass ratio, then in inert-gas environment, zinc-copper powder compound is put into high energy ball mill ball milling 30min, surface Zn-Cu alloy powder in the form of sheets can be obtained, wherein in zinc-copper powder compound and high energy ball mill, the mass ratio of steel ball is 1:5, the granularity of zinc powder, copper powder is 40 orders, and purity is more than 99%;
(2) mineralizer is added in the Zn-Cu alloy powder obtained to step (1), pressure be 1Mpa, temperature reacts 4h under being 100 DEG C of conditions, ZnO-CuO composite metal oxide powder semi-finished product are obtained after finally being naturally cooled to room temperature, wherein the quality of Zn-Cu alloy powder and the volume ratio of mineralizer are 1:40g/ml, mineralizer is NaOH, and concentration is 0.5mol/L;
(3) under stir speed (S.S.) is 100r/min stirring condition, the pH value ZnO-CuO composite metal oxide powder semi-finished product that step (2) obtains being washed with water to filtrate is 7, absolute ethanol washing 20min is added again after filtration, filtered filtration residue dry 3h under temperature is 60 DEG C of conditions, namely obtains ZnO-CuO composite metal oxide powder again.
Embodiment 2
The method of this making ZnO-CuO composite metal oxide powder, its concrete steps are as follows:
(1) be first that the zinc powder of 10:1 mixes with copper powder and obtains zinc-copper powder compound by mass ratio, then in inert-gas environment, zinc-copper powder compound is put into high energy ball mill ball milling 240min, surface Zn-Cu alloy powder in the form of sheets can be obtained, wherein in zinc-copper powder compound and high energy ball mill, the mass ratio of steel ball is 1:20, the granularity of zinc powder, copper powder is 100 orders, and purity is more than 99%;
(2) mineralizer is added in the Zn-Cu alloy powder obtained to step (1), pressure be 3Mpa, temperature reacts 48h under being 200 DEG C of conditions, ZnO-CuO composite metal oxide powder semi-finished product are obtained after finally being naturally cooled to room temperature, wherein the quality of Zn-Cu alloy powder and the volume ratio of mineralizer are 1:10g/ml, mineralizer is NaOH and the potassium hydroxide mixed solution of mass ratio 1:1, and concentration is 5mol/L;
(3) under stir speed (S.S.) is 300r/min stirring condition, the pH value ZnO-CuO composite metal oxide powder semi-finished product that step (2) obtains being washed with water to filtrate is 7, absolute ethanol washing 120min is added again after filtration, filtered filtration residue dry 10h under temperature is 100 DEG C of conditions, namely obtains ZnO-CuO composite metal oxide powder again.
Embodiment 3
The method of this making ZnO-CuO composite metal oxide powder, its concrete steps are as follows:
(1) be first that the zinc powder of 8:1 mixes with copper powder and obtains zinc-copper powder compound by mass ratio, then in inert-gas environment, zinc-copper powder compound is put into high energy ball mill ball milling 120min, surface Zn-Cu alloy powder in the form of sheets can be obtained, wherein in zinc-copper powder compound and high energy ball mill, the mass ratio of steel ball is 1:15, the granularity of zinc powder, copper powder is 80 orders, and purity is more than 99%;
(2) mineralizer is added in the Zn-Cu alloy powder obtained to step (1), pressure be 2Mpa, temperature reacts 24h under being 150 DEG C of conditions, ZnO-CuO composite metal oxide powder semi-finished product are obtained after finally being naturally cooled to room temperature, wherein the quality of Zn-Cu alloy powder and the volume ratio of mineralizer are 1:25g/ml, mineralizer is potassium hydroxide, and concentration is 3mol/L;
(3) under stir speed (S.S.) is 200r/min stirring condition, the pH value ZnO-CuO composite metal oxide powder semi-finished product that step (2) obtains being washed with water to filtrate is 7, absolute ethanol washing 100min is added again after filtration, filtered filtration residue dry 5h under temperature is 80 DEG C of conditions, namely obtains ZnO-CuO composite metal oxide powder again.
Claims (4)
1. a method for making ZnO-CuO composite metal oxide powder, is characterized in that concrete steps are as follows:
(1) be first that the zinc powder of 1 ~ 10:1 mixes with copper powder and obtains zinc-copper powder compound by mass ratio, then in inert-gas environment, by zinc-copper powder compound mill 30 ~ 240min, surface Zn-Cu alloy powder in the form of sheets can be obtained;
(2) add mineralizer in the Zn-Cu alloy powder obtained to step (1), pressure be 1 ~ 3MPa, temperature be 100 ~ 200 DEG C of conditions under reaction 4 ~ 48h, obtain ZnO-CuO composite metal oxide powder semi-finished product after finally being naturally cooled to room temperature;
(3) under agitation, the pH value ZnO-CuO composite metal oxide powder semi-finished product that step (2) obtains being washed with water to filtrate is 7, absolute ethanol washing 20 ~ 120min is added again after filtration, filtered filtration residue dry 3 ~ 10h under temperature is 60 ~ 100 DEG C of conditions, namely obtains ZnO-CuO composite metal oxide powder again.
2. the method for making ZnO-CuO composite metal oxide powder according to claim 1, is characterized in that: the granularity of described zinc powder, copper powder is 40 ~ 100 orders, and purity is more than 99%.
3. the method for making ZnO-CuO composite metal oxide powder according to claim 1, is characterized in that: the quality of described Zn-Cu alloy powder and the volume ratio of mineralizer are 1:10 ~ 40g/ml.
4. the method for making ZnO-CuO composite metal oxide powder according to claim 1, is characterized in that: described mineralizer is the mixed solution of one or both arbitrary proportions in NaOH, potassium hydroxide, and concentration is 0.5 ~ 5mol/L.
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| CN105148983B (en) * | 2015-09-29 | 2017-11-03 | 滨州学院 | Photochemical catalyst of dyestuff and preparation method thereof in a kind of degrading waste water |
| CN105582935B (en) * | 2016-03-07 | 2018-03-30 | 中国科学院过程工程研究所 | A kind of copper zinc composite oxide, preparation method and the usage |
| CN107233889B (en) * | 2017-05-03 | 2020-04-07 | 昆明理工大学 | Preparation method of Cu/ZnO photocatalyst |
| CN108579752A (en) * | 2018-04-17 | 2018-09-28 | 昆明理工大学 | A kind of preparation method of CuO/ZnO composite photo-catalysts |
| CN110327932B (en) * | 2019-07-03 | 2021-07-23 | 昆明理工大学 | Cu2Preparation method of O/ZnO composite photocatalyst |
| CN110882701A (en) * | 2019-12-13 | 2020-03-17 | 北京化工大学 | Gold-based bimetallic/ZnO-CuO catalyst for preparing dihydroxyacetone from glycerol and preparation method thereof |
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| CN1421383A (en) * | 2002-11-26 | 2003-06-04 | 复旦大学 | Amorphous skeletal-nickel hydrogenating catalyst for anthraquinone process of preparing hydrogen peroxide and its prepn |
| CN102989463A (en) * | 2012-12-04 | 2013-03-27 | 昆明理工大学 | High-energy ball milling preparation method of CuZnO catalyst for methanol synthesis |
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| PT105613A (en) * | 2011-04-04 | 2012-10-04 | Univ Do Porto | METAL OXIDE SUPPORT AND CATALYST, PREPARATION METHOD AND ITS APPLICATIONS |
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| CN1421383A (en) * | 2002-11-26 | 2003-06-04 | 复旦大学 | Amorphous skeletal-nickel hydrogenating catalyst for anthraquinone process of preparing hydrogen peroxide and its prepn |
| CN102989463A (en) * | 2012-12-04 | 2013-03-27 | 昆明理工大学 | High-energy ball milling preparation method of CuZnO catalyst for methanol synthesis |
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