CN113976116B - Variable-speed ball milling preparation of ternary copper Cu-Cu 2 O-CuO catalyst and method thereof - Google Patents
Variable-speed ball milling preparation of ternary copper Cu-Cu 2 O-CuO catalyst and method thereof Download PDFInfo
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- CN113976116B CN113976116B CN202111238044.4A CN202111238044A CN113976116B CN 113976116 B CN113976116 B CN 113976116B CN 202111238044 A CN202111238044 A CN 202111238044A CN 113976116 B CN113976116 B CN 113976116B
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- 239000010949 copper Substances 0.000 title claims abstract description 109
- 238000000498 ball milling Methods 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000004615 ingredient Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000000843 powder Substances 0.000 abstract description 10
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000875 high-speed ball milling Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 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
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing ternary copper Cu-Cu by variable-speed ball milling 2 An O-CuO catalyst and a method thereof, which relate to the technical field of catalyst preparation. The invention comprises the following steps: step one: mixing simple substance copper powder and copper oxide powder according to a designed mass ratio, and placing the mixture in a ball mill; step two: placing zirconia balls in a ball mill in the first step; step three: starting the ball mill in the second step, mechanically ball-milling the ingredients in the ball mill at a high rotating speed, and then mechanically ball-milling at a low rotating speed to obtain ternary copper Cu-Cu 2 O-CuO catalyst. The invention prepares ternary copper Cu-Cu by variable-speed ball milling 2 The O-CuO catalyst is prepared through ball milling, mechanical ball milling at high rotation speed and low rotation speed, friction heat generated during ball milling to promote the centering reaction of the components in the material, and regulating the rotation speed, the proportion of the material powder and other parameters to obtain ternary copper catalyst with adjustable composition ratio and controllable granularity.
Description
Technical Field
The invention belongs toThe technical field of catalyst preparation, in particular to a method for preparing ternary copper Cu-Cu by variable-speed ball milling 2 O-CuO catalyst and method thereof.
Background
The organic silicon material is a polymer synthetic material with Si bonded with organic groups as main characteristics, integrates the characteristics of inorganic matters and the functions of organic matters, can be widely applied to the fields of electronics, electrical appliances, aerospace, construction, medicine and the like, and is an indispensable material in national production and life. Dimethyl dichlorosilane (M2 for short) is the most valuable and most used organosilicon monomer in the whole organosilicon material industry chain, and is an important pillar of the organosilicon industry. The method has the advantages of simple process, high yield, high safety and contribution to realizing continuous mass production, however, the reaction system is complex, a plurality of side reactions such as pyrolysis and disproportionation are carried out in the reaction process, and the byproducts are more and are also interfered by other numerous factors. The selectivity and the yield of M2 are one of important standards for measuring the level of direct production technology, wherein the high-efficiency copper-based catalyst has great influence on direct synthesis reaction and is an important way for improving the selectivity and the yield of M2;
the copper catalyst is a classical catalyst for synthesizing M2 by a direct method, and the copper catalyst used for the direct method is subjected to the steps of preparing a catalyst from electrolytic copper powder, copper salt (CuCl), metallic copper (Cu), cuprous oxide (Cu 2 O), copper oxide (CuO) to composite ternary copper (Cu, cu) 2 O, cuO) are provided. Ternary copper Cu-Cu compared with the catalyst used in the past 2 The O-CuO catalyst has the advantages of strong catalytic activity, high selectivity, short induction period, easy storage and the like, and is the most used catalyst in the production of the organosilicon monomer at present.
Currently, ternary copper Cu-Cu 2 The O-CuO catalyst is subjected to two steps: such as ball milling and heating and ball milling under protective atmosphere, low-pressure copper oxide powder reduction and low-pressure diffusion, hydrothermal method and the like, and the preparation process is complex, so that the development process is simple, the process is controllable, the cost is low, and the ternary copper Cu-Cu can be prepared in a large scale 2 The production process of O-CuO catalyst is to raise methyl radicalOne of the important points in the efficiency of the chlorosilane synthesis process.
Disclosure of Invention
The invention aims to provide a method for preparing ternary copper Cu-Cu by variable-speed ball milling 2 O-CuO catalyst and method thereof, solving the problem of ternary copper Cu-Cu in the prior art 2 The preparation process of the O-CuO catalyst is complex, multiple steps are needed, multiple devices are involved, high-temperature heating is needed in the reaction, a large amount of protective gas and chemical reagent are used, and the cost is high.
In order to achieve the purpose, the invention is realized by the following technical scheme:
variable-speed ball milling preparation of ternary copper Cu-Cu 2 A method of O-CuO catalyst comprising the steps of:
step one: mixing simple substance copper powder and copper oxide powder according to a designed mass ratio, and placing the mixture in a ball mill;
step two: placing zirconia balls in a ball mill in the first step;
step three: starting the ball mill in the second step, mechanically ball-milling the ingredients in the ball mill at a high rotating speed, and then mechanically ball-milling at a low rotating speed to obtain ternary copper Cu-Cu 2 O-CuO catalyst.
Optionally, in the first step, the mass ratio of the elemental copper powder to the copper oxide powder is 1:2-2:1.
Optionally, in the second step, the particle size of the zirconia balls is 5mm.
Optionally, the ball-to-material ratio of the total mass of the zirconia balls in the second step to the total mass of the elemental copper powder and the copper oxide powder in the first step is 3:1-5:1.
Optionally, in the third step, the rotating speed of the high-rotating-speed mechanical ball milling is 300rpm-400rpm, and the ball milling time of the high-rotating-speed mechanical ball milling is 5min-35min.
Optionally, in the third step, the rotating speed of the low-rotating-speed mechanical ball milling is 180rpm-280rpm, and the ball milling time of the low-rotating-speed mechanical ball milling is 10min-40min.
Variable-speed ball milling preparation of ternary copper Cu-Cu 2 An O-CuO catalyst characterized by ternary copper Cu-Cu 2 The O-CuO catalyst is according to the weightPreparation of ternary copper Cu-Cu by variable speed ball milling according to any one of claims 1-6 2 The O-CuO catalyst is prepared by a method.
Alternatively, ternary copper Cu-Cu 2 The O-CuO catalyst comprises the following components in percentage by mass: 0.5% -15%; cu (Cu) 2 O：75％-95％；CuO：15％-30％。
Alternatively, ternary copper Cu-Cu 2 The average particle size of the O-CuO catalyst is 3-10 μm.
The embodiment of the invention has the following beneficial effects:
one embodiment of the invention prepares ternary copper Cu-Cu by a variable speed ball milling 2 The O-CuO catalyst and the method thereof improve the ball milling mode, set high-rotation speed and low-rotation speed two-stage mechanical ball milling, utilize friction heat generated in the ball milling process to advance the centering reaction among all components in the material, obtain the ternary copper catalyst with adjustable composition proportion and controllable granularity by adjusting the parameters of ball milling rotation speed, raw material powder proportion and the like, and prepare ternary copper Cu-Cu by the proposed variable-speed ball milling 2 The method for preparing the O-CuO catalyst only needs one device of a ball mill, simplifies the process for preparing the catalyst, does not need chemical reagent or heating, has low cost and no environmental pollution, and is suitable for industrial production.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a flow chart of a catalyst preparation method according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
In order to keep the following description of the embodiments of the present invention clear and concise, the detailed description of known functions and known components thereof have been omitted.
Referring to FIG. 1, in this embodiment, a variable speed ball milling process for preparing ternary Cu-Cu is provided 2 A method of O-CuO catalyst comprising the steps of:
step one: mixing simple substance copper powder and copper oxide powder according to a designed mass ratio, and placing the mixture in a ball mill;
step two: placing zirconia balls in a ball mill in the first step;
step three: starting the ball mill in the second step, mechanically ball-milling the ingredients in the ball mill at a high rotating speed, and then mechanically ball-milling at a low rotating speed to obtain ternary copper Cu-Cu 2 O-CuO catalyst.
Under the high-speed ball milling of the embodiment, the collision probability between the milling ball and the powder is increased, and copper oxide raw materials are rapidly consumed and undergo a centering reaction to generate a large amount of cuprous oxide; however, as the collision probability increases, the energy aggregation of the powder generated by collision increases, the specific surface energy also increases correspondingly, the surface activity of the powder is greatly improved, and the agglomeration phenomenon of the powder is further aggravated, so that the trend of coarsening the powder granularity appears;
the occurrence rate of the return reaction is reduced under the low-speed ball milling, but the spheres are always contacted with the materials and are not separated, so that the grinding effect is very strong, the powder of the catalyst can be thinned, and the ternary components of copper, copper oxide and cuprous oxide are uniformly mixed;
the rotation speed ratio and the ball milling time ratio of the high-speed ball milling and the low-speed ball milling are controlled, so that partial centering reaction occurs, and the ternary catalyst with controllable component content and uniform and adjustable granularity is obtained.
The application of one aspect of the embodiment is: it is necessary to prepare ternary copper Cu-Cu 2 In the O-CuO catalyst, the elemental copper powder and the copper oxide powder are prepared according to the designed qualityMixing, placing in a ball mill, placing zirconia balls in the ball mill, starting the ball mill, mechanically ball-milling the ingredients in the ball mill at a high rotating speed, and mechanically ball-milling at a low rotating speed to obtain ternary copper Cu-Cu 2 O-CuO catalyst. It should be noted that all the electric devices involved in the present application can be powered by a storage battery or an external power supply.
Ternary copper Cu-Cu prepared by variable speed ball milling 2 The O-CuO catalyst method improves ball milling mode, sets high-rotation speed and low-rotation speed two-stage mechanical ball milling, utilizes friction heat generated in the ball milling process to advance the centering reaction between each component in the material, obtains ternary copper catalyst with adjustable composition proportion and controllable granularity by adjusting parameters such as ball milling rotation speed, raw material powder proportion and the like, and prepares ternary copper Cu-Cu by the proposed variable-speed ball milling 2 The method for preparing the O-CuO catalyst only needs one device of a ball mill, simplifies the process for preparing the catalyst, does not need chemical reagent or heating, has low cost and no environmental pollution, and is suitable for industrial production.
In the first step of this embodiment, the mass ratio of the elemental copper powder to the copper oxide powder is 1:2 to 2:1.
In the second step of this example, the particle size of the zirconia balls was 5mm.
The ball-to-material ratio of the total mass of the zirconia balls in the second step to the total mass of the elemental copper powder and the copper oxide powder in the first step is 3:1-5:1.
In the third step of the embodiment, the rotation speed of the high-rotation-speed mechanical ball milling is 300rpm-400rpm, and the ball milling time of the high-rotation-speed mechanical ball milling is 5min-35min.
In the third step of the embodiment, the rotation speed of the low rotation speed mechanical ball milling is 180rpm-280rpm, and the ball milling time of the low rotation speed mechanical ball milling is 10min-40min.
Variable-speed ball milling preparation of ternary copper Cu-Cu 2 An O-CuO catalyst characterized by ternary copper Cu-Cu 2 The O-CuO catalyst is ternary copper Cu-Cu prepared by variable speed ball milling according to any one of claims 1 to 6 2 The O-CuO catalyst is prepared by a method.
Ternary copper Cu-Cu of the present example 2 The O-CuO catalyst comprises the following components in percentage by mass: 0.5% -15%; cu (Cu) 2 O：75％-95％；CuO：15％-30％。
Ternary copper Cu-Cu of the present example 2 The average particle size of the O-CuO catalyst is 3-10 μm.
Specifically, the present invention is described in detail below with reference to examples: .
Example 1
Preparation of the catalyst:
(1) Mixing commercial elemental copper powder and commercial copper oxide powder with the mass ratio of 43:57 to obtain a reaction raw material;
(2) The reaction raw materials are put into a ball mill, and the ball-material ratio is 5:1, ball milling for 20 minutes at a high speed at 400rpm, and ball milling for 25 minutes at a low speed at 280rpm, thereby obtaining ternary copper Cu-Cu 2 O-CuO catalyst.
The obtained copper catalyst is analyzed by a chemical method, and each component comprises the following components in percentage by mass: cu:2.5%, cu 2 O：87％，CuO：10.5％。
Example 2
(1) Mixing commercial elemental copper powder and commercial copper oxide powder with the mass ratio of 34:66 to form a reaction raw material;
(2) Putting the reaction raw materials into a ball mill, ball-milling at a high speed for 50 minutes at a rotating speed of 300rpm, and ball-milling at a low speed for 10 minutes at a rotating speed of 180rpm to obtain ternary copper Cu-Cu, wherein the ball-material ratio is 3:1 2 O-CuO catalyst.
The obtained copper catalyst is analyzed by a chemical method, and each component comprises the following components in percentage by mass: cu:0.5%, cu 2 O：75％，CuO：15％.
Example 3
(1) Mixing commercial elemental copper powder and commercial copper oxide powder with the mass ratio of 66:34 to form a reaction raw material;
(2) The reaction raw materials are put into a ball mill, and the ball-material ratio is 5:1, ball milling for 35 minutes at a high speed at 400rpm, and ball milling for 40 minutes at a low speed at 280rpm at a reduced speed to obtain ternary copper Cu-Cu 2 O-CuO catalyst.
The obtained copper catalyst is analyzed by a chemical method, and each component comprises the following components in percentage by mass: cu:15%, cu 2 O：95％，CuO：30％。
Comparative example 1
The procedure was as in example 1, except that low-speed mechanical ball milling was not performed and the material was taken out after high-speed mechanical ball milling.
Comparative example 2
The procedure was as in example 1, except that high-speed mechanical ball milling was not performed and the material was taken out after low-speed mechanical ball milling.
Comparative example 3
Catalyst performance was evaluated using commercial copper powder as catalyst.
Comparative example 4
Catalyst performance was evaluated using commercial copper oxide powder as catalyst.
Comparative example 5
A catalyst is composed of Cu and Cu 2 O, cuO, wherein the powder is obtained by directly mixing the following three materials in percentage by mass: cu:2.5%, cu 2 O：87％，CuO：10.5％。
TABLE 1 results of catalytic Activity tests
Ternary copper Cu-Cu prepared by the preparation method of the embodiment of the invention 2 The O-CuO catalyst, when used for synthesizing M2 by a direct method, shows higher selectivity of dimethyl dichlorosilane and conversion rate of silicon powder raw materials than commercial catalysts.
The above embodiments may be combined with each other.
It should be noted that the terms "first," "second," and the like in the description and claims of the present application and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that embodiments of the present application described herein may be implemented in sequences other than those illustrated or described herein.
In the description of the present invention, it should be understood that the azimuth or positional relationships indicated by the azimuth terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal", and "top, bottom", etc., are generally based on the azimuth or positional relationships shown in the drawings, merely to facilitate description of the present invention and simplify the description, and these azimuth terms do not indicate and imply that the apparatus or elements referred to must have a specific azimuth or be constructed and operated in a specific azimuth, and thus should not be construed as limiting the scope of protection of the present invention; the orientation word "inner and outer" refers to inner and outer relative to the contour of the respective component itself.
Claims (6)
1. Variable-speed ball milling preparation of ternary copper Cu-Cu 2 The method of the O-CuO catalyst is characterized by comprising the following steps:
step one: mixing simple substance copper powder and copper oxide powder according to a designed mass ratio, and placing the mixture in a ball mill;
step two: placing zirconia balls in a ball mill in the first step;
step three: starting the ball mill in the second step, mechanically ball-milling the ingredients in the ball mill at a high rotating speed, and then mechanically ball-milling at a low rotating speed to obtain ternary copper Cu-Cu 2 An O-CuO catalyst;
in the first step, the mass ratio of the simple substance copper powder to the copper oxide powder is 1:2-2:1;
in the second step, the particle size of the zirconia balls is 5mm;
the ball-material ratio of the total mass of the zirconia balls in the second step to the total mass of the simple substance copper powder and the copper oxide powder in the first step is 3:1-5:1.
2. The method for preparing ternary copper Cu-Cu by variable speed ball milling according to claim 1 2 The O-CuO catalyst method is characterized in that in the third step, the rotating speed of high-rotating-speed mechanical ball milling is 300rpm-400rpm, and the ball milling time of the high-rotating-speed mechanical ball milling is 5min-35min.
3. The method for preparing ternary copper Cu-Cu by variable speed ball milling according to claim 1 2 The O-CuO catalyst method is characterized in that in the third step, the rotating speed of the low-rotating-speed mechanical ball milling is 180rpm-280rpm, and the ball milling time of the low-rotating-speed mechanical ball milling is 10min-40min.
4. Variable-speed ball milling preparation of ternary copper Cu-Cu 2 An O-CuO catalyst characterized by ternary copper Cu-Cu 2 The O-CuO catalyst is ternary copper Cu-Cu prepared by variable speed ball milling according to any one of claims 1-3 2 The O-CuO catalyst is prepared by a method.
5. A variable speed ball milling process for preparing ternary Cu-Cu as claimed in claim 4 2 An O-CuO catalyst characterized by ternary copper Cu-Cu 2 The O-CuO catalyst comprises the following components in percentage by mass: 0.5% -15%; cu (Cu) 2 O：75％-95％；CuO：15％-30％。
6. A variable speed ball milling process for preparing ternary Cu-Cu as claimed in claim 4 2 An O-CuO catalyst characterized by ternary copper Cu-Cu 2 The average particle size of the O-CuO catalyst is 3-10 μm.
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| 冷森林.《材料合成实验》.西安交通大学出版社,2020,第2-3页. * |
| 张玉台.《科技工程与经济社会协调发展》.中国科学技术出版社,2004,第63页第4段. * |
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