CN117101653A - Copper-based powder with high specific surface composite morphology and preparation method thereof - Google Patents
Copper-based powder with high specific surface composite morphology and preparation method thereof Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 239000010949 copper Substances 0.000 title claims abstract description 111
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 96
- 239000000843 powder Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 16
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 16
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 13
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 13
- 239000005751 Copper oxide Substances 0.000 claims abstract description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims description 66
- 230000009467 reduction Effects 0.000 claims description 38
- 238000007254 oxidation reaction Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 28
- 238000000227 grinding Methods 0.000 claims description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 12
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 13
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 17
- 230000008901 benefit Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Classifications
-
- 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
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/125—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving both Si-C and Si-halogen linkages, the Si-C and Si-halogen linkages can be to the same or to different Si atoms, e.g. redistribution reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The application provides copper-based powder with a high specific surface composite morphology and a preparation method thereof, wherein the copper-based powder with the high specific surface composite morphology consists of flaky copper powder and flower-shaped porous structure cuprous oxide and copper oxide; copper powder is a matrix material, the microscopic morphology is a sheet structure, the microscopic morphology of cuprous oxide and cupric oxide is a flower-shaped porous structure, and the copper powder is embedded on the surface of the sheet copper powder, so that the specific surface area can be increased, a large number of attachment sites can be provided for a catalyst, the contact area with catalytic substances is increased, and the catalytic efficiency is further improved. The copper-based powder with the high specific surface composite morphology can be used as a catalyst in the field of methyl chlorosilane synthesis, solves the problem of active metal agglomeration on the copper-based catalyst in the prior art, ensures that the catalyst has higher catalytic activity, improves the silicon powder conversion rate, and simultaneously increases the selectivity of a main product M2.
Description
Technical Field
The application relates to the technical field of catalysts for synthesizing dimethyl dichlorosilane, in particular to copper-based powder with high specific surface composite morphology and a preparation method thereof.
Background
The organic silicon material is a polymer synthetic material with Si bonded with organic groups as a main characteristic, has the dual characteristics of organic materials and inorganic materials, and can be widely applied to the fields of electronics, electrical appliances, aerospace, construction, medicine and the like. The dimethyl dichlorosilane (M2 for short) is the most valuable and most used organic silicon monomer in the whole organic silicon material industry chain, and occupies about 90% of the monomer yield in the organic silicon industry, and is an important pillar in the organic silicon industry. In industry, a direct method is generally used for synthesizing M2, namely, silicon powder and methyl chloride gas are directly reacted under the action of a copper-based main catalyst and a small amount of auxiliary agents to generate methyl chlorosilane. 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 yield of M2 are one of the important criteria for measuring the level of direct production technology, wherein the high-efficiency catalyst has a great influence on the direct synthesis reaction, and is an important way for improving the selectivity and yield of M2.
Copper and its compoundIs a classical catalyst for synthesizing methyl chlorosilane by a direct method. The contact activity (silicon conversion and monomer yield) and the selectivity of dimethyldichlorosilane are closely related to the chemical composition, particle size and particle size distribution of the catalyst, the surface state and the preparation method, and also related to silicon powder and the cocatalyst. Copper catalysts for the direct process have undergone a process from the group consisting of 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). Ternary copper catalyst CuO-Cu 2 The O-Cu 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 methyl chlorosilane at present.
The existing ternary copper catalyst is generally in a lamellar structure or a spherical structure, is easy to accumulate in a catalytic system, has insufficiently developed particle surfaces, and cannot provide more catalytic active sites. In addition, the ternary copper catalyst needs better dispersibility in the catalytic use process, so that hardening and agglomeration of the catalyst are prevented, the activity of the catalyst is reduced, and the catalytic effect of the ternary copper catalyst is influenced. Accordingly, there is a need for an improved technique to address the problems currently faced.
Disclosure of Invention
In order to overcome the defects in the prior art, the main purpose of the application is to provide copper-based powder with high specific surface composite morphology and a preparation method thereof, wherein the copper-based powder with high specific surface composite morphology consists of flaky copper powder and flower-shaped porous structure cuprous oxide and copper oxide; copper powder is a matrix material, the microscopic morphology is a sheet structure, the microscopic morphology of cuprous oxide and cupric oxide is a flower-shaped porous structure, and the copper powder is embedded on the surface of the sheet copper powder, so that the specific surface area can be increased, a large number of attachment sites can be provided for a catalyst, the contact area with catalytic substances is increased, and the catalytic efficiency is further improved.
In order to achieve the above object, according to a first aspect of the present application, there is provided a copper-based powder having a high specific surface composite morphology.
The copper-based powder with the high specific surface composite morphology consists of sheet copper powder, cuprous oxide with a flower-shaped porous structure and cupric oxide, wherein the cuprous oxide with the flower-shaped porous structure is inlaid on the sheet copper powder.
Further, the specific surface area of the copper-based powder is 0.8-2.0 m 2 /g。
In order to achieve the above object, according to a second aspect of the present application, there is provided a method for preparing a copper-based powder having a high specific surface composite morphology.
The preparation method of the copper-based powder with the high specific surface composite morphology comprises the following steps:
s1: weighing a proper amount of copper powder, adding a dispersing agent, and placing the mixture in a ball mill for ball milling to obtain flaky copper powder;
s2: weighing a proper amount of copper oxide powder and the flaky copper powder, and placing the copper oxide powder and the flaky copper powder in a ball mill for ball milling to obtain mixed copper-based powder;
s3: sequentially carrying out thermal reduction treatment and oxidation reaction on the mixed copper-based powder to obtain flower-shaped porous Cu 2 And the O-CuO structure is inlaid in the copper-based powder with the composite morphology on the flaky copper powder.
Further, in step S1,
the copper powder includes, but is not limited to, electrolytic copper powder, water atomized copper powder, ultrafine copper powder, low apparent copper powder;
preferably, the purity of the copper powder is more than or equal to 97 percent, and the granularity range is-50 to +400 meshes.
Preferably, the dispersing agent is at least one of polyacrylamide, zinc stearate, stearic acid, paraffin wax and polyethylene wax, and the adding mass percentage is 0.1-1.0wt%.
Further, in step S2,
the copper oxide powder includes but is not limited to copper oxide and cuprous oxide powder, and D50 is 0.5-5 μm.
Further, in step S1 and in step S2,
the ball milling time is 0.5-4 h, and the ball milling rotating speed is 50-400 rpm;
preferably, the ball milling process is performed in an air atmosphere or a nitrogen atmosphere.
Further, in step S1 and in step S2,
in the ball milling process, the mass ratio of the powder to the grinding balls is 1 (1-20);
preferably, the grinding ball adopted in the ball milling process is made of zirconia, and the diameter of the grinding ball is 1-10 mm.
Further, in step S3,
the temperature of the thermal reduction treatment is 300-900 ℃, and the heat preservation time is 1-8 h;
preferably, the reducing gas is at least one of hydrogen, ammonia decomposition gas, and carbon monoxide.
Further, in step S3,
the oxidation temperature of the oxidation reaction is 250-650 ℃, and the heat preservation time is 1-8 h;
preferably, the oxidizing gas is at least one of high-purity oxygen, compressed air, and industrial oxygen.
In order to achieve the above object, according to a third aspect of the present application, there is provided an application of a copper-based powder having a high specific surface composite morphology.
The copper-based powder with the high specific surface composite morphology is applied as a catalyst for synthesizing the dimethyl dichlorosilane, the selectivity of the catalytic performance of the catalyst for synthesizing the dimethyl dichlorosilane is 80-88% in a fixed bed test M2, and the conversion rate of silicon powder is 10-50%;
the conversion rate of the silicon powder is preferably 20-50%.
The application has the advantages that:
1) The copper-based powder with the composite morphology consists of flaky copper powder and cuprous oxide with a flower-shaped porous structure, wherein the flaky copper powder is prepared from copper oxide; wherein, the copper powder is a matrix material, and the microstructure is a sheet structure; the cuprous oxide and the cupric oxide are embedded on the surface of the flaky copper, the microcosmic appearance is a flower-shaped porous structure, the specific surface area is improved, a large number of attachment sites can be provided for the catalyst, the contact area with catalytic substances is increased, and the catalytic efficiency is further improved.
2) The special structure of the flower-shaped porous structure embedded on the flaky copper powder can effectively avoid aggregation of the flaky structure and simultaneously has Cu and Cu 2 The performance of the ternary components of O and CuO, and the ternary components generate a synergistic effect, so that the interaction between active components in the catalyst is enhanced, thereby obviously improving the activity of the catalyst and the selection of target productsThe content of the ternary components can be accurately regulated and controlled, so that the catalyst achieves the best catalytic activity and dimethyl selectivity.
3) The microcosmic morphology of the copper-based powder with the composite morphology is a mosaic flower-like structure on a sheet-like structure, so that the oxygen storage and release performance and the carbon deposition resistance of the catalyst can be effectively enhanced, and the activity and the service life of the catalyst are greatly improved.
4) The preparation raw materials of the copper-based powder with the composite morphology are low, the uniformity and the stability of the product are high, the reaction equipment is simple, the operation steps are simple and convenient, and the ternary copper catalyst for synthesizing the dimethyl dichlorosilane can be efficiently and continuously produced.
5) Compared with the traditional ternary copper catalyst, the copper-based powder with the composite morphology is used for catalyzing the synthesis reaction of the organic silicon monomer, shows more excellent catalyst performance, increases the synthesis of the organic silicon monomer, improves the selectivity of the dimethyl dichlorosilane, and creates higher economic benefit.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to designate like parts throughout the figures. In the drawings:
FIG. 1 is a scanning electron microscope morphology diagram of the flaky copper powder prepared in the example provided by the application;
fig. 2 is a scanning electron microscope morphology diagram of the copper-based powder with composite morphology prepared in the example provided by the application.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The first aspect of the application provides copper-based powder with a high specific surface composite morphology.
The copper-based powder with high specific surface composite morphology can be used as a catalyst in the field of methyl chlorosilane synthesis, solves the problem of active metal agglomeration on the copper-based catalyst in the prior art, ensures that the catalyst has higher catalytic activity, improves the silicon powder conversion rate and simultaneously increases the selectivity of a main product M2.
The copper-based powder with the composite morphology consists of copper powder, cuprous oxide and copper oxide powder; the copper powder has a sheet-shaped microstructure, and the cuprous oxide and copper oxide powder has a flower-shaped porous structure and is embedded on the surface of the sheet-shaped copper powder.
The flower-shaped porous structure is inlaid in the special morphology structure of the sheet-shaped structure, so that aggregation of the sheet-shaped structure can be effectively avoided. At the same time have Cu, cu 2 The performance of the three components of O and CuO has synergistic effect, so that the interaction between active components in the catalyst is enhanced, and the activity of the catalyst and the selectivity of target products are obviously improved.
In the embodiment of the application, the specific surface area of the copper-based powder with the composite morphology is 0.8-2.0 m 2 /g。
Exemplary, the specific surface area of the copper-based powder with the composite morphology is 0.8m 2 /g、0.9m 2 /g、1.0m 2 /g、1.1m 2 /g、1.2m 2 /g、1.3m 2 /g、1.4m 2 /g、1.5m 2 /g、1.6m 2 /g、1.7m 2 /g、1.8m 2 /g、1.9m 2 /g、2.0m 2 However, the values of/g are not limited to the values recited, but are equally applicable to other values not recited in the range.
The second aspect of the application provides a preparation method of copper-based powder with a high specific surface composite morphology.
The preparation method is environment-friendly, simple in process, low in cost and suitable for industrial mass production.
The preparation method of the copper-based powder with the high specific surface composite morphology comprises the following steps:
s1: weighing a proper amount of copper powder, adding a dispersing agent, and placing in a ball mill for ball milling to obtain flaky copper powder.
In an embodiment of the present application, the copper powder is selected from at least one of the following materials: electrolytic copper powder, water atomized copper powder, superfine copper powder and copper powder with low apparent density.
As one embodiment of the application, the purity of copper powder is more than or equal to 97 percent, and the purity refers to the mass percentage content of metal copper.
As one embodiment of the present application, the copper powder has a particle size distribution between-50 and +400 mesh. Wherein "+" in front of the mesh number represents sieving and "-" represents non-sieving; the 50 mesh corresponds to 270. Mu.m, and the 400 mesh corresponds to 38. Mu.m.
In an embodiment of the present application, the dispersant is at least one of the following materials: polyacrylamide, zinc stearate, stearic acid, paraffin wax, polyethylene wax.
As one embodiment of the application, the addition mass percent of the dispersing agent is controlled to be 0.1-1.0 wt%.
Illustratively, the dispersant is added in a mass percent of 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 1.0wt%, but is not limited to the recited values, as other non-recited values within this range are equally applicable.
In the embodiment of the application, the ball mill can adopt a planetary ball mill, an attritor mill and a horizontal ball mill, the ball milling time can be 0.5-4 h, and the ball milling rotating speed is 50-400 rpm.
Illustratively, the ball milling time is 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The ball milling speeds are exemplified by, but not limited to, 50rpm, 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, and other non-recited values within the range of values are equally applicable.
In the examples of the present application, the ball milling process is performed in an air atmosphere or a nitrogen atmosphere.
In the embodiment of the application, the material of the grinding balls used in the ball milling process can be zirconia, and the diameter of the grinding balls is 1-10 mm, for example, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm or 10mm, but the grinding balls are not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
In the embodiment of the application, in the ball milling process, the mass ratio of the powder to the grinding balls is 1 (1-20), for example, 1:1, 1:2, 1:3, 1:5, 1:10, 1:15 or 1:20, but the application is not limited to the listed values, and other non-listed values in the range of the values are equally applicable, preferably 1 (5-10).
S2: weighing a proper amount of copper oxide powder and flake copper powder according to a set proportion, and placing the mixture in a ball mill for ball milling to obtain mixed copper-based powder.
In an embodiment of the application, the copper oxide powder is selected from at least one of the following materials: copper oxide, cuprous oxide, copper oxide after copper oxidation, and the like.
As one embodiment of the present application, the D50 of the copper oxide powder is 0.5 to 5. Mu.m.
In the embodiment of the application, the ball mill can adopt a planetary ball mill, an attritor mill and a horizontal ball mill, the ball milling time can be 0.5-4 h, and the ball milling rotating speed is 50-400 rpm.
Illustratively, the ball milling time is 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The ball milling speeds are exemplified by, but not limited to, 50rpm, 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, and other non-recited values within the range of values are equally applicable.
In the examples of the present application, the ball milling process is performed in an air atmosphere or a nitrogen atmosphere.
In the embodiment of the application, the material of the grinding balls used in the ball milling process can be zirconia, and the diameter of the grinding balls is 1-10 mm, for example, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm or 10mm, but the grinding balls are not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
In the embodiment of the application, in the ball milling process, the mass ratio of the powder to the grinding balls is 1 (1-20), for example, 1:1, 1:2, 1:3, 1:5, 1:10, 1:15 or 1:20, but the application is not limited to the listed values, and other non-listed values in the range of the values are equally applicable, preferably 1 (5-10).
S3: carrying out thermal reduction treatment on the mixed copper-based powder to obtain a reduction pretreatment substance;
then, the reduction pretreatment is subjected to inheritance oxidation reaction, which can be understood as in-situ oxidation reaction under the condition that the reduction pretreatment is not subjected to further treatment, thus obtaining the flower-shaped porous structure Cu 2 O-CuO is inlaid in copper-based powder with composite morphology on sheet copper powder.
It is worth mentioning that the flower-like porous structure Cu obtained in the embodiment of the application 2 The O-CuO has the advantages of diversified micropore structures, adjustable aperture range and multi-layer pore structures.
In the embodiment of the application, the thermal reduction treatment is performed in a reduction furnace, which may be a pusher furnace, a mesh belt furnace, or an atmosphere protection furnace.
As one embodiment of the application, the temperature of the thermal reduction treatment is 300-900 ℃ and the heat preservation time is 1-8 h.
The temperature of the thermal reduction treatment is, for example, 300 ℃,400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
The heat-retaining time of the thermal reduction treatment is exemplified by 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In an embodiment of the present application, the reducing gas of the thermal reduction treatment is at least one gas selected from the group consisting of: hydrogen, ammonia decomposition gas, carbon monoxide.
As one embodiment of the application, the oxidation temperature of the oxidation reaction is 250-650 ℃ and the heat preservation time is 1-8 h.
The oxidation temperature of the oxidation reaction is, for example, 250 ℃, 300 ℃, 350 ℃,400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
The incubation times for the oxidation reactions are exemplified by, but not limited to, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, and other non-exemplified values within this range are equally applicable.
In an embodiment of the present application, the oxidizing gas is at least one selected from the group consisting of: high purity oxygen, compressed air, industrial oxygen.
In the embodiment of the application, the oxidation reaction can be carried out in an oxidation furnace, and the oxidation furnace can be a muffle furnace, a tube furnace, an atmosphere furnace and a roller kiln.
The copper-based powder with high specific surface composite morphology and the preparation method thereof in the present application will be described in detail by means of specific examples.
The following components are all weight percentages in the present application unless otherwise indicated. By changing the proportion of raw materials and preparation parameters, the copper-based powder with the composite morphology and different specific surface areas can be prepared.
Example 1
Specific surface area of 1.98m 2 The preparation method of the copper-based powder with the composite morphology comprises the following specific steps:
1) Weighing 20g of atomized copper powder, adding polyacrylamide, selecting 5mm zirconia grinding balls with a ball-to-material ratio of 10:1, placing the mixture into a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 4 hours, so as to obtain flaky copper powder, and the morphology is shown in figure 1;
weighing 20g of copper oxide powder and 5g of flaky copper powder prepared in the step 1), selecting 5mm zirconium oxide grinding balls, and ball-to-material ratio of 10:1, placing the balls in a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 30min, so as to obtain mixed copper-based powder;
3) Transferring the mixed copper-based powder obtained in the step 2) into a tube furnace, and performing thermal reduction treatment under the conditions of hydrogen reduction atmosphere, reduction temperature of 350 ℃ and heat preservation time of 2 hours to obtain a reduction pretreatment substance; carrying out inheritance oxidation reaction on the base, carrying out oxidation treatment under air atmosphere, wherein the oxidation temperature is 300 ℃, the heat preservation time is 2 hours, and finally obtaining flower-shaped porous Cu 2 The morphology of the copper-based powder with the composite structure of O-CuO structure embedded on the flaky copper powder is shown in figure 2.
Example 2
Specific surface area of 1.87m 2 The preparation method of the copper-based powder with the composite morphology comprises the following specific steps:
1) Weighing 20g of atomized copper powder, adding polyacrylamide, selecting 5mm zirconia grinding balls with a ball-to-material ratio of 10:1, placing the mixture into a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 4 hours, so as to obtain flaky copper powder, and the morphology is shown in figure 1;
2) Weighing 15g of copper oxide powder and 5g of flaky copper powder prepared in the step 1), selecting 5mm zirconium oxide grinding balls, and ball-to-material ratio of 10:1, placing the balls in a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 30min, so as to obtain mixed copper-based powder;
3) Transferring the mixed copper-based powder obtained in the step 2) into a tube furnace, and performing thermal reduction treatment under the conditions of hydrogen reduction atmosphere, reduction temperature of 350 ℃ and heat preservation time of 2 hours to obtain a reduction pretreatment substance; carrying out inheritance oxidation reaction on the base, carrying out oxidation treatment under air atmosphere, wherein the oxidation temperature is 300 ℃, the heat preservation time is 2 hours, and finally obtaining flower-shaped porous Cu 2 The morphology of the copper-based powder with the composite structure of O-CuO structure embedded on the flaky copper powder is shown in figure 2.
Example 3
Specific surface area of 1.75m 2 The preparation method of the copper-based powder with the composite morphology comprises the following specific steps:
1) Weighing 20g of atomized copper powder, adding polyacrylamide, selecting 5mm zirconia grinding balls with a ball-to-material ratio of 10:1, placing the mixture into a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 2 hours, so as to obtain flaky copper powder, and the morphology is shown in figure 1;
2) Weighing 20g of copper oxide powder and 5g of flaky copper powder prepared in the step 1), selecting 5mm zirconium oxide grinding balls, and ball-to-material ratio of 10:1, placing the balls in a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 30min, so as to obtain mixed copper-based powder;
3) Transferring the mixed copper-based powder obtained in the step 2) into a tube furnace, and performing thermal reduction treatment under the conditions of hydrogen reduction atmosphere, reduction temperature of 350 ℃ and heat preservation time of 2 hours to obtain a reduction pretreatment substance; carrying out inheritance oxidation reaction on the base, carrying out oxidation treatment under air atmosphere, wherein the oxidation temperature is 300 ℃, the heat preservation time is 2 hours, and finally obtaining flower-shaped porous Cu 2 The morphology of the copper-based powder with the composite structure of O-CuO structure embedded on the flaky copper powder is shown in figure 2.
Example 4
Specific surface area of 1.62m 2 The preparation method of the copper-based powder with the composite morphology comprises the following specific steps:
1) Weighing 20g of atomized copper powder, adding polyacrylamide, selecting 5mm zirconia grinding balls with a ball-to-material ratio of 10:1, placing the mixture into a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 2 hours, so as to obtain flaky copper powder, and the morphology is shown in figure 1;
2) Weighing 15g of copper oxide powder and 5g of flaky copper powder prepared in the step 1), selecting 5mm zirconium oxide grinding balls, and ball-to-material ratio of 10:1, placing the balls in a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 30min, so as to obtain mixed copper-based powder;
3) Transferring the mixed copper-based powder obtained in the step 2) into a tube furnace, and performing thermal reduction treatment under the conditions of hydrogen reduction atmosphere, reduction temperature of 350 ℃ and heat preservation time of 2 hours to obtain a reduction pretreatment substance; carrying out inheritance oxidation reaction on the base, carrying out oxidation treatment under air atmosphere, wherein the oxidation temperature is 300 ℃, the heat preservation time is 2 hours, and finally obtaining flower-shaped porous Cu 2 The morphology of the copper-based powder with the composite structure of O-CuO structure embedded on the flaky copper powder is shown in figure 2.
Example 5
Specific surface area of 1.59m 2 The preparation method of the copper-based powder with the composite morphology comprises the following specific steps:
1) Weighing 20g of atomized copper powder, adding polyacrylamide, selecting 5mm zirconia grinding balls with a ball-to-material ratio of 10:1, placing the mixture into a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 2 hours, so as to obtain flaky copper powder, and the morphology is shown in figure 1;
2) Weighing 10g of copper oxide powder and 5g of flaky copper powder prepared in the step 1), selecting 5mm zirconium oxide grinding balls, ball-to-material ratio of 10:1, placing the balls in a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 30min, so as to obtain mixed copper-based powder;
3) Transferring the mixed copper-based powder obtained in the step 2) into a tube furnace, and performing thermal reduction treatment under the conditions of hydrogen reduction atmosphere, reduction temperature of 350 ℃ and heat preservation time of 2 hours to obtain a reduction pretreatment substance; carrying out inheritance oxidation reaction on the base, carrying out oxidation treatment under air atmosphere, wherein the oxidation temperature is 300 ℃, the heat preservation time is 2 hours, and finally obtaining flower-shaped porous Cu 2 The morphology of the copper-based powder with the composite structure of O-CuO structure embedded on the flaky copper powder is shown in figure 2.
Example 6
Specific surface area of 1.29m 2 The preparation method of the copper-based powder with the composite morphology comprises the following specific steps:
1) Weighing 20g of atomized copper powder, adding polyacrylamide, selecting 5mm zirconia grinding balls with a ball-to-material ratio of 10:1, placing the mixture into a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 2 hours, so as to obtain flaky copper powder, and the morphology is shown in figure 1;
2) Weighing 5g of copper oxide powder and 5g of flaky copper powder prepared in the step 1), selecting 5mm zirconium oxide grinding balls, and ball-to-material ratio of 10:1, placing the balls in a planetary ball mill for ball milling under nitrogen atmosphere, wherein the ball milling speed is 300rpm, and the ball milling time is 30min, so as to obtain mixed copper-based powder;
3) Transferring the mixed copper-based powder obtained in the step 2) into a tube furnace, and performing thermal reduction treatment under the conditions of hydrogen reduction atmosphere, reduction temperature of 350 ℃ and heat preservation time of 2 hours to obtain a reduction pretreatment substance; at the position ofOn the basis, carrying out inheritance oxidation reaction, carrying out oxidation treatment under air atmosphere, wherein the oxidation temperature is 300 ℃, the heat preservation time is 2 hours, and finally obtaining flower-shaped porous Cu 2 The morphology of the copper-based powder with the composite structure of O-CuO structure embedded on the flaky copper powder is shown in figure 2.
The catalytic performance of the copper-based powder with high specific surface composite morphology prepared in the examples of the present application will be described below by using a comparative test.
Comparative example 1
The implementation procedure is the same as in example 1, wherein the flake copper powder prepared in step 1) is selected to have a specific surface area of 0.8m 2 /g。
Comparative example 2
Commercial ternary copper catalysts are purchased on the market.
Catalytic performance evaluation:
in a fixed bed with the diameter of 30mm, adding a uniform mixture formed by 10g of silicon powder and 0.5g of copper-based powder prepared in the embodiment, heating to 325 ℃, introducing preheated chloromethane for reaction, wherein the flow rate of the chloromethane is 25mL/min, reacting for 24 hours to obtain a mixed product, and analyzing and calculating by a gas chromatograph to obtain the catalytic performance results (see table 1) such as the selectivity of the dimethyldichlorosilane, the silicon powder conversion rate and the like.
TABLE 1 evaluation results of catalytic Performance
Note that: m1 in Table 1 is monomethyl trichlorosilane; m2 is dimethyldichlorosilane; m3 is trimethyl chlorosilane; M1H is monomethyl hydrogen-containing silane; M2H is dimethyl hydrogen-containing silane; LBR is a low boiling point substance; HBR is a high boiling substance.
The conversion of silicon powder is the ratio of the difference in mass before and after the reaction to the total mass before the reaction, namely (before the reaction of m-after the reaction of m)/100% before the reaction of m, wherein: m is the mass of the contact.
As can be seen from the catalytic performance evaluation results in the table 1 and the specific surface area test results, the copper powder with the high specific surface area composite morphology prepared by the method not only has higher specific surface area, but also has higher silicon powder conversion rate and selectivity of target product dimethyl dichlorosilane in the reaction of synthesizing methyl chlorosilane as a catalyst, and has good catalytic performance.
In the application, the catalytic performance of the prepared copper-based powder with the high specific surface composite morphology has the selectivity of 80-88% in a fixed bed test M2, and the silicon powder conversion rate is 10-50%, and can be kept above 20%.
The foregoing is merely an embodiment of the present application, and a specific structure and characteristics of common knowledge in the art, which are well known in the scheme, are not described herein, and a person of ordinary skill in the art knows all the prior art in the application date or before the priority date, can know all the prior art in the field, and has the capability of applying the conventional experimental means before the date, so that a person of ordinary skill in the art can complete and implement the present embodiment in combination with his own capability in the light of the present application, and some typical known structures or known methods should not be an obstacle for a person of ordinary skill in the art to implement the present application. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the structure of the present application, and these should also be considered as the scope of the present application, which does not affect the effect of the implementation of the present application and the utility of the patent. The protection scope of the present application is subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (10)
1. The copper-based powder with the high specific surface composite morphology is characterized by comprising flake copper powder, flower-shaped porous structure cuprous oxide and cupric oxide, wherein the flower-shaped porous structure cuprous oxide and the cupric oxide are inlaid on the flake copper powder.
2. The copper-based powder with high specific surface area and composite morphology as claimed in claim 1, wherein the specific surface area of the copper-based powder is 0.8-2.0 m 2 /g。
3. A method for preparing the copper-based powder with the high specific surface area and the composite morphology according to any one of claims 1 to 2, which comprises the following steps:
s1: weighing a proper amount of copper powder, adding a dispersing agent, and placing the mixture in a ball mill for ball milling to obtain flaky copper powder;
s2: weighing a proper amount of copper oxide powder and the flaky copper powder, and placing the copper oxide powder and the flaky copper powder in a ball mill for ball milling to obtain mixed copper-based powder;
s3: sequentially carrying out thermal reduction treatment and oxidation reaction on the mixed copper-based powder to obtain flower-shaped porous Cu 2 And the O-CuO structure is inlaid in the copper-based powder with the composite morphology on the flaky copper powder.
4. The method for producing a copper-based powder having a high specific surface area composite morphology according to claim 3, wherein in step S1,
the copper powder includes, but is not limited to, electrolytic copper powder, water atomized copper powder, ultrafine copper powder, low apparent copper powder;
preferably, the purity of the copper powder is more than or equal to 97 percent, and the granularity range is-50 to +400 meshes.
Preferably, the dispersing agent is at least one of polyacrylamide, zinc stearate, stearic acid, paraffin wax and polyethylene wax, and the adding mass percentage is 0.1-1.0wt%.
5. The method for producing a copper-based powder having a high specific surface area composite morphology according to claim 3, wherein in step S2,
the copper oxide powder includes but is not limited to copper oxide and cuprous oxide powder, and D50 is 0.5-5 μm.
6. The method for preparing copper-based powder with a high specific surface area and composite morphology according to claim 3, wherein in the step S1 and the step S2,
the ball milling time is 0.5-4 h, and the ball milling rotating speed is 50-400 rpm;
preferably, the ball milling process is performed in an air atmosphere or a nitrogen atmosphere.
7. The method for preparing copper-based powder with a high specific surface area and composite morphology according to claim 3, wherein in the step S1 and the step S2,
in the ball milling process, the mass ratio of the powder to the grinding balls is 1 (1-20);
preferably, the grinding ball adopted in the ball milling process is made of zirconia, and the diameter of the grinding ball is 1-10 mm.
8. The method for producing a copper-based powder having a high specific surface area composite morphology according to claim 3, wherein in step S3,
the temperature of the thermal reduction treatment is 300-900 ℃, and the heat preservation time is 1-8 h;
preferably, the reducing gas is at least one of hydrogen, ammonia decomposition gas, and carbon monoxide.
9. The method for producing a copper-based powder having a high specific surface area composite morphology according to claim 3, wherein in step S3,
the oxidation temperature of the oxidation reaction is 250-650 ℃, and the heat preservation time is 1-8 h;
preferably, the oxidizing gas is at least one of high-purity oxygen, compressed air, and industrial oxygen.
10. An application of the copper-based powder with high specific surface composite morphology as a catalyst for synthesizing dimethyl dichlorosilane, which is characterized in that the selectivity of the catalytic performance from a fixed bed test M2 is 80-88%, and the silicon powder conversion rate is 10-50%;
the conversion rate of the silicon powder is preferably 20-50%.
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