CN114392742A - Copper oxide powder catalyst and application thereof - Google Patents
Copper oxide powder catalyst and application thereof Download PDFInfo
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- CN114392742A CN114392742A CN202210107123.XA CN202210107123A CN114392742A CN 114392742 A CN114392742 A CN 114392742A CN 202210107123 A CN202210107123 A CN 202210107123A CN 114392742 A CN114392742 A CN 114392742A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000005751 Copper oxide Substances 0.000 claims abstract description 45
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 45
- 238000000498 ball milling Methods 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 238000002360 preparation method Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 239000011863 silicon-based powder Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000005049 silicon tetrachloride Substances 0.000 description 4
- 229910003822 SiHCl3 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003921 particle size analysis Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000007038 hydrochlorination reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 150000004754 hydrosilicons Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
- C01B33/10742—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material
- C01B33/10757—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane
- C01B33/10763—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane from silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Engineering & Computer Science (AREA)
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Abstract
The invention provides a copper oxide powder catalyst and application thereof, wherein the powder catalyst only contains copper oxide and is prepared by a ball milling method. The powder catalyst has excellent selectivity in the synthesis of trichlorosilane by a hydrosilylation method, can directly use the original non-catalytic production device, does not need to change the main equipment, and has the characteristics of strong operation elasticity, low reaction temperature, small equipment corrosion and high productivity; the preparation method has simple process and low cost, and is easy for industrial implementation.
Description
Technical Field
The invention belongs to the field of catalysts, relates to a copper oxide catalyst, and particularly relates to a copper oxide powder catalyst and application thereof.
Background
The polysilicon material is an important intermediate product in the silicon product industry chain, is the most main and basic functional material in the semiconductor industry, the electronic information industry and the solar photovoltaic cell industry, and is trichlorosilane (SiHCl)3) Is the most important raw material for manufacturing polycrystalline silicon, and in addition, is an important intermediate for producing silane coupling agents and other organosilicon products. In recent years, with the development of economy in China, particularly the rapid development of semiconductor industry, solar cells and organic silicon industry, the demand for trichlorosilane is also rapidly increased. At present, the industry mainly adopts the non-catalytic reaction of the silicon hydrochlorination method to produce the trichloro chlorideThe hydrosilicon, namely, the metal silicon powder (also called metallurgical silicon powder (Si)) and HCl gas are used as raw materials, and the synthesis is carried out by carrying out gas-solid phase reaction in a fluidized bed reactor under the conditions of 350-400 ℃ and 0.1-0.2 MPa, wherein the reaction process is shown as the equation:
2Si+7HCl＝SiHCl3+SiCl4+3H2
because the existing production process does not use a catalyst, the selectivity of the product is uncontrollable and completely depends on the property of the raw material silicon powder, so that the silicon tetrachloride (SiCl) as a byproduct is generated4) The content is too high, the selectivity of trichlorosilane is generally about 80-85% (CN101665254A and CN101279734B), and pressure is brought to the subsequent rectification separation process. In addition, the reaction temperature is high (350-400 ℃), the raw material HCl gas has great corrosion to equipment, and internal components of the reactor need to be frequently replaced, so that the equipment maintenance cost is high. CN106861693B and CN110711581A disclose that copper-based metal oxide mesomorphic materials can be used as catalysts for silicon hydrochlorination, and although the catalysts of the type improve the selectivity of trichlorosilane and the conversion rate of silicon, the preparation cost is high, the preparation process is complex, and the conditions for large-scale production and use are not met. The literature (Chemical Conmunicaiton,1998,1275-1276) reports that commercial cuprous chloride can be used as a catalyst for the reaction, and higher selectivity of trichlorosilane can be obtained, but the unique preparation process of the catalyst, including dispersion of the carrier, control of the size of particles, and the like, is not involved, and the catalyst is not beneficial to industrial application. CN106378133A discloses that cuprous chloride and cupric chloride can be used as catalysts to prepare trichlorosilane after being mixed with a cocatalyst, but various elements in the cocatalyst can increase the load of rectification separation and improve the separation cost of reaction products. Therefore, on the premise of not changing the original production process route and equipment of the non-catalytic silicon-hydrogen chlorination method, the catalyst with low development cost and simple preparation can be used for improving the selectivity of trichlorosilane and the conversion rate of silicon, reducing the reaction temperature, reducing the corrosion of equipment and reducing the production cost, and has important significance to trichlorosilane production enterprises undoubtedly.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a copper oxide powder catalyst and an application thereof, wherein the copper oxide powder catalyst has excellent selectivity in trichlorosilane synthesis by a hydrosilylation method, can directly use the original non-catalytic production device, does not need to change the main equipment, and has the characteristics of strong operation elasticity, low reaction temperature, small equipment corrosion and high productivity; the preparation method has simple process and low cost, and is easy for industrial implementation.
In order to achieve the technical effect, the invention adopts the following technical scheme:
an object of the present invention is to provide a copper oxide powder catalyst containing only copper oxide, which is prepared by a ball milling method.
The powder catalyst only contains copper oxide, the raw material is single, the components are easy to control, the particle size of the copper oxide can be greatly reduced in the ball milling process due to the brittleness of the copper oxide, the particle size distribution is uniform, the better fluidization state can be kept in an industrial fluidized bed reactor, and meanwhile, the high-energy ball milling reduces the grain size, so that a large number of defects and oxygen vacancies are generated on the surface of the copper oxide, abundant active sites are formed, the catalysis is promoted, and the selectivity of a reaction main product and the conversion rate of silicon powder are improved.
In a preferred embodiment of the present invention, the particle size distribution of the powder catalyst is in the range of 0.4 to 4.0. mu.m, such as 0.5. mu.m, 1.0. mu.m, 1.5. mu.m, 2.0. mu.m, 2.5. mu.m, 3.0. mu.m, or 3.5. mu.m, but the particle size distribution is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable, and preferably 0.6 to 3.0. mu.m.
As a preferred embodiment of the present invention, the copper oxide includes any one or a combination of at least two of copper oxide obtained by oxidizing elemental copper and/or lower copper, commercial copper oxide powder, or copper oxide obtained by calcining copper salt, and the combination is typically but not limited to: the combination of copper oxide obtained by oxidizing elemental copper and/or low-valent copper and commercial copper oxide powder, the combination of commercial copper oxide powder and copper oxide obtained by calcining copper salt, the combination of copper oxide obtained by calcining copper salt and copper oxide obtained by oxidizing elemental copper and/or low-valent copper, or the combination of elemental copper and/or low-valent copper and copper oxide obtained by oxidizing commercial copper oxide powder and copper oxide obtained by calcining copper salt, and the like.
As a preferable technical scheme of the invention, the ball milling method is dry stirring ball milling.
In the present invention, the ball milling is performed in a dry type agitator ball mill, and the method of performing ball milling using the dry type agitator ball mill is well known in the art, and specific conditions may be selected according to actual specifications of materials and products, and are not specifically limited herein.
As a preferred technical scheme of the invention, the material of the grinding beads used in the ball milling method comprises zirconium oxide and/or stainless steel, preferably stainless steel,
in a preferred embodiment of the present invention, the diameter of the beads is 2 to 10mm, such as 3mm, 4mm, 5mm, 6mm, 7mm, 8mm or 9mm, but the beads are not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, and preferably 3 to 8 mm.
In a preferred embodiment of the present invention, the mass ratio of the mixed material to the beads is 1 (1 to 7), for example, 1:2, 1:3, 1:4, 1:5, or 1:6, but the ratio is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, and 1 (3 to 5) is preferable.
In a preferred embodiment of the present invention, the rotation speed of the ball milling method is 100 to 500rpm, preferably 200 to 400rpm, but the rotation speed is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the ball milling time is 0.5 to 4 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, or 3.5 hours, but the time is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable, preferably 1 to 2 hours.
The second purpose of the invention is to provide application of the powder catalyst provided by the first purpose, and the catalyst is used for selectively synthesizing trichlorosilane by a silicon-hydrogen chlorination method.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention provides a copper oxide powder catalyst which is uniform in particle size distribution, rich in defect sites and oxygen vacancies, rich in active sites, and capable of accelerating the reaction process and simultaneously showing excellent selectivity to the synthesis of a target product;
(2) the invention provides a copper oxide powder catalyst, which can directly use the original non-catalytic production device, has no need of changing the main equipment, and has the characteristics of strong operation elasticity, low reaction temperature, small equipment corrosion and high productivity;
(3) the invention provides a copper oxide powder catalyst, and the preparation method of the powder catalyst has the advantages of simple process, low cost and easy industrial implementation.
Drawings
FIG. 1 is an XRD pattern of a copper oxide powder catalyst prepared in example 1 of the present invention and a copper oxide raw material used therefor;
FIG. 2 is a particle size distribution diagram of a copper oxide powder catalyst prepared in example 1 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
carrying out dry ball milling on 50kg of commercial copper oxide and 150kg of stainless steel grinding balls with the diameter of 5mm together, wherein the stirring rotation speed is 300rpm, and the copper oxide powder catalyst is obtained after ball milling for 2 hours, and the particle size distribution range of the catalyst is 0.6-2.5 microns.
Performing SEM analysis and particle size analysis on the prepared copper oxide composite catalyst, which specifically comprises the following steps:
(1) XRD test analysis: the XRD test was carried out on the commercial copper oxide raw material prepared as described above and the copper oxide powder catalyst obtained in example 1 using an X' PertPRO MPD type multifunctional X-ray diffractometer manufactured by Panalytical corporation of the netherlands (panarec), and the XRD spectrum is shown in fig. 1, and it can be seen from fig. 1 that the shoulder consisting of 35.5 ° 2 θ and 38.7 ° 2 θ is a characteristic peak of CuO, and the copper oxide powder catalyst of example 1 obtained by subjecting the copper oxide raw material to ball milling treatment has a significantly lowered peak intensity, an increased half-peak width, and a reduced grain size from 40.8nm to 18.0nm (calculated using the scherrer equation), thereby generating more defect sites and oxygen vacancies at the site of grain breakage.
(2) And (3) particle size analysis: particle size analysis is carried out by using a Dandongbertt BT-9300Z laser particle size distribution instrument, and as can be seen from figure 2, the particle size range of the prepared copper oxide composite catalyst is 0.6-2.5 mu m.
Example 2
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
carrying out dry ball milling on 50kg of commercial copper oxide and 150kg of stainless steel grinding balls with the diameter of 2mm together, wherein the stirring rotation speed is 300rpm, and the copper oxide powder catalyst is obtained after ball milling for 2 hours, and the particle size distribution range of the catalyst is 0.6-2.5 microns.
Example 3
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
carrying out dry ball milling on 50kg of commercial copper oxide and 150kg of stainless steel grinding balls with the diameter of 10mm together, wherein the stirring rotation speed is 300rpm, and the copper oxide powder catalyst is obtained after ball milling for 2 hours, and the particle size distribution range of the catalyst is 0.8-4.0 mu m.
Example 4
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
carrying out dry ball milling on 50kg of commercial copper oxide and 50kg of stainless steel grinding balls with the diameter of 5mm together, wherein the stirring rotation speed is 300rpm, and the copper oxide powder catalyst is obtained after ball milling for 4 hours, and the particle size distribution range of the catalyst is 0.7-3.0 mu m.
Example 5
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
50kg of copper oxide obtained by calcining basic copper carbonate and 350kg of stainless steel grinding balls with the diameter of 5mm are subjected to dry ball milling together, the stirring speed is 300rpm, and the copper oxide powder catalyst is obtained after ball milling for 0.5h, wherein the particle size distribution range of the catalyst is 0.7-2.3 mu m.
Example 6
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
50kg of copper oxide obtained by calcining and oxidizing industrial atomized copper powder and 150kg of stainless steel grinding balls with the diameter of 5mm are subjected to dry ball milling together, the stirring speed is 100rpm, and the copper oxide powder catalyst is obtained after ball milling for 4 hours, wherein the particle size distribution range of the catalyst is 0.8-3.9 microns.
Example 7
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
carrying out dry ball milling on 50kg of commercial copper oxide and 150kg of stainless steel grinding balls with the diameter of 5mm together, wherein the stirring rotation speed is 400rpm, and the copper oxide powder catalyst is obtained after ball milling for 1h, and the particle size distribution range of the catalyst is 0.8-2.5 mu m.
Example 8
The embodiment provides a preparation method of a copper oxide composite catalyst, which comprises the following steps:
carrying out dry ball milling on 50kg of commercial copper oxide and 250kg of stainless steel grinding balls with the diameter of 8mm together, wherein the stirring rotation speed is 500rpm, and the copper oxide powder catalyst is obtained after ball milling for 1h, and the particle size distribution range of the catalyst is 0.8-3.0 mu m.
Comparative example 1
This comparative example prepared the same commercial copper oxide as in example 1 into a powder catalyst having a particle size distribution in the range of 0.6 to 2.5 μm using a jet mill.
Comparative example 2
This comparative example prepared the same commercial copper oxide as in example 1 into a powder catalyst having a particle size distribution ranging from 7.6 to 20.5 μm using a centrifugal roll mill.
Comparative example 3
This comparative example prepared the same commercial copper oxide as in example 1 using a pendulum hammer mill into a powder catalyst having a particle size distribution ranging from 5.6 to 26.5 μm.
In order to examine the catalytic performance of the copper chloride catalyst provided by the invention in a hydrosilation method, the catalytic performance tests of examples 1-8, comparative examples 1-3, commercial copper oxide and the condition without any catalyst are carried out, and specifically comprise the following steps: a micro fixed bed device is adopted for carrying out catalytic performance test, 10g of industrial raw material silicon powder and 0.05g of catalyst are weighed, the mixture of the two substances is loaded into a reactor, nitrogen is introduced to purge a reaction system for 1h, then the temperature is raised to a set reaction temperature, HCl gas is introduced, the flow is 40mL/min, the reaction pressure is normal pressure, and the reaction time is controlled to be 6 h. Condensing a reaction product by using a condensing tube, collecting the reaction product by using toluene, and exhausting the residual tail gas after absorbing the residual tail gas by using an alkali liquor; the collected mixture was quantitated by capillary gas chromatography (Agilent7890A, KB-210 column, TCD detector) after volume measurement. The conversion rate of the silicon powder is obtained by dividing the mass difference of the silicon powder before and after the reaction by the mass of the silicon powder before the reaction. The catalytic test results are shown in table 1.
TABLE 1
Description of Table 1:
(1) product selectivity: the ratio of the mass of the target product to the sum of the masses of all reaction products (calculated by the sum of trichlorosilane and silicon tetrachloride) is obtained by chromatographic decomposition;
(2) the Si conversion calculation formula is as follows:
(3)SiHCl3The yield calculation method comprises the following steps: SiHCl3The selectivity is multiplied by the Si conversion rate to obtain;
as can be seen from the performance evaluation results in Table 1, under the same reaction temperature, the trichlorosilane selectivity, the silicon powder conversion rate and the trichlorosilane yield of the copper oxide powder catalyst obtained in examples 1 to 8 are obviously higher than those of the powder catalyst obtained by an air flow pulverizer (comparative example 1), the powder catalyst obtained by a centrifugal roller mill (comparative example 2), the powder catalyst obtained by a swinging hammer mill (comparative example 3), the copper oxide raw material and the reaction result without the catalyst, and meanwhile, the selectivity of the silicon tetrachloride serving as a byproduct is greatly reduced, which indicates that the prepared catalyst has very good catalytic performance; especially, at 275 ℃, no catalyst is added, and no reaction occurs on silicon powder, so that the copper oxide powder catalyst obtained in examples 1 to 8 still has good trichlorosilane selectivity and silicon powder conversion rate, which indicates that the reaction temperature can be greatly reduced by using the copper oxide powder catalyst. Therefore, the method has the advantages of outstanding innovation, simple production process, no pollution and easy industrialization and practicability.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A copper oxide powder catalyst, characterized in that the powder catalyst comprises only copper oxide and is prepared by a ball milling process.
2. The powder catalyst according to claim 1, wherein the particle size distribution of the powder catalyst is in the range of 0.4 to 4.0 μm, preferably 0.6 to 3.0 μm.
3. A powder catalyst as claimed in claim 1 or 2, wherein the copper oxide comprises any one of, or a combination of at least two of, elemental copper and/or copper suboxides obtained by oxidation of copper, commercial copper oxide powders, or copper oxides obtained by calcination of copper salts.
4. A powder catalyst according to any one of claims 1 to 3, wherein the ball milling process is dry stirred ball milling.
5. A powder catalyst according to any one of claims 1 to 4, wherein the material of the beads used in the ball milling process comprises zirconia and/or stainless steel, preferably stainless steel.
6. A powder catalyst according to claim 5, wherein the beads have a diameter of 2 to 10mm, preferably 3 to 8 mm.
7. The powder catalyst of claim 5, wherein the mass ratio of the mixed material to the grinding beads is 1 (1-7), preferably 1 (3-5).
8. A powder catalyst according to any of claims 1 to 7, wherein the rotation speed of the ball milling process is in the range of 100 to 500rpm, preferably 200 to 400 rpm.
9. A powder catalyst according to any of claims 1 to 8, wherein the ball milling is carried out for a period of 0.5 to 4 hours, preferably 1 to 2 hours.
10. Use of the powder catalyst according to any one of claims 1 to 8 for the selective synthesis of trichlorosilane by the hydrosilylation process.
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| CA1240306A (en) * | 1985-05-07 | 1988-08-09 | Don H. Hashiguchi | Halosilane catalyst and process for making same |
| JP2003275592A (en) * | 2002-03-19 | 2003-09-30 | Osaka Gas Co Ltd | Carbon monoxide conversion catalyst |
| CN104941653A (en) * | 2015-05-29 | 2015-09-30 | 中国科学院过程工程研究所 | Copper-tin composite oxide catalyst, and preparation method and use thereof |
| CN106378133A (en) * | 2016-10-24 | 2017-02-08 | 中国科学院过程工程研究所 | Catalyst for producing trichlorosilane with silicon-hydrogen chlorination process, preparation method of catalyst and method for catalytically producing trichlorosilane |
| CN106861693A (en) * | 2017-04-07 | 2017-06-20 | 中国科学院过程工程研究所 | A kind of copper based composite metal oxidate mesomorphic material and its production and use |
| CN113634259A (en) * | 2021-08-16 | 2021-11-12 | 中国科学院过程工程研究所 | Copper oxide composite catalyst and preparation method and application thereof |
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| CA1240306A (en) * | 1985-05-07 | 1988-08-09 | Don H. Hashiguchi | Halosilane catalyst and process for making same |
| JP2003275592A (en) * | 2002-03-19 | 2003-09-30 | Osaka Gas Co Ltd | Carbon monoxide conversion catalyst |
| CN104941653A (en) * | 2015-05-29 | 2015-09-30 | 中国科学院过程工程研究所 | Copper-tin composite oxide catalyst, and preparation method and use thereof |
| CN106378133A (en) * | 2016-10-24 | 2017-02-08 | 中国科学院过程工程研究所 | Catalyst for producing trichlorosilane with silicon-hydrogen chlorination process, preparation method of catalyst and method for catalytically producing trichlorosilane |
| CN106861693A (en) * | 2017-04-07 | 2017-06-20 | 中国科学院过程工程研究所 | A kind of copper based composite metal oxidate mesomorphic material and its production and use |
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