CN113842931A - Composite catalyst for synthesizing organic silicon monomer and preparation method and application thereof - Google Patents
Composite catalyst for synthesizing organic silicon monomer and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000000178 monomer Substances 0.000 title claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 9
- 239000010703 silicon Substances 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000013543 active substance Substances 0.000 claims abstract description 3
- 239000008247 solid mixture Substances 0.000 claims description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000000498 ball milling Methods 0.000 claims description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 33
- 229910052718 tin Inorganic materials 0.000 claims description 33
- 238000000227 grinding Methods 0.000 claims description 30
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 23
- 239000010935 stainless steel Substances 0.000 claims description 22
- 229910001220 stainless steel Inorganic materials 0.000 claims description 22
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 229940116318 copper carbonate Drugs 0.000 claims description 20
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 239000011787 zinc oxide Substances 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 11
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 9
- 239000005751 Copper oxide Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 3
- 238000009837 dry grinding Methods 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 239000006229 carbon black Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052681 coesite Inorganic materials 0.000 description 14
- 229910052906 cristobalite Inorganic materials 0.000 description 14
- 229910052682 stishovite Inorganic materials 0.000 description 14
- 229910052905 tridymite Inorganic materials 0.000 description 14
- 239000011863 silicon-based powder Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- SOYFYCJCFAHQDV-UHFFFAOYSA-J copper zinc dicarbonate Chemical compound [Cu++].[Zn++].[O-]C([O-])=O.[O-]C([O-])=O SOYFYCJCFAHQDV-UHFFFAOYSA-J 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 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
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1813—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with germanium, tin or lead
-
- 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
-
- 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
- B01J37/04—Mixing
-
- 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
- B01J37/08—Heat treatment
-
- 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
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a composite catalyst for synthesizing an organic silicon monomer, which comprises a carrier, wherein the carrier is loaded with a copper-based active substance and an active auxiliary agent, and the active auxiliary agent comprises Zn element, Sn element and P element. The composite catalyst solves the problems of complex preparation method, high cost, low activity and the like of the catalyst in the prior art, can replace the traditional catalyst, and realizes more efficient catalytic action in the synthetic reaction of the organic silicon monomer.
Description
Technical Field
The invention belongs to the field of catalysts, relates to a composite catalyst, and particularly relates to a composite catalyst synthesized by organic silicon monomers, and a preparation method and application thereof.
Background
Dimethyldichlorosilane is the most important one of organosilicon monomers, and the dosage of the dimethyldichlorosilane accounts for 90 percent of the yield of the organosilicon monomers, so the dimethyldichlorosilane is widely used in the industries of electronics, medicines, automobiles, buildings and the like. By the end of 2020, the total production capacity of 11 silicone monomer production enterprises in China can reach about 370 ten thousand tons/year, and the market demand of silicone shows a rapidly increasing situation. In recent years, efforts have been made to develop more efficient and lower cost catalysts for dimethyldichlorosilane synthesis, and therefore, control of the composition of the catalyst and selection of the preparation method are key to improving the selectivity and silicon powder conversion of dimethyldichlorosilane (M2).
The Rochow direct synthesis is the most economical route to M2 and has been used to date. The synthesis of M2 did not leave the catalyst, whereas copper-based catalysts proved to be the most effective catalysts. Currently, the most used copper-based catalysts for silicone monomer synthesis include copper and copper oxides, ternary copper complexes, CuCl, and the like. The addition of a small proportion of substances, which are promoters, to the catalyst, which are not or only little reactive to the reaction themselves, but which can modify certain properties of the catalyst, such as surface composition, chemical structure, etc., leads to improved activity, selectivity and stability of the catalyst. The most commonly used promoters in the Rochow reaction are the simple substances of Zn, Sn, P and their compounds. The SCM company (US7323583B2, CN1812834A) teaches that dispersing a zinc promoter in copper oxide allows the copper oxide and zinc oxide to come into intimate contact and combine to form agglomerated particles and increases the selectivity of M2. The dow corning company (US4602101) indicated that the addition of phosphorus element can increase the M2 selectivity but decrease the Si conversion, but the specific mechanism for P is not clear. CN 106423175A discloses a method for preparing a copper-based catalyst for catalyzing carbon dioxide hydrogenation reduction by adopting a wet ball milling method, wherein the method adopts acetone as a solvent and has certain toxicity. CN105664952A adopts a carbon black template to dip copper ions and zinc ions from the solution, and then the copper oxide and zinc oxide composite catalyst is prepared by high-temperature calcination for Rochow reaction, and the method can generate waste water and greenhouse gas carbon dioxide, and is not beneficial to environmental protection. CN101143324A takes silicon dioxide as a carrier, copper oxide as a main active component and alkali metal or alkaline earth metal as an auxiliary agent to prepare the catalyst for preparing 2-methylfuran by furfural gas phase hydrogenation by an impregnation method, which shows that the carrier silicon dioxide has good dispersion effect. Zou et al (RSC Advanc, 2015, 5, 63355) foundSnO2Compared with an additive mode, the rod-shaped compound of CuO can enhance the selectivity of catalyzing M2 and the conversion rate of Si, but the process uses a surfactant, a large amount of ethanol, sodium hydroxide and other reagents through a hydrothermal method, so that the preparation period is long, the operation is complex, the process is not environment-friendly, waste alkali water is discharged, the environment is polluted, and the prepared catalyst has low yield and is not beneficial to application. At present, the research on the synergistic action mode between the main catalyst and the cocatalyst is gradually concerned, and the application of the cocatalyst to the supported catalyst for catalyzing the reaction of Rochow has not been reported.
In the scheme, the preparation technology of the copper-based catalyst mostly stays in the non-supported catalyst, and has the defects of long process flow, difficult operation, poor controllability of components and granularity, environmental pollution, higher production cost and the like. In the current stage of research, high cost, low selectivity and low silicon powder conversion rate of the copper-based catalyst are important factors for restricting the industrialization of the synthesis of the organic silicon monomer.
Disclosure of Invention
The composite catalyst solves the problems of complex preparation method, high cost, low activity and the like of the catalyst in the prior art, can replace the traditional catalyst, and realizes more efficient catalytic action in the organosilicon monomer synthesis reaction.
In order to achieve the technical effect, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a composite catalyst for synthesizing an organic silicon monomer, which is characterized by comprising a carrier, wherein the carrier is loaded with a copper-based active substance and a coagent, and the coagent comprises Zn element, Sn element and P element.
As a preferable technical scheme of the invention, the copper-based active component is copper oxide.
Preferably, the copper-based active component content in the composite catalyst is 20 to 60 wt%, such as 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt% or 55 wt%, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the content of Zn element in the composite catalyst is 0.005 to 1 wt%, for example, 0.01 wt%, 0.02 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, or 0.8 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable.
Preferably, the content of Sn element in the composite catalyst is 0.005 to 0.05 wt%, such as 0.01 wt%, 0.02 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, or 0.4 wt%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the content of the P element in the composite catalyst is 0.005 to 0.05 wt%, such as 0.01 wt%, 0.02 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, or 0.4 wt%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the carrier is silica.
Preferably, the particle size of the composite catalyst is 0.3 to 10 μm, such as 0.5 μm, 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, or 9 μm, but is not limited to the recited values, and other values not recited in this range are also applicable, preferably 1.0 to 5.0 μm.
The second purpose of the present invention is to provide a method for preparing the composite catalyst, which comprises the following steps:
(1) mixing a copper source, a zinc source and a carrier, and crushing to obtain a first solid mixture;
(2) calcining the first solid mixture crystal form to obtain a second solid mixture;
(3) and mixing the second solid mixture with a tin source and a phosphorus source, and crushing to obtain the composite catalyst.
In the invention, the copper-based active component and the active assistant are loaded on the surface of the solid carrier by dry grinding, and the silicon dioxide is used as a common carrier, has a larger specific surface area and plays a good role in dispersion; the active components are dispersed in the calcining and reacting processes, and the activity of the catalyst can be obviously improved.
In a preferred embodiment of the present invention, the copper source in step (1) includes basic copper carbonate.
Preferably, the zinc source in step (1) comprises any one of zinc oxide, elemental zinc powder, copper-zinc alloy, basic zinc carbonate or zinc acetate, or a combination of at least two of the following, typical but non-limiting examples being: the zinc carbonate is preferably zinc oxide and/or basic zinc carbonate, and the like.
In a preferred embodiment of the present invention, the crushing in step (1) is performed by ball milling.
Preferably, the ball-milled grinding beads are any one or a combination of at least two of zirconia balls, stainless steel balls, tungsten carbide balls and corundum balls, and are preferably stainless steel balls.
Preferably, the beads have a diameter of 1 to 10mm, such as 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm or 9mm, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
The mass ratio of the grinding beads to the mixed powder is preferably (1 to 10):1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, or 9:1, but the ratio is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are also applicable, and preferably (1 to 5): 1.
Preferably, the stirring speed of the ball mill is 50 to 500r/min, such as 100r/min, 150r/min, 200r/min, 250r/min, 300r/min, 350r/min, 400r/min or 450r/min, but not limited to the listed values, and other non-listed values within the range of the values are also applicable, preferably 100 to 400 r/min.
Preferably, the ball milling time is 0.5 to 5 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours or 4.5 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 1 to 3 hours.
Preferably, the ball milling is dry milling.
Preferably, the atmosphere of the ball mill is air.
In the present invention, the crushing treatment in step (1) may be carried out in a stirred ball mill.
As a preferable embodiment of the present invention, the calcination treatment in the step (2) is performed in an air atmosphere.
Preferably, the temperature of the calcination in step (2) is 300 to 800 ℃, such as 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ or 750 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 400 to 600 ℃.
Preferably, the calcination time in step (2) is 0.5 to 10 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours or 9 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 1 to 4 hours.
In the present invention, the calcination treatment may be carried out in any equipment selected from a tube furnace, a box-type atmosphere furnace, a converter, and a fluidized bed.
As a preferable technical scheme of the invention, the tin source in the step (3) comprises elemental tin powder and/or copper-tin alloy.
Preferably, the phosphorus source in step (3) is CuP8。
Preferably, the crushing treatment in the step (3) is ball milling.
In the present invention, the ball milling conditions in step (3), such as the kind, mixing ratio, rotation speed, time, and atmosphere of the milling balls, are the same as the ball milling conditions defined in step (1).
The third purpose of the invention is to provide an application of the composite catalyst, which is applied to organosilicon monomer synthesis reaction.
Preferably, the composite catalyst is applied to the selective synthesis of dimethyldichlorosilane.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the preparation method of the composite catalyst provided by the invention has the advantages of simple process, low cost, easy control of each component, environmental friendliness and suitability for industrial large-scale production;
(2) the composite catalyst provided by the invention is applied to the synthesis reaction of organic silicon monomers, and compared with a commercial catalyst, the composite catalyst has higher selectivity of dimethyldichlorosilane and higher silicon powder conversion rate.
Drawings
FIG. 1 is an XRD pattern of the catalyst prepared in example 1;
FIG. 2 is a particle size distribution plot for the catalyst prepared in example 1;
FIG. 3 is a graphical comparison of dimethyldichlorosilane selectivity for fixed bed stable catalytic reactions of example 1 and comparative example 4.
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
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) mixing 55.28g of basic copper carbonate, 40g of white carbon black and 1.0g of zinc oxide, and carrying out ball milling on the mixture and 482g of stainless steel grinding balls together, wherein the ball milling time is 2 hours, and the rotating speed is 400r/min, so as to obtain a first solid mixture;
(2) calcining the first solid mixture at 400 ℃ for 1h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.015g of elemental tin and 0.031g of CuP8And 250g of stainless steel grinding balls for mixing and ball-millingThe ball milling time is 2h, and the rotating speed is 400r/min, so as to obtain the composite catalyst. The composite catalyst comprises 49.5 percent of CuO, 1 percent of Zn, 0.03 percent of Sn, 0.005 percent of P and the balance of SiO2The particle size is 1.0 to 10 μm.
(A) The XRD pattern of the organosilicon monomer synthesis reaction catalyst is shown in figure 1, the XRD test is carried out on an X' Pert PRO MPD type multifunctional X-ray diffractometer produced by Panalytical corporation (Pa Naceae), and as can be seen from figure 1, a broadened characteristic diffraction peak is at 23 degrees 2 theta, which is amorphous SiO2The characteristic peak of (2 theta) is 35.5 degrees, the shoulder peak of (2 theta) is 38.7 degrees and the shoulder peak of (2 theta) is 48.8 degrees is the characteristic peak of CuO, and because the loading amounts of ZnO, Sn and P are small (less than or equal to 5 percent), the instrument detection limit is exceeded, and the characteristic diffraction peak is not detected.
(B) The particle size distribution diagram of the organosilicon monomer synthesis reaction catalyst is shown in fig. 2, the sample particle size distribution analysis is carried out on a BT-9300Z laser particle sizer manufactured by dandong particle sizer limited, and as can be seen from fig. 2, the particle size of the prepared organosilicon monomer synthesis reaction catalyst is 1-10 μm.
Example 2
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) mixing 55.28g of basic copper carbonate, 40g of white carbon black and 1.0g of basic copper zinc carbonate, and ball-milling together with 96g of zirconia grinding balls for 2 hours at the rotating speed of 400r/min to obtain a first solid mixture;
(2) calcining the first solid mixture at 400 ℃ for 1h to obtain a second solid mixture;
(3) 50g of the second solid mixture were mixed with 0.0025g of elemental tin and 0.030g of CuP8And 50g of zirconia grinding balls are mixed and ball-milled for 2 hours at the rotating speed of 400r/min to obtain the composite catalyst. The composite catalyst comprises 50 percent of CuO, 0.005 percent of Zn, 0.005 percent of Sn, 0.005 percent of P and the balance of SiO2The particle size is 1.0 to 10 μm.
Example 3
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) 66.33g of basic copper carbonate, 32g of white carbon black and 0.01g of basic copper zinc carbonate are mixed and are ball-milled together with 983g of zirconia grinding balls, the ball-milling time is 0.5h, and the rotating speed is 500r/min, so that a first solid mixture is obtained;
(2) calcining the first solid mixture at 400 ℃ for 1h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.015g of elemental tin and 0.31g of CuP8And 500g of zirconia grinding balls are mixed and ball-milled for 0.5h at the rotating speed of 500r/min to obtain the composite catalyst. The composite catalyst comprises, by mass, CuO 60%, Zn 0.005%, Sn 0.03%, P0.05%, and the balance of SiO2The particle size is 2.0 to 10 μm.
Example 4
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) mixing 22.11g of basic copper carbonate, 64g of white carbon black and 0.08g of zinc powder, and carrying out ball milling on the mixture and 256g of zirconia grinding balls together, wherein the ball milling time is 2 hours, and the rotating speed is 400r/min, so as to obtain a first solid mixture;
(2) calcining the first solid mixture at 400 ℃ for 8h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.015g of elemental tin and 0.31g of CuP8And 150g of zirconia grinding balls are mixed and ball-milled for 2 hours at the rotating speed of 400r/min to obtain the composite catalyst. The composite catalyst comprises 20 mass percent of CuO, 0.1 mass percent of Zn, 0.03 mass percent of Sn and 0.005 mass percent of P, and the balance of SiO2The particle size is 1.0 to 10 μm.
Example 5
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) mixing 55.28g of basic copper carbonate, 40g of white carbon black and 0.23g of zinc acetate, and carrying out ball milling on the mixture and 286g of tungsten carbide grinding balls together, wherein the ball milling time is 3 hours, and the rotating speed is 100r/min, so as to obtain a first solid mixture;
(2) calcining the first solid mixture at 800 ℃ for 0.5h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.015g of elemental tin and 0.31g of CuP8And 150g of tungsten carbide grinding balls are mixed and ball-milled for 3 hours at the rotating speed of 100r/min to obtain the composite catalyst. The composite catalyst comprises 50% of CuO, 0.1% of Zn, 0.05% of Sn and 0.05% of P by mass, and the balance of SiO2The particle size is 1.0 to 10 μm.
Example 6
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) 66.33g of basic copper carbonate, 32g of white carbon black and 0.21g of basic zinc carbonate are mixed, and are ball-milled together with 296g of corundum grinding balls, wherein the ball-milling time is 2 hours, and the rotating speed is 400r/min, so that a first solid mixture is obtained;
(2) calcining the first solid mixture at 300 ℃ for 10 hours to obtain a second solid mixture;
(3) 50g of the second solid mixture were mixed with 0.0025g of elemental tin and 0.19g of CuP8And 150g of corundum grinding balls are mixed and ball-milled for 2 hours at the rotating speed of 400r/min to obtain the composite catalyst. The composite catalyst comprises, by mass, CuO 60%, Zn 0.1%, Sn 0.005% and P0.03%, and the balance of SiO2The particle size is 1.0 to 10 μm.
Example 7
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) mixing 22.11g of basic copper carbonate, 64g of white carbon black and 2.12g of basic zinc carbonate, and carrying out ball milling on the mixture and 442g of zirconia grinding balls together, wherein the ball milling time is 5 hours, and the rotating speed is 50r/min, so as to obtain a first solid mixture;
(2) calcining the first solid mixture at 400 ℃ for 1h to obtain a second solid mixture;
(3) mixing 50g of the second solid mixture with0.0025g elemental tin and 0.31g CuP8And 250g of zirconia grinding balls are mixed and ball-milled for 5 hours at the rotating speed of 50r/min to obtain the composite catalyst. The composite catalyst comprises, by mass, 19.5% of CuO, 1% of Zn, 0.005% of Sn and 0.05% of P, and the balance of SiO2The particle size is 1.0 to 10 μm.
Example 8
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) mixing 55.28g of basic copper carbonate, 40g of white carbon black and 2.12g of basic zinc carbonate, and carrying out ball milling on the mixture and 292g of stainless steel grinding balls together, wherein the ball milling time is 5 hours, and the rotating speed is 500r/min, so as to obtain a first solid mixture;
(2) calcining the first solid mixture at 400 ℃ for 1h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.015g of elemental tin and 0.19g of CuP8And 150g of stainless steel grinding balls are mixed and subjected to ball milling for 5 hours at the rotating speed of 500r/min to obtain the composite catalyst. The composite catalyst comprises, by mass, 49.5% of CuO, 1% of Zn, 0.03% of Sn and 0.03% of P, and the balance of SiO2The particle size is 0.3 to 10 μm.
Example 9
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) 66.33g of basic copper carbonate, 32g of white carbon black and 0.32g of copper-zinc alloy (the mass fraction of Zn is 40%) are subjected to ball milling together with 300g of stainless steel grinding balls, the ball milling time is 1h, and the rotating speed is 400r/min, so that a first solid mixture is obtained;
(2) calcining the first solid mixture at 400 ℃ for 1h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.025g of elemental tin and 0.031g of CuP8And 150g of stainless steel grinding balls are mixed and subjected to ball milling for 1h at the rotating speed of 400r/min to obtain the composite catalyst. The mass fraction of each component of the composite catalyst is 19.5 percent of CuOZn 1%, Sn 0.05% and P0.005%, the rest is SiO2The particle size is 1.0 to 10 μm.
Example 10
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) carrying out ball milling on 22.11g of basic copper carbonate, 64g of white carbon black and 0.01g of basic zinc carbonate and 260g of stainless steel grinding balls together, wherein the ball milling time is 2 hours, and the rotating speed is 400r/min, so as to obtain a first solid mixture;
(2) calcining the first solid mixture at 400 ℃ for 1h to obtain a second solid mixture;
(3) 50g of the second solid mixture were mixed with 0.025g of elemental tin and 0.19g of CuP8And 150g of stainless steel grinding balls are mixed and subjected to ball milling for 2 hours at the rotating speed of 400r/min to obtain the composite catalyst. The composite catalyst comprises 20 mass percent of CuO, 0.005 mass percent of Zn, 0.05 mass percent of Sn and 0.03 mass percent of P, and the balance of SiO2The particle size is 1.0 to 10 μm.
Example 11
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) ball milling 55.28g of basic copper carbonate, 40g of white carbon black and 0.1g of zinc oxide together with 286g of stainless steel balls for 2 hours at a rotation speed of 400r/min to obtain a first solid mixture;
(2) calcining the first solid mixture at 400 ℃ for 1h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.15g of a copper-tin alloy (Sn 10%) and 0.031g of CuP8And 150g of stainless steel grinding balls are mixed and subjected to ball milling for 2 hours at the rotating speed of 400r/min to obtain the composite catalyst. The composite catalyst comprises 50 percent of CuO, 0.1 percent of Zn, 0.03 percent of Sn and 0.005 percent of P by mass percent, and the balance of SiO2The particle size is 1.0 to 10 μm.
Example 12
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) ball-milling 55.28g of basic copper carbonate, 40g of white carbon black and 1.0g of zinc oxide together with 289g of stainless steel balls for 4 hours at the rotating speed of 400r/min to obtain a first solid mixture;
(2) calcining the first solid mixture at 400 ℃ for 2h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.015g of elemental tin and 0.031g of CuP8And 150g of stainless steel grinding balls are mixed and subjected to ball milling for 4 hours at the rotating speed of 300r/min to obtain the composite catalyst. The composite catalyst comprises 50% of CuO, 1% of ZnO, 0.03% of Sn and 0.005% of P by mass, and the balance of SiO2The particle size is 1.0 to 10 μm.
Example 13
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) ball-milling 55.28g of basic copper carbonate, 40g of white carbon black and 1.0g of zinc oxide together with 289g of stainless steel balls for 3 hours at the rotating speed of 400r/min to obtain a first solid mixture;
(2) calcining the first solid mixture at 400 ℃ for 6h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.015g of elemental tin and 0.031g of CuP8And 150g of stainless steel grinding balls are mixed and subjected to ball milling for 4 hours at the rotating speed of 300r/min to obtain the composite catalyst. The composite catalyst comprises 50% of CuO, 1% of ZnO, 0.03% of Sn and 0.005% of P by mass, and the balance of SiO2The particle size is 1.0 to 10 μm.
Example 14
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) ball-milling 55.28g of basic copper carbonate, 40g of white carbon black and 1.0g of zinc oxide together with 289g of stainless steel balls for 2 hours at the rotating speed of 400r/min to obtain a first solid mixture;
(2) calcining the first solid mixture at 400 ℃ for 4h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.015g of elemental tin and 0.031g of CuP8And 150g of stainless steel grinding balls are mixed and subjected to ball milling for 2 hours at the rotating speed of 400r/min to obtain the composite catalyst. The composite catalyst comprises 50% of CuO, 1% of ZnO, 0.03% of Sn and 0.005% of P by mass, and the balance of SiO2The particle size is 1.0 to 10 μm.
Example 15
This embodiment provides a preparation method of a composite catalyst, including the following steps:
(1) ball-milling 55.28g of basic copper carbonate, 40g of white carbon black and 1.0g of zinc oxide together with 289g of stainless steel balls for 2 hours at the rotating speed of 400r/min to obtain a first solid mixture;
(2) calcining the first solid mixture at 600 ℃ for 1h to obtain a second solid mixture;
(3) 50g of the second solid mixture was mixed with 0.015g of elemental tin and 0.031g of CuP8And 150g of stainless steel grinding balls are mixed and subjected to ball milling for 2 hours at the rotating speed of 400r/min to obtain the composite catalyst. The mass fraction of each component of the composite catalyst is 50 percent, and the SiO content is2 ZnO 1%, Sn 0.03%, P0.005%, and SiO in balance2The particle size is 1.0 to 10 μm.
Comparative example 1
Weighing 55.28g of basic copper carbonate, 40.0g of white carbon black and 2.12g of basic zinc carbonate, adding no Sn and P auxiliary agent, and completely using other parameters and conditions as in example 1 to finally obtain the composite copper oxide based catalyst.
Comparative example 2
This comparative example was carried out under the same conditions as example 1 except that 0.015g of elemental tin was not added in step (3).
Comparative example 3
This comparative example did not add 0.031g of CuP except for step (3)8Otherwise, the other conditions were the same as in example 1.
Comparative example 4
Weighing 55.28g of basic copper carbonate and 40.0g of white carbon black, adding no Zn, Sn and P auxiliaries, and finally obtaining the composite copper oxide based catalyst, wherein other parameters and conditions are completely the same as those in example 1.
Comparative example 5
Only 55.28g of basic copper carbonate were weighed, and the other parameters and conditions were exactly the same as in example 1, to obtain a catalyst.
Comparative example 6
The catalyst was a commercially available catalyst.
And (3) performance testing:
the catalysts obtained in examples 1 to 15 and comparative examples 1 to 4 were subjected to a catalytic activity test, which was carried out in a mini fixed bed apparatus: uniformly mixing Si powder and the catalyst in a ratio of 100:5, and filling the mixture into a fixed bed reactor (phi 20) to form a mixed contact; during the reaction, N is firstly adopted2Purging the reaction system, and then switching to CH3Cl gas with the flow rate of 25mL/min and the reaction time of 24h is preheated and then contacts with a contact body, and the reaction temperature is 325 ℃; the product after reaction flows out from the lower end of the reactor, is condensed by a condenser pipe and then is collected by toluene, and the redundant tail gas is absorbed by alkaline liquor and then is exhausted; and carrying out chromatographic analysis on the collected mixed solution after the volume is determined by adopting methylbenzene, and calculating the conversion rate of the Si powder and the distribution of products. M1: methyl trichlorosilane; m2: dimethyldichlorosilane; m3: trimethylchlorosilane; M1H: a methyl hydrosilane; M2H: dimethyl hydrosilane; LBR: a low boiling point substance; HBR: a high boiling residue; the product distribution is calculated as the percentage of the corresponding area of the reaction product.
The stable catalytic performance test is carried out on the example 1 and the comparative example 4, the reaction temperature is 295 ℃, the reaction time is 96 hours, samples are taken every 8 hours for measurement, and the rest reaction conditions are the same as the catalytic activity test.
The Si powder conversion was calculated by the following formula:
in the formula mBefore reactionAnd mAfter the reactionThe mass of Si before the reaction and the mass of Si after the reaction were measured.
The mass of dimethyldichlorosilane obtained with activity as copper per unit mass of time, gM2/(gCuH), the calculation formula is as follows:
wherein mSi is the mass of Si powder added before reaction; CSi is the Si powder conversion rate; mr (M2) is the relative molecular mass of M2, 129.06 g/mol; SM2 is M2 selective; mr (Si) is the relative molecular mass of Si, 28.09 g/mol; mCu is the mass of Cu in the added catalyst; t is the reaction time.
The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, when the organosilicon monomer synthesis reaction catalysts of examples 1-15 are used for catalyzing the synthesis reaction of M2 monomer, the catalytic performance is different due to different component contents, but the selectivity and activity of the catalyst M2 are obviously higher than those of comparative examples 1-5 and a commercial copper catalyst (comparative example 6), the M2 selectivity is optimally 88.4%, and the silicon powder conversion rate is 24.0%.
The addition of Sn and CuP as additives can be obtained by comparing examples 1-15 with comparative examples 1-38After that, the catalyst activity and the M2 selectivity are both obviously improved, and the silicon powder conversion rate is also obviously improved.
The M2 selectivity versus the fixed bed stable catalytic reaction for example 1 and comparative example 6 is shown in fig. 3, and it can be seen from fig. 3 that the catalyst prepared by the present invention is significantly more selective than the commercial catalyst, has higher selectivity, shorter induction period, and long stability period.
The above results all confirm that the organosilicon monomer synthesis reaction provided by the invention is relative to a commercial ternary copper catalystThe selectivity and the silicon powder conversion rate of the catalyst M2 are obviously increased, and the catalytic activity is improved by times. The main reason is that the active components in the catalyst of the invention are highly dispersed on the white carbon black carrier, the addition of the Zn, Sn, P and other element additives changes the electronic structure of the main catalyst and promotes the reaction of the active phase CuxAnd forming Si. The synergistic catalytic action exists between various auxiliary agents and the active component CuO, so that the selectivity of the reaction and the activity of the catalyst are greatly improved.
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. The composite catalyst for synthesizing the organic silicon monomer is characterized by comprising a carrier, wherein a copper-based active substance and a coagent are loaded on the carrier, and the coagent comprises Zn element, Sn element and P element.
2. The composite catalyst according to claim 1, wherein the copper-based active component is copper oxide;
preferably, the content of the copper-based active component in the composite catalyst is 20-60 wt%.
3. The composite catalyst according to claim 1 or 2, wherein the content of Zn element in the composite catalyst is 0.005 to 1 wt%;
preferably, the content of Sn element in the composite catalyst is 0.005-0.05 wt%;
preferably, the content of the P element in the composite catalyst is 0.005-0.05 wt%.
4. The composite catalyst according to any one of claims 1 to 3, wherein the support is silica;
preferably, the particle size of the composite catalyst is 0.3-10 μm, preferably 1.0-5.0 μm.
5. A method for preparing the composite catalyst according to any one of claims 1 to 4, wherein the method for preparing comprises the steps of:
(1) mixing a copper source, a zinc source and a carrier, and crushing to obtain a first solid mixture;
(2) calcining the first solid mixture crystal form to obtain a second solid mixture;
(3) and mixing the second solid mixture with a tin source and a phosphorus source, and crushing to obtain the composite catalyst.
6. The method of claim 5, wherein the copper source of step (1) comprises basic copper carbonate;
preferably, the zinc source in step (1) comprises any one or a combination of at least two of zinc oxide, elemental zinc powder, copper-zinc alloy, basic zinc carbonate or zinc acetate, preferably zinc oxide and/or basic zinc carbonate.
7. The production method according to claim 5 or 6, wherein the crushing treatment in step (1) is performed by ball milling;
preferably, the ball-milled grinding beads are any one or a combination of at least two of zirconia balls, stainless steel balls, tungsten carbide balls and corundum balls, and are preferably stainless steel balls;
preferably, the diameter of the grinding bead is 1-10 mm;
preferably, the mass ratio of the grinding beads to the mixed powder is (1-10): 1, preferably (1-5): 1;
preferably, the stirring speed of the ball mill is 50-500 r/min, preferably 100-400 r/min;
preferably, the ball milling time is 0.5-5 h, preferably 1-3 h;
preferably, the ball milling is dry milling;
preferably, the atmosphere of the ball mill is air.
8. The production method according to any one of claims 5 to 7, wherein the calcination treatment in step (2) is performed in an air atmosphere;
preferably, the calcining temperature in the step (2) is 300-800 ℃, preferably 400-600 ℃;
preferably, the calcining time in the step (2) is 0.5-10 h, preferably 1-4 h.
9. The production method according to any one of claims 5 to 8, wherein the tin source of step (3) comprises elemental tin powder and/or a copper-tin alloy;
preferably, the phosphorus source in step (3) is CuP8；
Preferably, the crushing treatment in the step (3) is ball milling.
10. Use of the composite catalyst according to any one of claims 1 to 4 in a silicone monomer synthesis reaction;
preferably, the composite catalyst is applied to the selective synthesis of dimethyldichlorosilane.
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| CN103316702A (en) * | 2012-03-22 | 2013-09-25 | 中国科学院过程工程研究所 | Cooper base catalyst and preparation method thereof |
| CN112246247A (en) * | 2020-10-15 | 2021-01-22 | 中国科学院过程工程研究所 | Organic silicon monomer synthesis reaction catalyst and preparation method and application thereof |
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| CN103316702A (en) * | 2012-03-22 | 2013-09-25 | 中国科学院过程工程研究所 | Cooper base catalyst and preparation method thereof |
| CN103127936A (en) * | 2013-02-04 | 2013-06-05 | 中国科学院过程工程研究所 | Method preparing catalyzer through liquid phase ball-milling partial reduction method and ternary copper catalyzer |
| CN112246247A (en) * | 2020-10-15 | 2021-01-22 | 中国科学院过程工程研究所 | Organic silicon monomer synthesis reaction catalyst and preparation method and application thereof |
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