CN117654486A - Silica powder supported catalyst and application thereof in improving content of dichlorosilane - Google Patents
Silica powder supported catalyst and application thereof in improving content of dichlorosilane Download PDFInfo
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- CN117654486A CN117654486A CN202311618725.2A CN202311618725A CN117654486A CN 117654486 A CN117654486 A CN 117654486A CN 202311618725 A CN202311618725 A CN 202311618725A CN 117654486 A CN117654486 A CN 117654486A
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- supported catalyst
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- dichlorosilane
- modified silane
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 title claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 20
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 title abstract description 23
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 29
- 239000004526 silane-modified polyether Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 22
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- 150000004756 silanes Polymers 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 229910021487 silica fume Inorganic materials 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 7
- 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 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000005049 silicon tetrachloride Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 4
- PZKOFHKJGUNVTM-UHFFFAOYSA-N trichloro-[dichloro(trichlorosilyl)silyl]silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)[Si](Cl)(Cl)Cl PZKOFHKJGUNVTM-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- -1 sodium alkoxide Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- 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
- 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
- C01B33/10778—Purification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a silicon powder supported catalyst and application thereof in improving content of dichlorosilane. The preparation method of the silica powder supported catalyst comprises the following steps: s1, preparing polyether modified silane by hydrosilylation reaction of allyl polyethylene glycol monomethyl ether and hydrogen-containing trimethoxy silane under the action of a catalyst; s2, mixing the aqueous solution of polyether modified silane obtained in the step S1 with nitrate aqueous solution, adding silicon powder, treating for 1-3 hours at 50-60 ℃, filtering to obtain solid, and calcining at 200-400 ℃ to obtain the polyether modified silane. The silicon powder supported catalyst obtained by the preparation method provided by the invention can effectively realize the synthesis of trichlorosilane and improve the synthesis proportion of dichlorosilane, and the method has low cost and higher content of the obtained dichlorosilane.
Description
Technical Field
The invention relates to the technical field of catalyst synthesis, in particular to a silicon powder supported catalyst and application thereof in improving the content of dichlorosilane.
Background
The application prospect of dichlorosilane as a silicon element gas in semiconductor epitaxy and chemical vapor deposition processes is continuously being explored. In the prior art, anion exchange resin or organic amine catalyst is mostly adopted in the industries of polysilicon and organic silicon to catalyze disproportionation of trichlorosilane to prepare silicon tetrachloride and obtain dichlorosilane, but in the method, the resin and the catalyst need to be subjected to water removal treatment in advance, the tower loading cost is high, the resin replacement period is 4-6 months, and the treatment cost is high. Meanwhile, in the prior art, such as CN201210047067.1, trichlorosilane is prepared by the trichlorosilane under the action of a catalyst, and the method has high cost and low conversion rate. In the synthesis reaction of organosilicon monomer trichlorosilane, the byproduct dichlorosilane in the obtained product accounts for about 0.2-0.4 wt% of the trichlorosilane, and partial dichlorosilane (dichlorosilane is unstable) is converted into polychlorinated silicon compounds such as silicon tetrachloride during distillation and purification, so that the finally actually produced dichlorosilane is about 0.08 wt%.
Disclosure of Invention
The first object of the invention is to provide a preparation method of a silica powder supported catalyst, wherein the silica powder supported catalyst obtained by the preparation method can economically and effectively realize the synthesis of trichlorosilane and simultaneously improve the synthesis proportion of dichlorosilane.
The preparation method of the silicon powder supported catalyst provided by the invention comprises the following steps:
s1, preparing polyether modified silane by hydrosilylation reaction of allyl polyethylene glycol monomethyl ether and hydrogen-containing trimethoxy silane under the action of a catalyst;
s2, mixing the aqueous solution of polyether modified silane obtained in the step S1 with nitrate aqueous solution, adding silicon powder, treating for 1-3 hours at 50-60 ℃, filtering to obtain solid, and calcining at 200-400 ℃ to obtain the polyether modified silane.
In the embodiment of the present invention, in step S1, the polyethylene glycol monomethyl ether in the allyl polyethylene glycol monomethyl ether may be ethylene glycol monomethyl ether, MPEG350, MPEG550, MPEG750, MPEG1000, etc., preferably MPEG350. In the step S1, allyl polyethylene glycol monomethyl ether can be purchased commercially or can be self-made. In one embodiment of the invention, the preparation method of allyl polyethylene glycol monomethyl ether can comprise the following steps: filtering after the polyethylene glycol monomethyl ether is subjected to sodium alkoxide alkylation reaction, and dripping chloropropene to prepare the product. In the preparation method, the polyethylene glycol monomethyl ether can be ethylene glycol monomethyl ether, MPEG350, MPEG550, MPEG750, MPEG1000, etc., preferably MPEG350. Wherein, the sodium alkoxide can be sodium methoxide and the like. Wherein, in order to improve the catalytic effect of the obtained catalyst, the molar ratio of polyethylene glycol monomethyl ether to sodium alkoxide is preferably 1 (1.05-1.1). Wherein, the mol ratio of polyethylene glycol monomethyl ether to chloropropene is preferably 1 (1.2-1.4).
In a preferred embodiment of the present invention, the process for preparing allyl polyethylene glycol monomethyl ether preferably comprises the steps of: mixing polyethylene glycol monomethyl ether and sodium methoxide according to a proportion, performing reduced pressure reaction at 100-120 ℃ while removing low boiling point under reduced pressure until no bubble is generated, cooling to 40-50 ℃ under the protection of nitrogen, dropwise adding chloropropene into the system, maintaining the temperature of the system to be not more than 60 ℃, dropwise adding for 1-2 h, performing heat preservation reaction for 1-2 h, neutralizing the system to pH of 4.5-6.5, and performing vacuum distillation and filtration to obtain the product. The system may be neutralized to a pH of 4.5 to 6.5 using a neutralizing agent commonly used in the art, for example, the neutralizing agent may be hydrochloric acid, acetic acid, or the like.
In a preferred embodiment of the present invention, in order to improve the catalytic effect of the obtained catalyst, in step S1, the molar ratio of allyl polyethylene glycol monomethyl ether to hydrogen-containing trimethoxysilane is 1: (1-1.2).
In a preferred embodiment of the present invention, in order to enhance the catalytic effect of the catalyst, in step S1, the catalyst is an isopropyl chloroplatinic acid solution. The concentration of the chloroplatinic acid isopropyl alcohol solution is conventionally selected, and may be, for example, 5wt%. The catalyst is used in such an amount that the Pt content in the system is preferably 10 to 50ppm.
In a preferred embodiment of the present invention, in step S1, the reaction temperature of the hydrosilylation reaction is 80 to 90 ℃ and the reaction time is 3 to 4 hours. In the specific embodiment of the present invention, allyl polyethylene glycol monomethyl ether and hydrogen-containing trimethoxysilane as raw materials in step S1 may be activated as needed. The specific activation step may include: under the protection of nitrogen, activating the catalyst and allyl polyethylene glycol monomethyl ether at 80-85 ℃ for 1h, and then dropwise adding hydrogen-containing trimethoxy silane to carry out hydrosilylation reaction.
In a preferred embodiment of the present invention, in step S2, the polyether-modified silane obtained in step S1 may be dissolved in water to obtain an aqueous solution of the polyether-modified silane, and the mass concentration of the aqueous solution is preferably 5 to 10% by weight. In the present invention, the polyether-modified silane is dissolved in water at normal temperature to obtain an aqueous solution of polyether-modified silane.
In a preferred embodiment of the present invention, in step S2, the aqueous nitrate solution may be copper nitrate or an aqueous nitrate solution. Wherein the concentration of the nitrate aqueous solution is preferably 0.1 to 0.5mol/L. In a preferred embodiment of the present invention, in order to enhance the catalytic effect of the resulting catalyst, the nitrate aqueous solution is used in an amount of 10 to 20% by weight based on the mass of the polyether-modified silane in step S2.
In one embodiment of the present invention, silicon powder may be used as a raw material for synthesizing silicon powder for trichlorosilane. In a preferred embodiment of the present invention, in order to enhance the catalytic effect of the obtained catalyst, the amount of silicon powder added in step S2 is 3 to 6 times the mass of the polyether-modified silane.
In a preferred embodiment of the present invention, in order to improve the catalytic effect of the obtained catalyst, in step S2, the specific step of calcining comprises: heating from 250 ℃ at a speed of 1-5 ℃/min, heating to 250-300 ℃ and preserving heat for 10-20 min, heating to 300-350 ℃ and preserving heat for 10-20 min, and heating to 350-400 ℃ and preserving heat for 30-60 min. In a preferred embodiment of the present invention, the specific steps preferably include: heating from 250 ℃ at a speed of 1-5 ℃/min, heating to 250-300 ℃ and preserving heat for 10-20 min, heating to 300-350 ℃ at 1-5 ℃/min and preserving heat for 10-20 min, and heating to 350-400 ℃ at 3-8 ℃/min and preserving heat for 30-60 min.
The silicon powder supported catalyst obtained by the preparation method provided by the invention can catalyze the reaction of silicon powder and hydrogen chloride, the content of dichlorosilane in the obtained product is at least 1wt%, preferably at least 1.5wt%, the obtained dichlorosilane accounts for not less than 1.5wt%, preferably not less than 2wt%, and the synthesis proportion of dichlorosilane in the trichlorosilane is effectively improved.
Namely, another object of the present invention is to provide a silica powder supported catalyst obtained by the above-mentioned production method.
The invention also aims to provide the application of the silicon powder supported catalyst obtained by the preparation method in synthesizing trichlorosilane.
In a preferred embodiment of the present invention, the step of synthesizing trichlorosilane comprises: premixing the silicon powder supported catalyst and silicon powder at 220-240 ℃, then introducing hydrogen chloride gas, and reacting at 350-370 ℃ and 0.09-0.1 MPa.
Wherein, the silicon powder supported catalyst is preferably 1 to 5 weight percent of the mass of the silicon powder. Wherein, 1kg of silicon powder is preferably corresponding to 2.8 to 3.0m of hydrogen chloride 3 。
In the synthesis reaction, the reaction is carried out at 350-370 ℃ under 0.09-0.1 MPa (the reaction of silicon powder and hydrogen chloride is instantaneous exothermic reaction, the reaction can be usually carried out for 10-30 min for full reaction), a small amount of unreacted silicon powder is removed from a synthesized gas-phase crude product through a cyclone dust collector and a bag filter after the reaction is finished, the trichlorosilane crude product obtained by the previous synthesis is used as spray liquid (if the first batch is, trichlorosilane with the trichlorosilane content of 99.5% and the dichlorosilane content of 0.12% is used as spray liquid), and the wet dust removal is carried out by a wet dust collector to obtain the trichlorosilane crude product.
The silicon powder supported catalyst obtained by the preparation method provided by the invention can effectively realize the synthesis of trichlorosilane and improve the synthesis proportion of dichlorosilane. Meanwhile, the catalyst provided by the invention is suitable for other anti-disproportionation reactions and reactions with requirements on metal ion control, and has wide applicability.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the present invention, "%" represents mass% unless otherwise specified.
Example 1
1. Synthesis of polyether modified silanes
Adding 700g of MPEG350 and 116.6g of solid sodium methoxide into a three-neck flask, slowly heating, distilling under negative pressure to remove low-boiling substances, keeping the temperature of the materials slowly raised to 118 ℃, dropwise adding 196g of chloropropene at 42 ℃ under the protection of nitrogen, keeping the dropwise adding temperature not higher than 58 ℃, keeping the dropwise adding time for 1h, preserving the heat for 1.5h, adding 10% hydrochloric acid aqueous solution to neutralize until the pH is 6.2, and removing the bubbles under vacuum, thus obtaining the product. 264g of hydrogen-containing trimethoxysilane and 5wt% of isopropyl alcohol solution of chloroplatinic acid are added into the mixture (the added amount of the isopropyl alcohol solution of chloroplatinic acid is such that the Pt content in the system is 15-20 ppm), the mixture is reacted for 4 hours at 82-85 ℃, the temperature is reduced and distilled until no bubbles are generated (low boiling point matters are removed), 992.3g of light yellow transparent polyether modified silane is obtained, the obtained solid content is 9.62%, the iodine value is 11.6%, the GC internal standard test methanol is 0.092%, the trimethoxy hydrogen-containing silane is 0.11%, and the tetramethoxy silane is 0.29%.
2. Preparation of silica powder supported catalyst
Adding 700g of polyether modified silane into 700g of tap water, stirring at room temperature to obtain a uniform aqueous solution, adding 7g of 0.26mol/L silver nitrate aqueous solution, fully stirring, adding 270g of silicon powder, heating at 52-54 ℃ for 100min, filtering to obtain solid, placing the obtained solid into a crucible, heating to 280 ℃ at 2 ℃/min to 10min after the temperature reaches 250 ℃, then heating to 350 ℃ at 2 ℃/min to 15min, heating to 370 ℃ at 5 ℃/min to 40min, and cooling to obtain 105.3g of silicon powder supported catalyst.
3. Synthesis of trichlorosilane
Treating 80g of the obtained silica powder supported catalyst and 3000g of silica powder in a premixing furnace at 220-240 ℃ for 20min, transferring the mixture into a synthesis furnace, and continuously introducing 8.7m into the synthesis furnace 3 After hydrogen chloride is reacted for 10min at the temperature of 350-370 ℃ and the pressure of 0.09-0.1 MPa in the furnace, a small amount of unreacted silicon powder is removed from the synthesized gas phase crude product by a cyclone dust collector and a bag filter, and then trichlorosilane with the content of 99.5% of trichlorosilane and the content of dichlorosilane of 0.12% is used as spray liquid (in the actual process, the trichlorosilane crude product obtained by the previous batch of synthesis is used as spray liquid), and wet dust removal is carried out by a wet dust collector to obtain the trichlorosilane crude product, and the GC content of the trichlorosilane crude product is tested: air 0.014%, hydrogen chloride 0.027%, dichlorosilane 1.61%, trichlorosilane 76.832%, silicon tetrachloride 20.75%, hexachlorodisilane 0.437% and octachlorotrisilane 0.276%.
Example 2
The method provided in this example is the same as that provided in example 1, except that: 1. synthesis of polyether modified silane:
1. synthesis of polyether modified silanes
Adding 152.2g of ethylene glycol monomethyl ether and 113.5g of solid sodium methoxide into a three-neck flask, slowly heating, distilling under negative pressure to remove low-boiling substances, slowly heating to 115 ℃ while maintaining the temperature of the materials without bubbles, dropwise adding 184g of chloropropene at 45 ℃ under the protection of nitrogen, maintaining the dropwise adding temperature not to exceed 58 ℃, dropwise adding for 1h, preserving heat for 2h, adding 10% hydrochloric acid aqueous solution to neutralize until the pH is 6.0, and vacuum removing low-boiling substances and filtering to obtain the product. 264g of hydrogen-containing trimethoxysilane and 5wt% of chloroplatinic acid in isopropanol solution were added thereto (the amount of the added chloroplatinic acid in isopropanol solution was such that the Pt content in the system was 15-20 ppm), the reaction was carried out at 82-85℃for 3 hours, and the reaction was cooled and distilled until no bubbles (except for low boilers) were formed, thus 451.3g of pale yellow transparent polyether-modified silane was obtained, which had a solid content of 25.83%, an iodine value of 0.18%, GC internal standard test methanol of 0.08%, trimethoxy hydrogen-containing silane of 0.12% and tetramethoxy silane of 0.19%.
The silica powder supported catalyst obtained in this example was synthesized using the method of "3, synthesis of trichlorosilane" in example 1 to obtain crude trichlorosilane. Testing GC content of crude trichlorosilane: air 0.016%, hydrogen chloride 0.027%, dichlorosilane 1.48%, trichlorosilane 77.03%, silicon tetrachloride 20.77%, hexachlorodisilane 0.453% and octachlorotrisilane 0.175%.
Example 3
The method provided in this example is the same as that provided in example 1, except that: 2. preparation of silica powder supported catalyst:
2. preparation of silica powder supported catalyst
60g polyether modified silane is added into 1140g tap water and stirred at room temperature to obtain a uniform aqueous solution, 11.4g 0.5mol/L silver nitrate aqueous solution is added and fully stirred, 300g silicon powder is added, the mixture is heated at 52-54 ℃ for 100min and filtered to obtain solid, the obtained solid is placed into a crucible, the temperature reaches 250 ℃ and is increased to 280 ℃ for 10min, then the temperature is increased to 350 ℃ for 15min at 2 ℃/min, finally the temperature is increased to 370 ℃ for 40min at 5 ℃/min, and the silica powder supported catalyst is obtained after cooling.
The silica powder supported catalyst obtained in this example was synthesized using the method of "3, synthesis of trichlorosilane" in example 1 to obtain crude trichlorosilane. Testing GC content of crude trichlorosilane: air 0.016%, hydrogen chloride 0.028%, dichlorosilane 1.56%, trichlorosilane 76.73%, silicon tetrachloride 20.84%, hexachlorodisilane 0.452% and octachlorotrisilane 0.183%.
Example 4
The method provided in this example is the same as that provided in example 1, except that: 2. preparation of silica powder supported catalyst:
2. preparation of silica powder supported catalyst
Adding 700g of tap water into 60g of polyether modified silane, stirring at room temperature to obtain a uniform aqueous solution, adding 7g of 0.26mol/L silver nitrate aqueous solution, fully stirring, adding 190g of silicon powder, heating at 52-54 ℃ for 100min, filtering to obtain solid, placing the obtained solid into a crucible, maintaining at 370 ℃ for 65min, and cooling to obtain the silicon powder supported catalyst.
The silica powder supported catalyst obtained in this example was synthesized using the method of "3, synthesis of trichlorosilane" in example 1 to obtain crude trichlorosilane. Testing GC content of crude trichlorosilane: air 0.018%, hydrogen chloride 0.031%, dichlorosilane 1.27%, trichlorosilane 76.43%, silicon tetrachloride 21.45%, hexachlorodisilane 0.452% and octachlorotrisilane 0.332%.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a silicon powder supported catalyst comprises the following steps:
s1, preparing polyether modified silane by hydrosilylation reaction of allyl polyethylene glycol monomethyl ether and hydrogen-containing trimethoxy silane under the action of a catalyst;
s2, mixing the aqueous solution of polyether modified silane obtained in the step S1 with nitrate aqueous solution, adding silicon powder, treating for 1-3 hours at 50-60 ℃, filtering to obtain solid, and calcining at 200-400 ℃ to obtain the polyether modified silane.
2. The preparation method according to claim 1, wherein in the step S1, the molar ratio of allyl polyethylene glycol monomethyl ether to hydrogen-containing trimethoxysilane is 1: (1-1.2).
3. The preparation method according to claim 1 or 2, wherein in step S1, the catalyst is a chloroplatinic acid isopropyl alcohol solution, and the catalyst is used in an amount such that the Pt content in the system is 10 to 50ppm.
4. A process according to any one of claims 1 to 3, wherein in step S1, the hydrosilylation reaction is carried out at a reaction temperature of 80 to 90 ℃ for a reaction time of 3 to 4 hours.
5. The method according to any one of claims 1 to 4, wherein in step S2, the aqueous solution of nitrate is 10 to 20wt% based on the mass of polyether-modified silane, the aqueous solution of polyether-modified silane has a concentration of 5 to 10wt%, and the aqueous solution of nitrate has a concentration of 0.1 to 0.5mol/L.
6. The method according to any one of claims 1 to 5, wherein in step S2, the amount of silicon powder added is 3 to 6 times the mass of the polyether silane.
7. The method according to any one of claims 1 to 6, wherein in step S2, the specific step of calcining comprises: heating from 250 ℃ at a speed of 1-5 ℃/min, heating to 250-300 ℃ and preserving heat for 10-20 min, heating to 300-350 ℃ and preserving heat for 10-20 min, and heating to 350-400 ℃ and preserving heat for 30-60 min.
8. A silica powder supported catalyst obtained by the production process according to any one of claims 1 to 7.
9. The use of the silica fume supported catalyst of claim 8 in the synthesis of trichlorosilane.
10. The use according to claim 9, characterized in that the silica powder supported catalyst is premixed with silica powder at 220-240 ℃, then hydrogen chloride gas is introduced and reacted at 350-370 ℃, 0.09-0.1 MPa.
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