CN109384233B - Method for treating silicon polymers - Google Patents
Method for treating silicon polymers Download PDFInfo
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- CN109384233B CN109384233B CN201811525561.8A CN201811525561A CN109384233B CN 109384233 B CN109384233 B CN 109384233B CN 201811525561 A CN201811525561 A CN 201811525561A CN 109384233 B CN109384233 B CN 109384233B
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- silicon
- polymer
- silicon polymer
- chlorosilane
- ionic liquid
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- 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
Abstract
The invention relates to a method for treating silicon polymer, which comprises the steps of taking ionic liquid as a catalyst, taking silicon polymer and anhydrous hydrogen chloride as raw materials, and reacting the silicon polymer and the anhydrous hydrogen chloride in a reactor at the temperature of 30-180 ℃ and under the pressure of 0.02-1.2MPa to obtain a chlorosilane product containing 1 silicon atom. The invention has the advantages of improving the processing capacity of the byproduct high boiling point polymer of polysilicon and organic silicon, reducing the catalyst loss and eliminating the environmental pollution.
Description
Technical Field
The invention relates to the field of polysilicon preparation and organic silicon preparation, in particular to a cracking method of byproduct silicon polymers in the production of polysilicon and organic silicon.
Background
During the production of polysilicon and organosilicon, a considerable amount of chlorosilane residual liquid is produced, and the components of the chlorosilane residual liquid comprise chlorosilane containing 1 silicon atom, silicon powder and other solid impurities, and high polymers (commonly called as high-boiling substances). Most of the solid impurities such as chlorosilane and silicon powder containing 1 silicon atom can be recovered through means of filtration, separation, rectification and the like, and comprehensive treatment can be performed, but the structure of high-boiling substances is complex, the components are uncertain, and conversion and utilization cannot be realized through simple organic separation. The continuous accumulation or backlog of high-boiling residues can cause the problems of increased production cost, environmental pollution and the like of enterprises, and prevent the development of polysilicon and organic silicon industries.
The patent CN101659672A discloses a cracking treatment method of waste residue slurry formed in the synthesis process of an organic silicon monomer, wherein a liquid-solid mixture with the solid content of the organic silicon waste residue slurry being 20 percent is added with high-boiling substances with the same mass to prepare a cracking raw material liquid; the catalyst is tributylamine, the cracking reaction temperature is 80-160 ℃, HCl gas is introduced, the feeding speed of hydrogen chloride and the ratio of the mixed solution of the HCl gas and the raw materials is 1:1.05-1:1.12; the invention makes the slag slurry with 20% solid content and high boiling point substance used together, the alkane with 1 silicon atom is directly separated in the cracking process, the conversion rate is above 70%, the selectivity of dimethyl dichlorosilane is above 35%, the selectivity of methylhydrosilane is above 40%, and the cracked slag slurry has certain fluidity and can be further processed.
At present, the existing catalyst and polysilane system are not mutually soluble, so that slag slurry after cracking or a reaction system is poor in fluidity, and the problem of nonuniform catalytic reaction and low conversion efficiency is caused, while patent CN103553056A utilizes ionic liquid to realize high-efficiency and rapid separation of silicon tetrachloride and trichlorosilane by a temperature control phase inversion means; and separating the two liquid phases, and then evaporating and condensing the two liquid phase layers at different temperatures respectively to separate and recover the high-purity chlorosilane with single component, which shows that the ionic liquid has better solubility for a chlorosilane system.
Therefore, in the prior art, there is still a need for a simple and effective method for treating silicon polymers, which can increase the treatment amount of silicon polymers such as polysilicon high boiling substances and organic silicon high boiling substances, and simultaneously reduce the cost, catalyst loss and environmental pollution. According to the invention, ionic liquid is used as a catalyst, and the aim of solvating a chlorosilane system for treating a silicon-containing polymer without introducing other impurities is fulfilled by utilizing the characteristic of good solubility of the ionic liquid to the chlorosilane system of the silicon-containing polymer by adopting a method of adopting the ionic liquid catalyst, and in a solvated ionic liquid-chlorosilane reaction system of the silicon-containing polymer, the silicon polymer is reacted with anhydrous hydrogen chloride to generate a chlorosilane compound containing only 1 silicon atom, such as trichlorosilane, dichlorosilane, silicon tetrachloride or methylchlorosilane.
Disclosure of Invention
The invention aims to provide a simple and effective method for treating silicon polymers, which solves the problem that when the problem that polysilicon, organic silicon byproducts, high boiling point silicon polymers and catalysts cannot be mutually dissolved is solved, a benzene-containing catalyst which is not friendly to the environment is introduced to cause new environmental protection risks, and reduces the cost, catalyst loss and environmental pollution while improving the treatment capacity of the silicon polymers such as polysilicon high boiling point substances, organic silicon high boiling point substances and the like.
The inventor finds that the ionic liquid not only can carry out disproportionation reaction of chlorosilane, but also can catalyze cracking reaction of polysilicon and organosilicon byproduct silicon polymer under different reaction conditions and different reaction systems, and the mixed solution of the silicon polymer is added with the cationic quaternary ammonium salt and the anionic CF 3 SO 3 - 、CF 3 COO - 、PF 6 - 、N(CF 3 SO 2 ) 2 - 、C(CF 3 SO 2 ) 3 - 、N(CN) 2 - 、Cl - According to the ionic liquid, the characteristic of good solubility of the ionic liquid to a chlorosilane system of a silicon-containing polymer is utilized, and the silane compound containing only 1 silicon atom is generated by reacting the anhydrous hydrogen chloride with the silicon polymer by taking the ionic liquid as a catalyst under the conditions of 30-180 ℃ and 0.02-1.2MPa, so that the aim of the invention is effectively realized.
The technical scheme adopted by the invention is as follows:
as shown in fig. 1, in the silicon polymer treatment reactor 2, a mixture of silicon polymer and chlorosilane containing 1 silicon atom is fed through a feed line 4, anhydrous HCl is fed into the silicon polymer treatment reactor 2 through a gas distributor 6 through a line 12, the flow rate of the mixture of silicon polymer and chlorosilane containing 1 silicon atom can be controlled by the valve 3, the flow rate of anhydrous hydrogen chloride can be controlled by a valve 13, and the mixture of silicon polymer and chlorosilane containing 1 silicon atom and the catalyst form a reaction mixture 5. The mixture of the reaction product containing 1 silicon atom chlorosilane and the unreacted completely anhydrous hydrogen chloride are taken out through a pipeline 11, the mixture containing 1 silicon atom chlorosilane after condensation is distilled and separated, the unreacted anhydrous hydrogen chloride is compressed through a compressor after condensation and separation and then is recycled, and the cracking reaction pressure of the silicon polymer can be controlled through a valve 10. Before or after the silicon polymer treatment, nitrogen can be introduced into the pipeline 8 and the valve 7 for purging, and tail gas is discharged through the pipeline 1 and the valve 9 and is absorbed by alkali liquor for discharging.
In the above scheme, the silicon polymer is a polymer formed by a silicon-silicon bond type.
In the above scheme, the silicon polymer can be represented as R a —SiH b Cl c —（SiH e Cl f R g -SiH i Cl j R k ） n —SiH x Cl y R z A form wherein a, b, c, x, y, z is one of 0, 1, 2, 3, e, f, g, i, j, k is one of 0, 1, 2, and a+b+c=3, e+f+g=2, i+j+k=2, x+y+z=3; n is a non-negative integer; r=h, cl, alkyl, benzene-containing alkyl, and the like.
In the above scheme, the catalyst is an ionic liquid catalyst, but preferably the ionic liquid is a quaternary ammonium salt ionic liquid.
In the above scheme, the added ionic liquid anion is CF 3 SO 3 - 、CF 3 COO - 、PF 6 - 、N(CF 3 SO 2 ) 2 - 、C(CF 3 SO 2 ) 3 - 、N(CN) 2 - 、Cl - One or more of the following.
In the above scheme, the chlorosilane product containing 1 silicon atom can be represented as R m —SiH n Cl p R=h, cl, alkyl, benzene-containing alkyl, etc., m, n, p are one of 0, 1, 2, 3, 4, and m+n+p=4.
In the above-mentioned scheme, the silicon polymer preferably refers to a mixture of a silicon polymer and chlorosilane containing 1 silicon atom.
In the above scheme, the silicon polymer preferably refers to polysilicon byproduct high boiling substances and organic silicon byproduct high boiling substances containing the silicon polymer.
In the above scheme, the catalyst can be added into the reactor 2 through the pipeline 4 and the valve 3, and the catalyst can be added together with the mixture of the silicon polymer and the chlorosilane containing 1 silicon atom, can be added in advance, can be added after the mixture of the silicon polymer and the chlorosilane containing 1 silicon atom is added, and can also be used for suspending the feeding during the treatment process and adding the supplementary catalyst through the pipeline 4 and the valve 3.
In the above-described scheme, the reactor 2 is between 0.02MPa and 1.2MPa, preferably between 0.05MPa and 0.5MPa, and more preferably between 0.1MPa and 0.45 MPa. The silicon polymer treatment temperature is between 30 and 180 ℃, preferably between 50 and 150 ℃, more preferably between 70 and 130 ℃.
In the above scheme, the molar ratio of anhydrous hydrogen chloride to silicon polymer and silicon polymer in the mixture of chlorosilanes containing 1 silicon atom is between 0.5 and 30:1, preferably between 1 and 10:1, and more preferably between 3 and 6:1.
In the above described variant, the feed to reactor 2 may be unconcentrated, but preferably the feed to reactor 2 is preconcentrated to a concentration of between 10% and 80%, preferably between 30% and 60% of the silicon polymer.
In the above scheme, the molar or mass ratio of the entering catalyst to the silicon polymer is between 1:1 and 200, but preferably between 1:9 and 99.
In the above scheme, the material entering reactor 2 may be untreated, but preferably, the material entering reactor 2 is pretreated to remove silicon powder and supersaturated metal compound impurities therefrom.
In the above-described scheme, the reactor 2 and the pipes and valves shown in FIG. 1 are preferably insulated or heated by a jacket or a heat-tracing pipe.
Drawings
FIG. 1 is a schematic diagram of a process for treating a silicon polymer in accordance with the present invention.
Wherein, 1 pipeline, 2 reactor, 3 valve, 4 pipeline, 5 reaction mixture, 6 gas distributor, 7 valve, 8 pipeline, 9 valve, 10 valve, 11 pipeline, 12, pipeline, 13 valve.
Detailed Description
According to the invention, the material entering reactor 2 may be unconcentrated, but preferably, the material entering reactor 2 is pre-concentrated to a concentration of between 10% and 80%, preferably between 30% and 60%, of the silicon polymer and filtered to remove silicon powder and supersaturated metal compounds.
For convenience, the silicon polymer treatment method of the present invention will be described with reference to FIG. 1. It should be noted, however, that the process of the present invention is not limited to a particular configuration. The feed location, nozzle location and number of feed channels of the processor can be varied simply as is well known to those skilled in the art.
According to the invention, the added ionic liquid cation is quaternary ammonium salt, and the ionic liquid anion is CF 3 SO 3 - 、CF 3 COO - 、PF 6 - 、N(CF 3 SO 2 ) 2 - 、C(CF 3 SO 2 ) 3 - 、N(CN) 2 - 、Cl - The following examples are given by way of further illustration of the invention, and are not intended to be limiting of the invention.
Example 1:
with the reactor shown in fig. 1, in the reactor 2, a silicon polymer, chlorosilane containing 1 silicon atom and a catalyst are added through a feed pipe 4 and a valve 3, anhydrous hydrogen chloride is added through a pipe 12 and a valve 13, a reaction product is withdrawn through a pipe 11 and a valve 10, and hydrogen chloride and chlorosilane are separated after condensation.
In the scheme, the adopted ionic liquid cation is hexyl triethyl ammonium ion, and the anion is N (CN) 2 - The ionic liquid is added in an amount of 144 kg of the mixture of the silicon polymer and the chlorosilane containing 1 silicon atom per 1800 kg of the mixture of the silicon polymer and the chlorosilane containing 1 silicon atom, and the concentration of the mixture of the silicon polymer and the chlorosilane containing 1 silicon atom is 30%. The pressure of the reactor was controlled at 0.25MPaG, the reaction temperature was 90 ℃, the molar ratio of anhydrous hydrogen chloride to polysilane was 3:1, and the conversion of the silicon polymer was 90%.
Example 2:
with the reactor shown in fig. 1, in the reactor 2, a silicon polymer, chlorosilane containing 1 silicon atom and a catalyst are added through a feed pipe 4 and a valve 3, anhydrous hydrogen chloride is added through a pipe 12 and a valve 13, a reaction product is withdrawn through a pipe 11 and a valve 10, and hydrogen chloride and chlorosilane are separated after condensation.
In the scheme, the adopted ionic liquid cation is hexyl triethyl ammonium ion, and the anion is N (CN) 2 - The ionic liquid is added in an amount of 200 kg per 1800 kg of the mixture of silicon polymer and chlorosilane containing 1 silicon atom, and the concentration of the mixture of silicon polymer and chlorosilane containing 1 silicon atom is 30%. The reactor pressure was controlled at 0.3MPaG, the reaction temperature was 100 ℃, the molar ratio of anhydrous hydrogen chloride to polysilane was 3:1, and the conversion of the silicon polymer was 91%.
Although specific embodiments of the invention have been described in detail and illustrated in the accompanying drawings, it is to be understood that various equivalent changes and modifications can be made by those skilled in the art without departing from the spirit of the invention as defined by the appended claims.
Claims (3)
1. A process for treating silicon polymer includes such steps as preparing chlorosilane containing 1 silicon atom by reaction of silicon polymer with anhydrous hydrogen chloride, and features that ionic liquid is used as catalyst, the silicon polymer and anhydrous hydrogen chloride are reacted in reactor at 30-180 deg.C and 0.02-1.2MPa to obtain chlorosilane product containing 1 silicon atom, the cation of ionic liquid is quaternary ammonium salt, and the anion of ionic liquid is CF 3 SO 3 - 、CF 3 COO - 、N(CF 3 SO 2 ) 2 - 、C(CF 3 SO 2 ) 3 - 、N(CN) 2 - The silicon polymer refers to a polysilicon byproduct high boiling substance containing the silicon polymer, and the silicon polymer and chlorosilane containing 1 silicon atom are added into a reactor together.
2. The method of claim 1, wherein the molar ratio of anhydrous hydrogen chloride to silicon polymer is between 0.5-30:1.
3. The method of claim 1, wherein the molar or mass ratio of catalyst to silicon polymer is between 1:1 and 200.
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| CN201811525561.8A CN109384233B (en) | 2018-12-13 | 2018-12-13 | Method for treating silicon polymers |
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| CN201811525561.8A CN109384233B (en) | 2018-12-13 | 2018-12-13 | Method for treating silicon polymers |
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| CN109384233B true CN109384233B (en) | 2023-10-20 |
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| CN113772677B (en) * | 2021-09-30 | 2023-03-28 | 四川永祥新能源有限公司 | Cracking reaction column and cracking process for byproduct chlorosilane high-boiling-point substances in polycrystalline silicon production |
| CN114288697A (en) * | 2022-01-11 | 2022-04-08 | 中国科学院过程工程研究所 | Cracking process method for reactive distillation of chlorosilane slag slurry |
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| CN1392151A (en) * | 2001-06-19 | 2003-01-22 | 浙江新安化工集团股份有限公司 | Process for preparing methyl silicane chloride |
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| CN101786629A (en) * | 2009-01-22 | 2010-07-28 | 陶氏康宁公司 | Method for recovering waste with high boiling point |
| JP2011026153A (en) * | 2009-07-22 | 2011-02-10 | Nippon Chem Ind Co Ltd | Ionic liquid-containing gel, producing method for the same and ion conductor |
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| CN105000564A (en) * | 2015-07-17 | 2015-10-28 | 江苏中能硅业科技发展有限公司 | Production method of dichlorosilane for preparing silane |
| CN105314637A (en) * | 2014-07-30 | 2016-02-10 | 江苏中能硅业科技发展有限公司 | Method and device for preparing halogenosilane through pyrolysis of halogen-silicon polymer |
| DE102016206090A1 (en) * | 2016-04-12 | 2017-10-12 | Wacker Chemie Ag | Process for the separation of aluminum chloride from silanes |
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2018
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Patent Citations (10)
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|---|---|---|---|---|
| US5292912A (en) * | 1993-07-19 | 1994-03-08 | Dow Corning Corporation | Catalytic conversion of direct process high-boiling component to chlorosilane monomers in the presence of hydrogen chloride |
| CN1126724A (en) * | 1994-09-08 | 1996-07-17 | 瓦克化学有限公司 | Method for preparation of methyl chlorsilane containing hydrogen |
| CN1392151A (en) * | 2001-06-19 | 2003-01-22 | 浙江新安化工集团股份有限公司 | Process for preparing methyl silicane chloride |
| DE102006029430A1 (en) * | 2006-06-27 | 2008-01-03 | Wacker Chemie Ag | Process for the preparation of organosilicon compounds by hydrosilylation in ionic liquids |
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| JP2011026153A (en) * | 2009-07-22 | 2011-02-10 | Nippon Chem Ind Co Ltd | Ionic liquid-containing gel, producing method for the same and ion conductor |
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| CN105314637A (en) * | 2014-07-30 | 2016-02-10 | 江苏中能硅业科技发展有限公司 | Method and device for preparing halogenosilane through pyrolysis of halogen-silicon polymer |
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