CN114505084B - Pretreatment method of cuprous chloride catalyst - Google Patents
Pretreatment method of cuprous chloride catalyst Download PDFInfo
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- CN114505084B CN114505084B CN202210053170.0A CN202210053170A CN114505084B CN 114505084 B CN114505084 B CN 114505084B CN 202210053170 A CN202210053170 A CN 202210053170A CN 114505084 B CN114505084 B CN 114505084B
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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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
- 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
Abstract
The application relates to the technical field of polysilicon production processes, in particular to a pretreatment method of a cuprous chloride catalyst. The method comprises the steps of filling cuprous chloride and Si silicon powder into a tube bullet reactor, increasing the partial pressure of the cuprous chloride through a vacuum environment, converting the solid phase into a gas phase, accelerating the diffusion rate of the cuprous chloride, and forming uniformly dispersed copper silicon active centers; thereby accelerating the adsorption, deposition and reaction of cuprous chloride on the surface of the silicon particles and reducing the deactivation caused by Cu sintering. The embodiment proves that the induction period can be shortened, the silicon tetrachloride catalysis efficiency can be improved, the reaction efficiency of cold hydrogenation can be improved, and the amount of copper impurities in a later system can be reduced by carrying out the cold hydrogenation reaction of the silicon tetrachloride after the pretreatment of the cuprous chloride and the Si silicon powder. The method provided by the application has the advantages of low equipment requirement, simple preparation process, low energy consumption and obvious promotion of cold hydrogenation reaction effect.
Description
Technical Field
The application relates to the technical field of polysilicon production processes, in particular to a pretreatment method of a cuprous chloride catalyst.
Background
The improved Siemens method is a main flow process for producing the polysilicon, and has the main defects that the hydrogenation efficiency of the silicon tetrachloride in the tail gas recovery unit is low, the byproduct of the silicon tetrachloride exceeds 15t per 1t of polysilicon produced, the silicon tetrachloride belongs to extremely toxic substances, the environment is seriously polluted, and the production and reduction of the polysilicon are regulated in ChinaThe recovery and utilization rate of the silicon tetrachloride in the tail gas is not lower than 98.5 percent. The most effective measure is to hydrogenate and convert silicon tetrachloride into trichlorosilane in the production process of polysilicon, and recycle the silicon tetrachloride. At present, the domestic polysilicon hydrogenation method mostly adopts a cold hydrogenation technology: siCl 4 +3Si+2H 2 →4SiHCl 3 Namely, silicon powder, hydrogen and silicon tetrachloride are subjected to gas-solid reaction in a fluidized bed/fixed bed under the action of a catalyst. The reaction temperature is 400-600 ℃, the pressure is 1-4MPa, the molar feed ratio of hydrogen to silicon tetrachloride is 1-10, and most of the used catalysts are copper-based catalysts.
It has been studied to consider the active phase of the catalyst in the cold hydrogenation process as copper silicon compounds. In the fluidized bed, the CuCl catalyst is contacted with silicon particles to be reduced, and SiCl is generated by reaction 4 And active free Cu, the irregular diffusion of Cu in the Si particle body causes the particle surface to discretely form "Cu-Si" compounds. When H is introduced into 2 And SiCl 4 After that, the "Cu-Si" compound catalyzes SiCl 4 Hydrogenation reaction of (C) to form HCl and SiHCl 3 Copper is continuously etched on the surface of the catalyst until the silicon reaction is complete. Therefore, accelerating the formation of "Cu-Si" compounds has become an important point for increasing the rate of cold hydrogenation reactions. In the current industrial production, copper catalyst is continuously lost due to low melting point and easy volatilization loss of cuprous chloride, and the cuprous chloride is continuously added into a fluidized bed reactor in use, so that the production cost is increased. At present, no better catalyst pretreatment method is reported.
Disclosure of Invention
Aiming at the technical problems, the application provides a cuprous chloride catalyst pretreatment method. The method effectively shortens the induction period of the catalyst in the cold hydrogenation process of the silicon tetrachloride, accelerates the reaction between the solid phase catalyst and the solid phase silicon powder, and improves the catalytic efficiency of the cuprous chloride.
The specific technical scheme of the application is as follows:
the application provides a pretreatment method of a catalyst in a silicon tetrachloride cold hydrogenation process, which comprises the following steps: putting CuCl and silicon powder into a closed reactor, replacing air in the closed reactor with inert gas, heating to react for a period of time, and cooling to room temperature to finish the pretreatment process.
Further, the mass ratio of the CuCl to the silicon powder is 10:1-2.
Preferably, the reaction temperature of the heating reaction is 400-550 ℃ and the reaction time is 1-10 hours.
The silicon powder is pickled silicon powder.
Preferably, the closed reactor is a tube bullet reactor, and further, the outlet of the tube bullet reactor is connected with an air bag or a vacuum air pump.
Preferably, the inert gas is nitrogen or argon.
Further, the pretreatment process is in a vacuum state, and the vacuum degree is-0.09 Mpa.
Compared with the prior art, the application has the beneficial effects that:
the application loads the uniformly mixed cuprous chloride and Si silicon powder into the tube bullet reactor, uses a vacuum pump to vacuumize in the heating process, increases the partial pressure of the cuprous chloride in the vacuum environment, makes the cuprous chloride converted from a solid phase into a gas phase, accelerates the diffusion rate of the cuprous chloride, and forms uniformly dispersed copper silicon active centers. Thereby accelerating the adsorption, deposition and reaction of cuprous chloride on the surface of the silicon particles and reducing the deactivation caused by Cu sintering. Meanwhile, the products such as gas generated by the reaction can be discharged in time, and the forward progress of the reaction, namely the generation of a copper silicon active phase, is promoted. And after the pretreatment is finished, directly placing the reaction product containing the copper silicon compound into a fixed bed to carry out silicon tetrachloride cold hydrogenation reaction. The embodiment proves that the pretreatment of the cuprous chloride and the Si silicon powder can shorten the induction period, improve the catalysis efficiency of the silicon tetrachloride, further improve the reaction efficiency of cold hydrogenation and reduce the amount of copper impurities in a later system. The method provided by the application has the advantages of low equipment requirement, simple preparation process, low energy consumption and obvious promotion of cold hydrogenation reaction effect.
Drawings
FIG. 1 is a schematic diagram of a tube bomb reactor; in the figure, (1) lining quartz glass, (2) graphite gasket, (3) flange, (4) pressure gauge, (5) needle valve, (6) three-way valve, (7) first export, and (8) second export.
FIG. 2 is a graph comparing the conversion after pretreatment of the catalyst without pretreatment and examples 2 to 4.
Detailed Description
The application is further illustrated by the following examples: those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present application. While the methods and applications of this application have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this application, without departing from the spirit or scope of the application. The experimental methods in the examples, for which specific conditions were not noted, were all according to conventional conditions; the reagents and biological materials used, unless otherwise specified, are commercially available.
Comparative example 1:
8g of the pickled silicon powder and 1.6g of cuprous chloride (CuCl) are weighed, fully mixed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, and the molar ratio of hydrogen to silicon tetrachloride is 4:1. The conversion of silicon tetrachloride after the reaction was found to be 14.61%.
Example 1:
2g of CuCl and 10g of Si powder after acid washing are fully mixed, placed in a closed reactor and replaced by nitrogen for a plurality of times, so as to ensure that the inside is free from air. Then heating to 450 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 3 hours, sealing the reaction system in the whole reaction process, and gradually raising the pressure to 4atm (standard atmospheric pressure) after the reaction is completed. After cooling to room temperature, 9.6g of treated silicon powder is weighed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, and the molar ratio of hydrogen to silicon tetrachloride is 4:1. The silicon tetrachloride conversion after the reaction was found to be 14.17%.
Example 2:
fully mixing 2g of CuCl and 10g of pickled Si powder, placing the mixture in a tube bullet reactor, introducing nitrogen, and replacing for a plurality of times to ensure that no air exists in the mixture, wherein an outlet of the tube bullet reactor is connected with an air bag with the volume of 10L, so that the pressure of a reaction system is always normal pressure. Heating to 450 ℃ at a heating rate of 10 ℃/min, and keeping the temperature for 3 hours. After cooling to room temperature, 9.6g of treated silicon powder is weighed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, the molar ratio of hydrogen to silicon tetrachloride is 4:1, and the silicon tetrachloride conversion rate is 15.48%.
FIG. 1 is a schematic diagram of a tube bullet reactor; as shown in fig. 1, the tube bullet reactor comprises (1) lining quartz glass, (2) a graphite gasket, (3) a flange, (4) a pressure gauge, (5) a needle valve, and (6) a three-way valve; the three-way valve (6) comprises a first outlet (7) connected with a steel cylinder for replacing gas in the tube bullet reactor and a second outlet (8) connected with an air bag or a vacuum pump.
Example 3:
fully mixing 2g of CuCl and 10g of pickled Si powder, placing the mixture in a tube bullet reactor, introducing nitrogen, and replacing for a plurality of times to ensure that the interior is free of air, and vacuumizing an outlet of the tube bullet reactor by a vacuum pump, wherein the vacuum degree is kept at-0.09 MPa in the whole process. Heating to 450 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 3 hours, and cooling to room temperature. 9.6g of the treated silicon powder is weighed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, the molar ratio of hydrogen to silicon tetrachloride is 4:1, and the silicon tetrachloride conversion rate is 21.15%.
Example 4:
fully mixing 1g of CuCl and 10g of pickled Si powder, placing the mixture in a tube bullet reactor, introducing nitrogen, and replacing for a plurality of times to ensure that the interior is free of air, and vacuumizing an outlet of the tube bullet reactor by a vacuum pump, wherein the vacuum degree is kept at-0.09 MPa in the whole process. Heating to 450 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 3 hours, and cooling to room temperature. 8.8g of the treated silicon powder is weighed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, the molar ratio of hydrogen to silicon tetrachloride is 4:1, and the silicon tetrachloride conversion rate is 19.14%.
FIG. 2 is a graph comparing the conversion after pretreatment of the catalyst without pretreatment and in examples 2-4; as can be seen from fig. 2, the conversion rate of silicon tetrachloride after pretreatment of the catalyst has a significant increase, and the conversion rate after pretreatment in a vacuum state is increased to about 20%.
Example 5:
2g of CuCl and 10g of Si powder after pickling are thoroughly mixed, placed in a tube bomb reactor and replaced with nitrogen for a plurality of times to ensure that the inside is free of air. Heating to 400 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 3 hours, and vacuumizing by using a vacuum pump in the whole process, wherein the vacuum degree is-0.09 MPa. 9.6g of the treated silicon powder is weighed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, the molar ratio of hydrogen to silicon tetrachloride is 4:1, and the silicon tetrachloride conversion rate is 20.61%.
Example 6:
2g of CuCl and 10g of Si powder after pickling are thoroughly mixed, placed in a tube bomb reactor and replaced with nitrogen for a plurality of times to ensure that the inside is free of air. Heating to 500 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 3 hours, and vacuumizing by using a vacuum pump in the whole process, wherein the vacuum degree is-0.09 MPa. 9.6g of the treated silicon powder is weighed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, the molar ratio of hydrogen to silicon tetrachloride is 4:1, and the silicon tetrachloride conversion rate is 19.66%.
Example 7:
2g of CuCl and 10g of Si powder after acid washing are fully mixed, placed in a closed reactor and replaced by nitrogen for a plurality of times, so as to ensure that the inside is free from air. Heating to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 3 hours, and vacuumizing by using a vacuum pump in the whole process, wherein the vacuum degree is-0.09 MPa. 9.6g of the treated silicon powder is weighed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, the molar ratio of hydrogen to silicon tetrachloride is 4:1, and the silicon tetrachloride conversion rate is 22.70%.
Example 8:
2g of CuCl and 10g of Si powder after acid washing are fully mixed, placed in a closed reactor and replaced by argon for a plurality of times, so as to ensure that the inside is free from air. Heating to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 1h, and vacuumizing by using a vacuum pump in the whole process, wherein the vacuum degree is-0.09 MPa. 9.6g of the treated silicon powder is weighed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, the molar ratio of hydrogen to silicon tetrachloride is 4:1, and the silicon tetrachloride conversion rate is 19.88%.
Example 9:
2g of CuCl and 10g of Si powder after acid washing are fully mixed, placed in a closed reactor and replaced by argon for a plurality of times, so as to ensure that the inside is free from air. Heating to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5 hours, and vacuumizing by using a vacuum pump in the whole process, wherein the vacuum degree is-0.09 MPa. 9.6g of the treated silicon powder is weighed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, the molar ratio of hydrogen to silicon tetrachloride is 4:1, and the silicon tetrachloride conversion rate is 21.07%.
Example 10:
2g of CuCl and 10g of Si powder after acid washing are fully mixed, placed in a closed reactor and replaced by argon for a plurality of times, so as to ensure that the inside is free from air. Heating to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 10 hours, and vacuumizing by using a vacuum pump in the whole process, wherein the vacuum degree is-0.09 MPa. 9.6g of the treated silicon powder is weighed and filled into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, the reaction pressure is normal pressure, the hydrogen flow rate is 200mL/min, the molar ratio of hydrogen to silicon tetrachloride is 4:1, and the silicon tetrachloride conversion rate is 21.35%.
TABLE 1 comparison of the influence of pretreatment on Cold hydrogenation reactions
From table 1, silicon tetrachloride cold hydrogenation reaction can be performed after silicon powder and cuprous chloride are pretreated, so that silicon tetrachloride catalytic efficiency can be improved, and further reaction efficiency of cold hydrogenation is improved. The pretreatment reaction increases the partial pressure of the cuprous chloride, so that the cuprous chloride is converted into a gas phase from a solid phase, the diffusion rate of the cuprous chloride is accelerated, and uniformly dispersed copper-silicon active centers are formed. And the pretreatment reaction accelerates the adsorption, deposition and reaction of cuprous chloride on the surface of the silicon particles and reduces the deactivation caused by Cu sintering. Meanwhile, the products such as gas generated by the reaction can be discharged in time, and the forward progress of the reaction is promoted.
The above list of detailed descriptions is only specific to practical embodiments of the present application, and they are not intended to limit the scope of the present application, and all equivalent embodiments or modifications that do not depart from the spirit of the present application should be included in the scope of the present application.
Claims (3)
1. The pretreatment method of the catalyst in the cold hydrogenation process of silicon tetrachloride is characterized by comprising the following steps: putting CuCl and silicon powder into a closed reactor, replacing air in the closed reactor with inert gas, heating to react for a period of time, and cooling to room temperature to complete the pretreatment process; the mass ratio of CuCl to silicon powder is 1-2:10, the pretreatment process is in a vacuum state, the vacuum degree is-0.09 Mpa, the reaction temperature of the heating reaction is 400-550 ℃, the reaction time is 1-10 hours, the closed reactor is a tube bullet reactor, and an outlet of the tube bullet reactor is connected with an air bag or a vacuum air pump.
2. The pretreatment method as recited in claim 1, wherein the silicon powder is a silicon powder after pickling.
3. The pretreatment method according to claim 1, wherein the inert gas is nitrogen or argon.
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