CN114505084A - Pretreatment method of cuprous chloride catalyst - Google Patents
Pretreatment method of cuprous chloride catalyst Download PDFInfo
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- CN114505084A CN114505084A CN202210053170.0A CN202210053170A CN114505084A CN 114505084 A CN114505084 A CN 114505084A CN 202210053170 A CN202210053170 A CN 202210053170A CN 114505084 A CN114505084 A CN 114505084A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- 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
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- C01B33/00—Silicon; Compounds thereof
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- 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
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Abstract
The invention relates to the technical field of polycrystalline silicon production processes, in particular to a pretreatment method of a cuprous chloride catalyst. Cuprous chloride and Si silicon powder are filled in a tube elastic reactor, the partial pressure of the cuprous chloride is increased through a vacuum environment, the cuprous chloride is converted from a solid phase to a gas phase, the diffusion rate of the cuprous chloride is accelerated, and a uniformly dispersed copper silicon active center is formed; thereby accelerating the adsorption, deposition and reaction of cuprous chloride on the surface of silicon particles and reducing the deactivation caused by Cu sintering. The embodiment proves that the cold hydrogenation reaction of the silicon tetrachloride after the cuprous chloride and the Si silicon powder are pretreated can shorten the induction period, improve the catalytic efficiency of the silicon tetrachloride, improve the reaction efficiency of the cold hydrogenation and reduce the amount of copper impurities in a rear system. The method provided by the invention has the advantages of low requirement on equipment, simple preparation process, low energy consumption and obvious promotion on cold hydrogenation reaction effect.
Description
Technical Field
The invention relates to the technical field of polycrystalline silicon production processes, in particular to a pretreatment method of a cuprous chloride catalyst.
Background
The improved Siemens method is a mainstream process for producing polycrystalline silicon, and has the main defects that the hydrogenation efficiency of silicon tetrachloride in a tail gas recovery unit is low, the by-product exceeds 15t of silicon tetrachloride when 1t of polycrystalline silicon is produced, the silicon tetrachloride belongs to a highly toxic substance and seriously pollutes the environment, and the recovery utilization rate of the silicon tetrachloride in the tail gas generated by reducing the polycrystalline silicon production is not lower than 98.5 percent according to the national regulations. The most effective measure is to hydrogenate the silicon tetrachloride to be converted into trichlorosilane in the production process of the polysilicon and recycle the silicon tetrachloride. At present, the domestic polycrystalline silicon hydrogenation method mostly adopts a cold hydrogenation technology: SiCl4+3Si+2H2→4SiHCl3Namely, the silicon powder, the hydrogen and the silicon tetrachloride generate 'gas-solid' reaction in a fluidized bed/fixed bed under the action of the catalyst. The reaction temperature is 400-600 ℃, the pressure is 1-4MPa, the molar feeding ratio of hydrogen to silicon tetrachloride is 1-10, and most of the used catalysts are copper-based catalysts.
It is believed that the active phase of the catalyst during cold hydrogenation is a copper silicon compound. The CuCl catalyst and silicon particles are reduced by mutual contact in the fluidized bed to generate SiCl4And active free Cu, wherein the irregular diffusion of Cu in the bulk of Si particles leads the surface of the particles to discretely form a Cu-Si compound. When H is introduced2And SiCl4The latter "Cu-Si" compound catalyzes SiCl4Hydrogenation reaction of (A) to form HCl and SiHCl3And the copper is continuously etched on the surface of the catalyst until the silicon reaction is complete. Therefore, the formation of the "Cu-Si" compound is accelerated, which is the key point for increasing the cold hydrogenation reaction rate. In the current industrial production, because cuprous chloride has low melting point and is easy to volatilize and lose, the copper catalyst is continuously lost, and the cuprous chloride needs to be continuously supplemented into the fluidized bed reactor when in use, thereby increasing the production cost. At present, no better catalyst pretreatment method is reported.
Disclosure of Invention
In order to solve 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 invention is as follows:
the invention provides a pretreatment method of a catalyst in a silicon tetrachloride cold hydrogenation process, which comprises the following steps: and (3) placing the CuCl and the silicon powder into a closed reactor, replacing air in the closed reactor with inert gas, heating for reaction 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 acid-washed silicon powder.
Preferably, the closed reactor is a tube bomb reactor, and further, an air bag or a vacuum air pump is connected to an outlet of the tube bomb reactor.
Preferably, the inert gas is nitrogen or argon.
Furthermore, the pretreatment process is in a vacuum state, and the vacuum degree is-0.09 Mpa.
Compared with the prior art, the invention has the beneficial effects that:
the invention is characterized in that the uniformly mixed cuprous chloride and Si silicon powder are filled in a tube elastic reactor, a vacuum pump is used for pumping vacuum in the temperature rising process, the partial pressure of the cuprous chloride is increased in the vacuum environment, the cuprous chloride is converted from a solid phase to a gas phase, the diffusion rate of the cuprous chloride is accelerated, and uniformly dispersed copper silicon active centers are formed. Thereby accelerating the adsorption, deposition and reaction of cuprous chloride on the surface of silicon particles and reducing the deactivation caused by Cu sintering. Meanwhile, products such as gases generated by the reaction can be discharged in time, and the forward progress of the reaction, namely the generation of the copper silicon active phase, is promoted. And after the pretreatment is finished, directly putting the reaction product containing the copper silicon compound into a fixed bed for carrying out a silicon tetrachloride cold hydrogenation reaction. The embodiment proves that the induction period can be shortened and the silicon tetrachloride catalytic efficiency can be improved after the cuprous chloride and the Si silicon powder are pretreated, so that the reaction efficiency of cold hydrogenation is improved, and the amount of copper impurities in a rear system can be reduced. The method provided by the invention has the advantages of low requirement on equipment, simple preparation process, low energy consumption and obvious promotion on cold hydrogenation reaction effect.
Drawings
FIG. 1 is a schematic view of a tube and bomb reactor; in the figure, (1) quartz glass is lined, (2) a graphite gasket, (3) a flange, (4) a pressure gauge, (5) a needle valve, (6) a three-way valve, (7) a first outlet and (8) a second outlet.
FIG. 2 is a graph comparing the conversion without pretreatment and after pretreatment of the catalyst in examples 2-4.
Detailed Description
The invention is further illustrated by the following examples: those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention. The experimental methods in the examples, which are not indicated for specific conditions, are carried out according to conventional conditions; the reagents and biological materials used, unless otherwise specified, are commercially available.
Comparative example 1:
weighing 8g of silicon powder after being washed by acid and 1.6g of cuprous chloride (CuCl), fully mixing, and filling into a fixed bed reactor for cold hydrogenation reaction. The reaction conditions are as follows: after nitrogen purging, heating to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, wherein 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 complete was determined to be 14.61%.
Example 1:
2g of CuCl and 10g of the Si powder after acid washing are fully mixed, placed in a closed reactor and replaced by nitrogen for many times, so that the inside is ensured to be free of air. Then the temperature is increased to 450 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 3h, the reaction system is closed in the whole reaction process, and the pressure is gradually increased to 4atm (standard atmospheric pressure) after the reaction is finished. After the temperature is reduced 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 ℃ in the nitrogen atmosphere at the heating rate of 10 ℃/min, 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 complete was determined to be 14.17%.
Example 2:
fully mixing 2g of CuCl and 10g of the acid-washed Si powder, placing the mixture in a tube bomb reactor, introducing nitrogen, performing multiple replacement to ensure that no air exists in the tube bomb reactor, and connecting an air bag with the volume of 10L to an outlet of the tube bomb reactor to ensure that the pressure of a reaction system is always normal pressure. Heating to 450 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 3 h. After the temperature is reduced 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 the heating rate of 10 ℃/min in the 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 illustration of a tube and bomb reactor; as shown in fig. 1, the tube elastic reactor comprises (1) a 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 bomb 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 the pickled Si powder, placing the mixture in a tube-bomb reactor, introducing nitrogen, repeatedly replacing the mixture to ensure that the interior of the tube-bomb reactor is free from air, connecting an outlet of the tube-bomb reactor with a vacuum pump for vacuum pumping, and keeping the vacuum degree at-0.09 MPa in the whole process. Heating to 450 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 3h, 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 the heating rate of 10 ℃/min in the 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:
and (3) fully mixing 1g of CuCl and 10g of the pickled Si powder, placing the mixture in a tube-bomb reactor, introducing nitrogen, repeatedly replacing to ensure that no air exists in the tube-bomb reactor, connecting an outlet of the tube-bomb reactor with a vacuum pump for vacuum pumping, and keeping the vacuum degree at-0.09 MPa in the whole process. Heating to 450 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 3h, and cooling to room temperature. And 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 the heating rate of 10 ℃/min in the 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 conversion without pretreatment and after pretreatment of the catalyst in examples 2-4; as can be seen from FIG. 2, the conversion rate of silicon tetrachloride of the catalyst after pretreatment is obviously increased, and the conversion rate after pretreatment in a vacuum state is increased to about 20%.
Example 5:
2g of CuCl and 10g of the Si powder after acid washing were thoroughly mixed, placed in a tube bomb reactor, and replaced with nitrogen for many times to ensure that the inside was free from air. Heating to 400 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 3h, 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 the heating rate of 10 ℃/min in the 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 the Si powder after acid washing were thoroughly mixed, placed in a tube bomb reactor, and replaced with nitrogen for many times to ensure that the inside was free from air. Heating to 500 deg.C at a heating rate of 10 deg.C/min, maintaining the temperature for 3h, and vacuumizing with a vacuum pump to-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 the heating rate of 10 ℃/min in the 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 the Si powder after acid washing are fully mixed, placed in a closed reactor and replaced by nitrogen for many times, so that the inside is ensured to be free of air. Heating to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 3h, 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 the heating rate of 10 ℃/min in the 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 the Si powder after acid washing are fully mixed, placed in a closed reactor and replaced by argon for multiple times, and the inside is ensured to be free of air. Heating to 550 ℃ at the 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 the heating rate of 10 ℃/min in the 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 the Si powder after acid washing are fully mixed, placed in a closed reactor and replaced by argon for multiple times, and the inside is ensured to be free of air. Heating to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 5h, 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 the heating rate of 10 ℃/min in the 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 the Si powder after acid washing are fully mixed, placed in a closed reactor and replaced by argon for multiple times, and the inside is ensured to be free of air. Heating to 550 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10h, 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 the heating rate of 10 ℃/min in the 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 Effect of pretreatment mode on Cold hydrogenation reactions
As can be seen from Table 1, the catalytic efficiency of silicon tetrachloride can be improved by pretreating silicon powder and cuprous chloride and then carrying out the cold hydrogenation reaction of silicon tetrachloride, so that the reaction efficiency of the cold hydrogenation is improved. The reason is that the partial pressure of cuprous chloride is increased by the pretreatment reaction, so that the cuprous chloride is converted from a solid phase to a gas 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 silicon particles and reduces the deactivation caused by Cu sintering. Meanwhile, products such as gas generated by the reaction can be discharged in time, and the forward progress of the reaction is promoted.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method for pretreating a catalyst in a silicon tetrachloride cold hydrogenation process is characterized by comprising the following steps: and (3) placing the CuCl and the silicon powder into a closed reactor, replacing air in the closed reactor with inert gas, heating for reaction for a period of time, and cooling to room temperature to finish the pretreatment process.
2. The pretreatment method according to claim 1, wherein the mass ratio of the CuCl to the silicon powder is 10: 1-2.
3. The pretreatment method according to claim 1, wherein the reaction temperature of the heating reaction is 400 to 550 ℃ and the reaction time is 1 to 10 hours.
4. The pretreatment method according to claim 1, wherein the silicon powder is acid-washed silicon powder.
5. The pretreatment method according to claim 1, wherein the closed reactor is a tube and bomb reactor.
6. The pretreatment method of claim 5, wherein an air bag or a vacuum air pump is connected to the outlet of the tube and bomb reactor.
7. The pretreatment method according to claim 1, wherein the inert gas is nitrogen or argon.
8. The pretreatment method according to claim 1, wherein the pretreatment process is carried out under a vacuum of-0.09 MPa.
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