CN113233420B - Method for purifying hydrogen for producing electronic grade polycrystalline silicon - Google Patents
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of polycrystalline silicon preparation, and particularly relates to a method for purifying hydrogen for producing electronic grade polycrystalline silicon. The main technical scheme is as follows: and tail gas in the CVD process system is separated from tail gas, crude pure hydrogen obtained after separation enters an active carbon adsorption tower system to be adsorbed by phosphine, high-purity hydrogen obtained by treatment of a hydrogen treatment system before CVD is treated, and the high-purity hydrogen returns to the vapor deposition process system to be reused. The invention provides a method for purifying hydrogen for producing electronic grade polysilicon, which adopts a hydrogen treatment system before loading active carbon and CVD to carry out two-stage purification on crude purified hydrogen, carries out targeted removal on phosphine, and greatly improves the purity of circulating hydrogen; and the loaded active carbon firstly purifies the crude purified hydrogen, so that most of phosphine is preliminarily removed, the treatment capacity of a hydrogen treatment system for phosphine before CVD is reduced, and the equipment cost is reduced while the hydrogen purity is ensured.
Description
Technical Field
The invention belongs to the technical field of polycrystalline silicon preparation, and particularly relates to a method for purifying hydrogen for producing electronic grade polycrystalline silicon.
Background
Electronic grade polysilicon is a basic raw material for the integrated circuit industry, and is generally produced by adopting an improved Siemens method. Because the hydrogen gas is used as a reaction gas in the process of producing the polycrystalline silicon rod by CVD and also has the function of a carrier gas, the purity of the hydrogen gas greatly influences the purity of the polycrystalline silicon product, the proportion of the hydrogen gas in the CVD tail gas is high, the hydrogen gas needs to be separated and purified and then recycled, and the hydrogen is also called as recycle hydrogen. Meanwhile, the system has partial hydrogen loss in the operation process, and a small amount of fresh hydrogen needs to be supplemented into the system to keep the hydrogen balance.
Generally, the purification of hydrogen in the industry is carried out by carrying out primary separation and purification on hydrogen in CVD tail gas through deep cooling and chlorosilane cold washing, and then adopting an activated carbon adsorption tower for adsorption, but in the CVD process, a large amount of impurities containing P can react with hydrogen to generate PH3And is enriched in recycle hydrogen, in the existing hydrogen purification technology, aiming at PH3The purification effect is not ideal, and the PH in the circulating hydrogen is increased3The content is too high to meet the production requirement of high-purity electronic grade polysilicon.
In view of the defects of the existing hydrogen purification method in the electronic grade polysilicon industry, the inventor of the invention actively carries out research and innovation based on practical experience and professional knowledge which is rich in years of design and manufacture of the products and by matching with the application of theory, in order to create a method for purifying hydrogen for producing electronic grade polysilicon, adopts a two-stage purification mode of a hydrogen treatment system before loading activated carbon and CVD, greatly improves the purity of purified hydrogen, and loads the activated carbon to PH3Reducing the pH of a hydrogen treatment system prior to CVD3The treatment capacity of the method reduces the treatment cost, makes the design of treatment equipment more reasonable, and is suitable for industrialization. After continuous research and design and repeated trial production and improvement, the invention with practical value is finally created.
Disclosure of Invention
The invention aims to provide a method for purifying hydrogen for producing electronic grade polysilicon, which adopts a hydrogen treatment system before loading activated carbon and CVD to carry out two-stage purification on crude purified hydrogen, carries out targeted removal on phosphine and greatly improves the purity of circulating hydrogen; and the loaded active carbon firstly purifies the crude purified hydrogen, so that most of phosphine is preliminarily removed, the treatment capacity of a hydrogen treatment system for phosphine before CVD is reduced, and the equipment cost is reduced while the hydrogen purity is ensured.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a method for purifying hydrogen for producing electronic grade polysilicon, tail gas after CVD process is finished is separated through tail gas, crude pure hydrogen obtained after separation enters an active carbon adsorption tower system to be adsorbed by phosphine, high-purity hydrogen obtained after treatment of a hydrogen treatment system before CVD is carried out, and the high-purity hydrogen returns to a vapor deposition process system to be reused.
Furthermore, the active carbon adsorption tower system is formed by connecting a first adsorption tower, a second adsorption tower and a third adsorption tower in series, wherein the fillers in the first adsorption tower and the second adsorption tower are both active carbon, and the filler in the third adsorption tower is a composite filler of an active carbon-loaded metal catalyst. Active carbon is used as a carrier in the third adsorption tower, and a metal catalyst is loaded, so that one part of phosphine in the hydrogen is physically adsorbed in the third adsorption tower, the other part of the phosphine is chemically adsorbed, and the generated chemical adsorption is used for oxidizing the phosphine into phosphorus or metal phosphide and hydrogen, thereby achieving the purpose of removing the phosphine.
Further, the series sequence of the activated carbon adsorption tower system is a first adsorption tower, a second adsorption tower and a third adsorption tower from front to back. The reason why the third adsorption tower is placed last is that the composite packing in the third adsorption tower is adhered with phosphorus or metal phosphide, only the packing needs to be replaced frequently, and the operation cost can be effectively reduced by placing the third adsorption tower last.
Further, the composite filler is Co-Cu/AC, Zn-Cu/AC or Zn-Co/AC.
Further, the preparation method of the composite filler adopts a co-impregnation method, and active carbon is impregnated in the nitrate solution of the metal and then is roasted for 4 hours at 400 ℃.
Further, the surface of the composite filler is treated by a silane coupling agent. Because the process of crude purification of hydrogen is cryogenic cooling and chlorosilane leaching, the temperature of hydrogen entering an activated carbon adsorption tower system is lower, and the adsorption performance of the activated carbon on phosphine is reduced at low temperature, so that the desorption of the phosphine is seriously influenced, but when silane groups exist, the adsorption capacity of the activated carbon on the phosphine is greatly improved at low temperature, so that in the invention, after the surface treatment is carried out on the composite filler by adopting the silane coupling agent, a part of silane groups are grafted on the surfaces of the activated carbon and the metal catalyst, so that the adsorption capacity of the activated carbon on the phosphine at low temperature is improved.
Further, the method for carrying out surface treatment on the composite filler by adopting the silane coupling agent comprises the following steps: preparing a silane coupling agent into a 1.4wt% solution, wherein the solvent is a mixed solvent of ethanol and water (the volume ratio of ethanol to water is 9: 1), adjusting the pH to 4.5-5.5 with acetic acid, stirring for 30min to prehydrolyze the coupling agent, adding a composite filler, heating to 70 ℃ while stirring, reacting for 3h, filtering, and finally drying in an oven at 60 ℃ for 24h to obtain the composite filler with the surface treated by the silane coupling agent.
Further, the silane coupling agent is 1, 2-diethoxysilane or gamma-aminopropylsilane (gamma-APS).
Furthermore, the hydrogen treatment system before CVD adopts molecular sieve loaded Fe-Ni-Co ternary amorphous alloy as a catalyst. The invention adopts the molecular sieve loaded Fe-Ni-Co ternary amorphous alloy as the catalyst, the structural characteristics of the alloy are short-range order and long-range disorder state, the short-range order enables the amorphous alloy to contain more coordination unsaturated atoms, so that the amorphous alloy has more surface active centers, compared with the crystalline alloy, the catalytic efficiency is higher, the decomposition of phosphine is more thorough, the purity of hydrogen is effectively improved, the catalyst can catalyze phosphine participated by hydrogen to form product phosphorus, the phosphorus is adhered to the catalyst, the purity of the hydrogen is not influenced, and meanwhile, the PH formed by not catalyzing the phosphine to be P completely in an active carbon adsorption tower system2Further catalysis can be carried out, and solid phosphorus is finally generated. In the prior art, the catalyst for catalyzing phosphine into P mostly has the catalytic temperature of more than 300 ℃, but when the system temperature is too high, a metal container in the heating process can be causedAnd the metal such as the heating wire and the like generates metal pollution on the hydrogen, so that the purity of the hydrogen is influenced, and the three-way catalyst provided by the invention has the highest catalytic efficiency at the catalytic temperature of 200-250 ℃, so that the hydrogen is not polluted again, the temperature is the same as the inlet temperature of the hydrogen in the CVD process, the process step of returning the circulating hydrogen to the temperature treatment in the CVD process is saved, the time is saved, and the energy is saved.
Further, the preparation process of the molecular sieve loaded Fe-Ni-Co ternary amorphous alloy is as follows: preparing 0.05-0.15 mol/L nickel nitrate, 0.1-0.2 mol/L ammonium ferrous sulfate, 0.05-0.2 mol/L cobalt nitrate and 0.05-0.2 mol/L potassium borohydride, then immersing the molecular sieve in the solution, keeping stirring, taking out after maintaining for 60-120 minutes, and blowing and drying by nitrogen. The catalyst needs to be subjected to heat treatment after preparation, the treatment process is carried out in an adaptive reactor, nitrogen is used as protective gas, the temperature is increased from room temperature to 100-180 ℃ at the speed of 5-10 ℃/min, the temperature is kept for 120min, then the temperature is naturally reduced to room temperature, and the catalyst is filled into a hydrogen treatment system before CVD.
Furthermore, fresh hydrogen is supplemented before the crude purified hydrogen enters the active carbon adsorption tower system. The fresh hydrogen supplemented to the river is added into the activated carbon adsorption tower system, and the newly supplemented hydrogen is purified by the activated carbon adsorption tower and the pre-CVD hydrogen treatment system, so that the purity of the circulating hydrogen entering the CVD system is improved, and the flow rate of the supplemented fresh hydrogen is 0.3-2.0% of the circulating amount of the circulating hydrogen.
Further, when the active carbon system of the adsorption tower is used for adsorbing phosphine in the crude purified hydrogen, the adsorption temperature is-25 to-5 ℃, and the pressure is 8-15 barg.
Further, the processing temperature of the hydrogen processing system before CVD is 200-250 ℃, and the pressure is 3-5 barg.
Furthermore, the temperature in the CVD process is 200-250 ℃.
In conclusion, the invention has the following beneficial effects:
the invention provides a method for purifying hydrogen for producing electronic grade polysilicon, which adopts a hydrogen treatment system before loading active carbon and CVD to carry out two-stage purification on crude purified hydrogen, carries out targeted removal on phosphine, and greatly improves the purity of circulating hydrogen; and the loaded active carbon firstly purifies the crude purified hydrogen, so that most of phosphine is preliminarily removed, the treatment capacity of a hydrogen treatment system for phosphine before CVD is reduced, and the equipment cost is reduced while the hydrogen purity is ensured.
Drawings
FIG. 1 is a main flow chart of hydrogen purification according to the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the detailed description of the embodiments, features and effects of the method for purifying hydrogen for producing electronic grade polysilicon according to the present invention is provided below.
Example 1: method for purifying hydrogen for producing electronic grade polycrystalline silicon
As shown in the flow chart of hydrogen purification of fig. 1, the method for purifying hydrogen for producing electronic grade polysilicon provided by this embodiment specifically comprises the following operation steps:
s1, carrying out tail gas treatment on the hydrogen extracted from the CVD process system, wherein the treatment operation comprises conventional deep cooling and chlorosilane leaching;
s2, after the tail gas is treated, hydrogen is introduced into the activated carbon adsorption tower system, and fresh hydrogen is supplemented into the activated carbon adsorption tower system at the flow rate of 0.5 percent of the circulation amount of the hydrogen, so that the fresh hydrogen and the hydrogen treated in the step S1 are treated at the temperature of minus 25 ℃;
s3, introducing the hydrogen treated in the step S2 into a hydrogen treatment system before CVD, and removing impurities at 200 ℃ to obtain high-purity hydrogen;
and S4, sending the high-purity hydrogen obtained after the treatment in the step S3 back to the CVD process system.
Example 2: method for purifying hydrogen for producing electronic grade polycrystalline silicon
As shown in the flow chart of hydrogen purification of fig. 1, the method for purifying hydrogen for producing electronic grade polysilicon provided by this embodiment specifically comprises the following operation steps:
s1, carrying out tail gas treatment on the hydrogen extracted from the CVD process system, wherein the treatment operation comprises conventional deep cooling and chlorosilane leaching;
s2, after the tail gas is treated, hydrogen is introduced into the activated carbon adsorption tower system, and fresh hydrogen is supplemented into the activated carbon adsorption tower system at the flow rate of 1.5% of the circulation amount of the hydrogen, so that the fresh hydrogen and the hydrogen treated in the step S1 are treated at the temperature of minus 20 ℃;
s3, introducing the hydrogen treated in the step S2 into a hydrogen treatment system before CVD, and carrying out catalytic treatment at 250 ℃ to obtain high-purity hydrogen;
and S4, sending the high-purity hydrogen obtained after the treatment in the step S3 back to the CVD process system.
The active carbon adsorption tower system comprises a first adsorption tower, a second adsorption tower and a third adsorption tower, wherein fillers in the first adsorption tower and the second adsorption tower are active carbon, and fillers in the third adsorption tower are composite fillers Co-Cu/AC, and the preparation method comprises the following steps: dipping the activated carbon into a distilled water solution of cobalt nitrate and copper nitrate by adopting a co-dipping method, stirring for 3h, standing, dipping for 12h, filtering, and roasting at 400 ℃ for 4h under a nitrogen atmosphere.
Example 3: method for purifying hydrogen for producing electronic grade polycrystalline silicon
As shown in the flow chart of hydrogen purification of fig. 1, the method for purifying hydrogen for producing electronic grade polysilicon provided by this embodiment specifically comprises the following operation steps:
s1, carrying out tail gas treatment on the hydrogen extracted from the CVD process system, wherein the treatment operation comprises conventional deep cooling and chlorosilane leaching;
s2, after the tail gas is treated, hydrogen is introduced into the activated carbon adsorption tower system, and fresh hydrogen is supplemented into the activated carbon adsorption tower system at the flow rate of 1.5% of the circulation amount of the hydrogen, so that the fresh hydrogen and the hydrogen treated in the step S1 are treated at-10 ℃;
s3, introducing the hydrogen treated in the step S2 into a hydrogen treatment system before CVD, and carrying out catalytic treatment at 210 ℃ to obtain high-purity hydrogen;
and S4, sending the high-purity hydrogen obtained after the treatment in the step S3 back to the CVD process system.
The active carbon adsorption tower system comprises a first adsorption tower, a second adsorption tower and a third adsorption tower, wherein fillers in the first adsorption tower and the second adsorption tower are active carbon, and fillers in the third adsorption tower are composite fillers Co-Cu/AC, and the preparation method comprises the following steps: soaking activated carbon in a distilled water solution of cobalt nitrate and copper nitrate by a co-soaking method, stirring for 3 hours, standing, soaking for 12 hours, filtering, roasting at 400 ℃ for 4 hours under a nitrogen atmosphere, preparing 1.4wt% solution by using 1, 2-diethoxysilylethane, adjusting the pH to 4.5-5.5 by using acetic acid, stirring for 30 minutes to prehydrolyze a coupling agent, adding a composite filler, heating to 70 ℃ while stirring, reacting for 3 hours, filtering, and finally drying for 24 hours at 60 ℃ in an oven.
Example 4: method for purifying hydrogen for producing electronic grade polycrystalline silicon
As shown in the flow chart of hydrogen purification of fig. 1, the method for purifying hydrogen for producing electronic grade polysilicon provided by this embodiment specifically comprises the following operation steps:
s1, carrying out tail gas treatment on the hydrogen extracted from the CVD process system, wherein the treatment operation comprises conventional deep cooling and chlorosilane leaching;
s2, after the tail gas is treated, hydrogen is introduced into the activated carbon adsorption tower system, and fresh hydrogen is supplemented into the activated carbon adsorption tower system at the flow rate of 1.0% of the circulation amount of the hydrogen, so that the fresh hydrogen and the hydrogen treated in the step S1 are treated at-18 ℃;
s3, introducing the hydrogen treated in the step S2 into a hydrogen treatment system before CVD, and carrying out catalytic treatment at 220 ℃ by using a molecular sieve-loaded Fe-Ni-Co ternary amorphous alloy as a catalyst to obtain high-purity hydrogen;
and S4, sending the high-purity hydrogen obtained after the treatment in the step S3 back to the CVD process system.
Wherein, the filler and the composite filler in the active carbon adsorption tower system are the same as those in the embodiment 3, and the preparation method of the molecular sieve loaded Fe-Ni-Co ternary amorphous alloy comprises the following steps: preparing 0.05mol/L nickel nitrate, 0.1mol/L ammonium ferrous sulfate, 0.05mol/L cobalt nitrate and 0.05mol/L potassium borohydride, immersing the molecular sieve in the solution, keeping stirring, taking out after maintaining for 60 minutes, and blowing and drying by nitrogen. The catalyst needs to be subjected to heat treatment after preparation, the treatment process is carried out in an adaptive reactor, nitrogen is used as protective gas, the temperature is increased from room temperature to 100 ℃ at the speed of 5 ℃/min, the temperature is kept for 120min, then the temperature is naturally reduced to room temperature, and then the catalyst is filled into a hydrogen treatment system before CVD.
Example 5: method for purifying hydrogen for producing electronic grade polycrystalline silicon
As shown in the flow chart of hydrogen purification of fig. 1, the method for purifying hydrogen for producing electronic grade polysilicon provided by this embodiment specifically comprises the following operation steps:
s1, carrying out tail gas treatment on the hydrogen extracted from the CVD process system, wherein the treatment operation comprises conventional deep cooling and chlorosilane leaching;
s2, after the tail gas is treated, hydrogen is introduced into the activated carbon adsorption tower system, and fresh hydrogen is supplemented into the activated carbon adsorption tower system at the flow rate of 1.0% of the circulation amount of the hydrogen, so that the fresh hydrogen and the hydrogen treated in the step S1 are treated at-18 ℃;
s3, introducing the hydrogen treated in the step S2 into a hydrogen treatment system before CVD, and carrying out catalytic treatment at 220 ℃ by using a molecular sieve-loaded Fe-Ni-Co ternary amorphous alloy as a catalyst to obtain high-purity hydrogen;
and S4, sending the high-purity hydrogen obtained after the treatment in the step S3 back to the CVD process system.
The active carbon adsorption tower system comprises a first adsorption tower, a second adsorption tower and a third adsorption tower, wherein the fillers in the first adsorption tower and the second adsorption tower are active carbon, the filler in the third adsorption tower is a composite filler Cu-Zn/AC, and the preparation method comprises the following steps: soaking activated carbon in distilled water solution of cobalt nitrate and copper nitrate by co-soaking method, stirring for 3 hr, standing, soaking for 12 hr, filtering, roasting at 400 deg.C under nitrogen atmosphere for 4 hr, and preparing 1.4wt% solution with 1, 2-diethoxysilylethane, wherein the solvent is mixed solvent of ethanol and water (ethanol and water)The product ratio is 9: 1) adjusting pH to 4.5-5.5 with acetic acid, stirring for 30min to prehydrolyze the coupling agent, adding composite filler, heating to 70 deg.C under stirring for 3h, filtering, and drying in oven at 60 deg.C for 24 h; the preparation method of the molecular sieve-loaded Fe-Ni-Co ternary amorphous alloy comprises the following steps: preparing 0.05mol/L nickel nitrate, 0.1mol/L ammonium ferrous sulfate, 0.05mol/L cobalt nitrate and 0.05mol/L potassium borohydride, immersing the molecular sieve in the solution, keeping stirring, taking out after maintaining for 60 minutes, and blowing and drying by nitrogen. The catalyst needs to be subjected to heat treatment after preparation, the treatment process is carried out in an adaptive reactor, nitrogen is used as protective gas, the temperature is increased from room temperature to 100 ℃ at the speed of 5 ℃/min, the temperature is kept for 120min, then the temperature is naturally reduced to room temperature, and then the catalyst is filled into a hydrogen treatment system before CVD. As the direct measurement and detection limit of phosphine in gas-phase hydrogen is higher, the PH value in hydrogen cannot be represented3The amount of impurities is characterized by adopting a mode of producing a polycrystalline silicon product by a small inspection furnace, wherein the phosphorus in the hydrogen which is sent back to the CVD process system in the embodiment 1-5 of the invention is represented, and during normal production, the average value of the phosphorus content in the polycrystalline silicon is 25pptw, and the result is as follows:
TABLE 1 phosphorus content in examples 1 to 5
| Examples | Phosphorus content/pptw |
| Example 1 | 18 |
| Example 2 | 17.5 |
| Example 3 | 17.2 |
| Example 4 | 16.9 |
| Example 5 | 16.5 |
The test results show that in the hydrogen purification scheme provided by the invention, phosphine in the circulating hydrogen can be effectively removed.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A method for purifying hydrogen used for producing electronic grade polysilicon is characterized in that tail gas in a CVD process system is separated through the tail gas, crude pure hydrogen obtained after separation enters an active carbon adsorption tower system to be adsorbed by phosphine, high-purity hydrogen obtained after treatment of a hydrogen treatment system before CVD is carried out, and the high-purity hydrogen returns to a vapor deposition process system to be reused; the hydrogen treatment system before CVD adopts a molecular sieve loaded Fe-Ni-Co ternary amorphous alloy as a catalyst; the preparation method of the molecular sieve-loaded Fe-Ni-Co ternary amorphous alloy comprises the following steps: preparing 0.05-0.15 mol/L nickel nitrate, 0.1-0.2 mol/L ammonium ferrous sulfate, 0.05-0.2 mol/L cobalt nitrate and 0.05-0.2 mol/L potassium borohydride, then immersing the molecular sieve in the solution, keeping stirring, taking out after maintaining for 60-120 minutes, and blowing and drying by nitrogen.
2. The method for purifying hydrogen used for producing electronic grade polysilicon according to claim 1, wherein the activated carbon adsorption tower system is composed of a first adsorption tower, a second adsorption tower and a third adsorption tower which are connected in series, wherein the fillers in the first adsorption tower and the second adsorption tower are both activated carbon, and the filler in the third adsorption tower is a composite filler of activated carbon loaded with metal catalyst.
3. The method for purifying hydrogen for producing electronic grade polysilicon according to claim 2, wherein the composite filler is Co-Cu/AC, Zn-Cu/AC or Zn-Co/AC.
4. The method for purifying hydrogen for producing electronic grade polysilicon according to claim 2 or 3, wherein the surface of the composite filler is treated by a silane coupling agent.
5. The method for purifying hydrogen for producing electronic grade polysilicon according to claim 1, wherein the silane coupling agent is 1, 2-diethoxysilane or gamma-aminopropylsilane (gamma-APS).
6. The method for purifying hydrogen used for producing electronic grade polysilicon according to claim 1, wherein the crude purified hydrogen is supplemented with fresh hydrogen before entering an activated carbon adsorption tower system.
7. The method for purifying hydrogen for producing electronic grade polysilicon according to claim 1, wherein the adsorption temperature of the activated carbon adsorption tower system is-25 to-5 ℃ and the pressure is 8 to 15barg when the activated carbon adsorption tower system adsorbs phosphine in the crude purified hydrogen.
8. The method for purifying hydrogen for producing electronic grade polycrystalline silicon according to claim 1, wherein the treatment temperature of the hydrogen treatment system before CVD is 200-250 ℃ and the pressure is 3-5 barg.
9. The method for purifying hydrogen for producing electronic grade polysilicon according to claim 1, wherein the temperature in the CVD process is 200-250 ℃.
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