CN105293438B - A kind of method and device of circulating hydrogen repurity - Google Patents
A kind of method and device of circulating hydrogen repurity Download PDFInfo
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- CN105293438B CN105293438B CN201510820198.2A CN201510820198A CN105293438B CN 105293438 B CN105293438 B CN 105293438B CN 201510820198 A CN201510820198 A CN 201510820198A CN 105293438 B CN105293438 B CN 105293438B
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Abstract
A kind of method and device of circulating hydrogen repurity provided by the invention, is related to field of polysilicon production.By circulating hydrogen by adsorption-edulcoration, boron and P elements impurity content in hydrogen is set to be down to a kind of 0.1 below ppba method and device by 10 ppba.Circulating hydrogen specifically is passed first into hydrogen cooler to be cooled down, by hydrogen_cooling between 0~30 DEG C, into primary adsorption reaction column, Adsorption is containing the impurity based on boron element；Circulating hydrogen after primary adsorption enters back into Hydrogen cryogenic device, by hydrogen_cooling between 88~68 DEG C, into secondary absorption reaction column, and the impurity based on Adsorption phosphorus element-containing.The present invention realizes that the adsorption reaction of circulating hydrogen removes the objectionable impurities such as boron, P elements, significantly reduce boracic in hydrogen, the content of P elements impurity, the quality of circulating hydrogen is improved, makes it possible improved Siemens stable yields electronic-grade polycrystalline silicon, breaches the technology blockage of foreign countries.The technological process is simple, easy to operate, and impurity-eliminating effect is obvious.
Description
Technical field
The present invention relates to returned in electronic-grade polycrystalline silicon production field, the particularly recovery of improved Siemens reduction tail gas dry process
Receive hydrogen（Circulating hydrogen）Boron, P elements impurity removal.
Background technology
Polysilicon is semiconductor, the basic material of solar energy industry, is to manufacture silicon polished, solar cell and HIGH-PURITY SILICON
The primary raw material of product, is Information of Development industry and the important foundation stone of New Energy Industry, and this causes being produced into for raw material polysilicon
For focus industry.In the last few years, polysilicon industry development in China's was swift and violent, and its size of capacity has leapt to the first in the world, but by skill
The various factors such as art block influence, and the country can not still realize the target of stable yields electronic-grade polycrystalline silicon.Therefore polysilicon purity is got over
Carry out higher requirement so that how effectively to remove the impurity in polysilicon, research and development electronic-grade polycrystalline silicon material production technology is simultaneously
The final emphasis direction realized stable yields and turn into the polysilicon industry development in China.
At present, the polysilicon production process of China's most enterprises is improved Siemens, and wherein hydrogen is as recycle
Expect that dosage is very big, if its purity can not ensure, polysilicon product is just unable to reach electron level level.Therefore circulating hydrogen is improved
Purity is all significant for stable yields electronic-grade polycrystalline silicon, or even the optimization of polysilicon production process.
Previous cycle hydrogen purification technique is：The high-temperature tail gas come out from reduction furnace first passes around multi-stage condensing, then passes through
Absorb, desorber, finally adsorbed by conventional activated carbon, obtain purer hydrogen and recycle.This technology is more ripe
Reliably, but there is hydrogen purity it is relatively low the problem of.Impurity in circulating hydrogen mainly includes the small molecular weight impurities such as boracic, phosphorus,
Such as B2H6、PH3、BCl3、PCl5Deng above-mentioned impurity is difficult effectively to remove by traditional handicraft.It is of the invention then pass through hydrogen repurity
（Modified activated carbon and modified silica-gel are as adsorption reaction agent, by adsorbing, reacting the boracic, the P elements that remove in circulating hydrogen
Impurity）, lifted hydrogen quality, solve well polysilicon enterprise can not stable yields electronic-grade polycrystalline silicon problem.
The content of the invention
It is an object of the invention to solve above-mentioned insufficient problem, there is provided a kind of improved Siemens prepare electronic-grade polycrystalline silicon
During hydrogen repurity method and device（Adsorption reaction removes boron, P elements impurity in hydrogen）, realize that stable yields electron level is more
The target of crystal silicon.
Technical scheme is as follows：
A kind of improved Siemens prepare hydrogen repurity method and device in electronic-grade polycrystalline silicon, by hydrogen cooler,
Primary adsorption reaction column, Hydrogen cryogenic device, secondary absorption reaction column composition, idiographic flow are as follows：
1st, circulating hydrogen passes first into hydrogen cooler cooling, by hydrogen_cooling between 0~30 DEG C；
2nd, primary adsorption reaction column will be passed through through overcooled circulating hydrogen to remove containing the impurity based on boron element, absorption temperature
Spend for 0~30 DEG C；
3rd, the circulating hydrogen after adsorption reaction is passed through Hydrogen cryogenic device, by between hydrogen_cooling extremely -88~-68 DEG C；
4th, the circulating hydrogen after supercooling enters secondary absorption reaction column, removes the impurity based on phosphorus element-containing, absorption
Temperature is -88~-68 DEG C.
Adsorption reaction agent in selected primary adsorption reaction column is to have loaded the modified activated carbon of oxidant, and two level is inhaled
Adsorption reaction agent in reaction enclosure post is modified chromatographic silica gel.
The modified activated carbon specific surface area for having loaded oxidant is 400~600 m2/ g, granularity are 12~40 mesh, and pore volume is
0.7~0.9 mL/g, intensity are 95 %；Modified chromatographic silica gel specific surface area is 600-800 m2/ g, granularity are 80~160 mesh,
Pore volume is 0.3~0.5 mL/g.
Hydrogen cooler is tubular heat exchanger, and tube side walks circulating hydrogen, and the cooling medium of shell side is chilled brine, temperature
For -12~-7 DEG C；Hydrogen cryogenic device is tubular heat exchanger, and tube side walks circulating hydrogen, and the cooling medium of shell side is ethene, temperature
Spend for -104 DEG C.
Primary adsorption reaction column and secondary absorption reaction column are fixed-bed structure.
The characteristics of technique, is：
1st, different from traditional absorbing process, by selecting suitable cleaner and being modified removal of impurities mechanism to inhale
Reacted while attached, make dedoping step more thorough, irreversible.
2nd, it is different according to the mechanism except boron, P elements, different adsorption reaction temperature is selected, temperature range is at 0~30 DEG C
When boron-containing impurities be more easy to be adsorbed, temperature range is more easy to be adsorbed at -88~-68 DEG C containing phosphorus impurities.
The present invention realizes that circulating hydrogen adsorption reaction removes boron, the work of P elements impurity in a kind of electronic-grade polycrystalline silicon production
Skill, boracic in hydrogen, the content of phosphorus impurities are significantly reduced, the quality of circulating hydrogen is improved, makes improved Siemens steady
Production electronic-grade polycrystalline silicon is possibly realized, and breaches the technology blockage of foreign countries.The technological process is simple, easy to operate, impurity-eliminating effect
Substantially.
Brief description of the drawings
Fig. 1 is that improved Siemens of the present invention prepare electronic-grade polycrystalline silicon adsorption reaction to remove boron, P elements miscellaneous
The process flow diagram of matter.
Figure number and explanation：1- hydrogen coolers, 2- primary adsorption reaction columns, 3- Hydrogen cryogenic devices, 4- secondary absorptions
Reaction column.
Embodiment
Below in conjunction with the accompanying drawings 1, the technical scheme in inventive embodiments is clearly and completely described, it is clear that described
Embodiment be only part of the embodiment of the present invention, rather than whole embodiment.Based on the embodiment in the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained under the premise of creative work is not made, belongs to guarantor of the present invention
The scope of shield.
Embodiment 1
A kind of method of circulating hydrogen repurity, the recovery hydrogen that the circulating hydrogen comes in autoreduction tail gas dry process recovery process
Gas, circulating hydrogen pass first into hydrogen cooler 1 and cooled down, will be through overcooled circulating hydrogen by hydrogen_cooling to 20 DEG C
Primary adsorption reaction column 2 is passed through, is removed containing the impurity based on boron element；Hydrogen is passed through by the reacted circulating hydrogen of primary adsorption
Gas deep freezer 3, by hydrogen_cooling to -80 DEG C, the circulating hydrogen after supercooling enters secondary absorption reaction column（4）, removing contains
Impurity based on P elements, adsorption temp are -80 DEG C.Hydrogen cooler 1 is tubular heat exchanger, and tube side walks circulating hydrogen, shell
The cooling medium of journey is chilled brine, and temperature is -10 DEG C；Hydrogen cryogenic device 3 is tubular heat exchanger, and tube side walks circulating hydrogen,
The cooling medium of shell side is ethene, and temperature is -104 DEG C.Adsorption reaction agent in selected primary adsorption reaction column 2 is negative
The modified activated carbon of oxidant is carried, the oxidant of load is nitric acid, and the adsorption reaction agent in secondary absorption reaction column 4 is passes through
The chromatographic silica gel of hydroxyl modification, the chromatographic silica gel have very big specific surface area, can reach 800 m2/g.Oxidant is loaded
Modified activated carbon specific surface area be 00 m2/ g, granularity are 40 mesh, and pore volume is 0.9 mL/g, and intensity is 95 %；Modified chromatography silicon
Glue specific surface area is 800 m2/ g, granularity are 120 mesh, and pore volume is 0.5 mL/g.
Embodiment 2
A kind of method of circulating hydrogen repurity, the recovery hydrogen that the circulating hydrogen comes in autoreduction tail gas dry process recovery process
Gas, circulating hydrogen pass first into hydrogen cooler 1 and cooled down, and by hydrogen_cooling to 0 DEG C, will lead to through overcooled circulating hydrogen
Enter primary adsorption reaction column 2, remove containing the impurity based on boron element；Hydrogen is passed through by the reacted circulating hydrogen of primary adsorption
Deep freezer 3, by hydrogen_cooling to -70 DEG C, the circulating hydrogen after supercooling enters secondary absorption reaction column 4, removes phosphorous member
Impurity based on element, adsorption temp are -88 DEG C.Hydrogen cooler 1 is tubular heat exchanger, and tube side walks circulating hydrogen, shell side
Cooling medium is chilled brine, and temperature is -12 DEG C；Hydrogen cryogenic device 3 is tubular heat exchanger, and tube side walks circulating hydrogen, shell side
Cooling medium be ethene, temperature is -104 DEG C.Adsorption reaction agent in selected primary adsorption reaction column 2 is to have loaded oxygen
The modified activated carbon of agent, the oxidant of load are nitric acid, and the adsorption reaction agent in secondary absorption reaction column 4 is changes by hydroxyl
The chromatographic silica gel of property, the chromatographic silica gel have very big specific surface area, can reach 600 m2/g.The modification of oxidant is loaded
Activated carbon specific surface area is 500 m2/ g, granularity are 30 mesh, and pore volume is 0.75 mL/g, and intensity is 95 %；Modified chromatographic silica gel ratio
Surface area is 700 m2/ g, granularity are 100 mesh, and pore volume is 0.4 mL/g.
Embodiment 3
A kind of device of circulating hydrogen repurity, the top of hydrogen cooler 1 is through conveying pipeline and the bottom of primary adsorption reaction column 2
Connection, the top of primary adsorption reaction column 2 are connected through conveying pipeline with the bottom of Hydrogen cryogenic device 3, and the top of Hydrogen cryogenic device 3 is through conveying pipeline
It is connected with the bottom of secondary absorption reaction column 4.Primary adsorption reaction column 2 and secondary absorption reaction column 4 are fixed-bed structure.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (2)
- A kind of 1. method of circulating hydrogen repurity, it is characterised in that the circulating hydrogen carrys out autoreduction tail gas dry process recovery process In recovery hydrogen, circulating hydrogen passes first into hydrogen cooler（1）Cooled down, will be through supercooling by hydrogen_cooling to 20 DEG C But circulating hydrogen is passed through primary adsorption reaction column（2）, remove containing the impurity based on boron element；It is reacted by primary adsorption Circulating hydrogen is passed through Hydrogen cryogenic device（3）, by hydrogen_cooling to -80 DEG C, the circulating hydrogen after supercooling enters secondary absorption Reaction column（4）, the impurity based on phosphorus element-containing is removed, adsorption temp is -80 DEG C, hydrogen cooler（1）For tubular heat exchanger, Tube side walks circulating hydrogen, and the cooling medium of shell side is chilled brine, and temperature is -10 DEG C；Hydrogen cryogenic device（3）Exchanged heat for shell and tube Device, tube side walk circulating hydrogen, and the cooling medium of shell side is ethene, and temperature is -104 DEG C, selected primary adsorption reaction column（2） In adsorption reaction agent be to have loaded the modified activated carbon of oxidant, the oxidant of load is nitric acid, secondary absorption reaction column（4） In adsorption reaction agent be that 800 m can reach by the chromatographic silica gel of hydroxyl modification, the specific surface area of the chromatographic silica gel2/ g, bear The modified activated carbon specific surface area for having carried oxidant is 400~600 m2/ g, granularity are 40 mesh, and pore volume is 0.9 mL/g, intensity For 95 %；Modified chromatographic silica gel specific surface area is 800 m2/ g, granularity are 120 mesh, and pore volume is 0.5 mL/g.
- A kind of 2. method of circulating hydrogen repurity, it is characterised in that the circulating hydrogen carrys out autoreduction tail gas dry process recovery process In recovery hydrogen, circulating hydrogen passes first into hydrogen cooler（1）Cooled down, will be through supercooling by hydrogen_cooling to 0 DEG C Circulating hydrogen be passed through primary adsorption reaction column（2）, remove containing the impurity based on boron element；Followed by primary adsorption is reacted Ring hydrogen is passed through Hydrogen cryogenic device（3）, by hydrogen_cooling to -70 DEG C, it is anti-that the circulating hydrogen after supercooling enters secondary absorption Ying Zhu（4）, the impurity based on phosphorus element-containing is removed, adsorption temp is -88 DEG C；Hydrogen cooler（1）For tubular heat exchanger, pipe Journey walks circulating hydrogen, and the cooling medium of shell side is chilled brine, and temperature is -12 DEG C；Hydrogen cryogenic device（3）Exchanged heat for shell and tube Device, tube side walk circulating hydrogen, and the cooling medium of shell side is ethene, and temperature is -104 DEG C；Selected primary adsorption reaction column（2） In adsorption reaction agent be to have loaded the modified activated carbon of oxidant, the oxidant of load is nitric acid, secondary absorption reaction column（4） In adsorption reaction agent be that there is very big specific surface area, can reach by the chromatographic silica gel of hydroxyl modification, the chromatographic silica gel 600 m2/g；The modified activated carbon specific surface area for having loaded oxidant is 500 m2/ g, granularity are 30 mesh, and pore volume is 0.75 mL/ G, intensity are 95 %；Modified chromatographic silica gel specific surface area is 700 m2/ g, granularity are 100 mesh, and pore volume is 0.4 mL/g.
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| CN106984060A (en) * | 2017-05-22 | 2017-07-28 | 东莞市莞碧环保工程有限公司 | A kind of acid solution reuse, hydrogen recovery process and its equipment |
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