CN109292780B - Process for purifying chlorosilane by reaction impurity removal - Google Patents
Process for purifying chlorosilane by reaction impurity removal Download PDFInfo
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- 239000012535 impurity Substances 0.000 title claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 40
- 239000005046 Chlorosilane Substances 0.000 title claims abstract description 36
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000001590 oxidative effect Effects 0.000 claims abstract description 21
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical group Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 32
- 239000005052 trichlorosilane Substances 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000008262 pumice Substances 0.000 claims description 3
- 239000005049 silicon tetrachloride Substances 0.000 claims description 3
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 abstract description 27
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 19
- 239000011574 phosphorus Substances 0.000 abstract description 19
- 239000013543 active substance Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- -1 trichlorosilane Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910015395 B-O-Si Inorganic materials 0.000 description 1
- 229910015403 B—O—Si Inorganic materials 0.000 description 1
- 229910004852 P—O—Si Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C01B33/10778—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a process for purifying chlorosilane by reaction impurity removal, which comprises the steps of introducing liquid phase or vaporized chlorosilane into an impurity removal reactor, carrying out reaction impurity removal treatment, introducing the treated material into a rectifying tower to remove heavy components, and obtaining purified chlorosilane; wherein, the impurity removal reactor is filled with oxidative inorganic salt. The invention can further remove the boron and phosphorus impurities at ppb level to ppt level, has simpler process, smaller reactor equipment, greatly reduced investment, easily available and cheap active substances, simple replacement, environmental protection and extremely low running cost compared with the impurity removal by a physical adsorption method.
Description
Technical Field
The invention belongs to the technical field of polysilicon preparation, and particularly relates to a process for purifying chlorosilane by reaction impurity removal.
Background
Currently, the global market basically adopts an improved siemens method and a fluidized bed method to manufacture high-purity polysilicon products, wherein the improved siemens method occupies 85 percent of market share, and is a very mature technology internationally through the development of half centuries. The improved Siemens method is to adopt trichlorosilane as a raw material to carry out hydrogen reduction reaction in a high-temperature environment, mainly electrifying and heating a polycrystalline silicon thin rod arranged in a reduction furnace reactor to more than 1100 ℃, introducing trichlorosilane and high-purity hydrogen to carry out reduction reaction, and depositing the generated new high-purity silicon on the silicon rod by chemical vapor deposition until the diameter of the silicon rod reaches 150-200 mm, thereby preparing the high-purity polycrystalline silicon product.
The reaction formula is as follows: siHCl (SiHCl) 3 +H 2 →Si+3HCl (1)
Or 2 (SiHCl) 3 )→Si+2HCl+SiCl 4 (2)
The above reaction produces, in addition to the intermediate trichlorosilane, additional products such as SiCl 4 、SiH 2 Cl 2 And FeCl 3 、 BCl 3 、PCl 3 And the like, and further rectification and purification are needed. In general, the impurity content of the trichlorosilane intermediate compound can be reduced to 10 through two processes of crude distillation and rectification -7 ～10 -10 On the order of magnitude.
In the prior art, the purification and refining technology of trichlorosilane is mainly a rectification method. Among the impurities in the trichlorosilane, boron and phosphorus impurities are the most difficult to remove, and if the boron and phosphorus impurities are controlled to be in ppm level, the boron and phosphorus impurities can be easily realized by rectification. If the requirements are increased, the control to ppb level requires that five or more rectification columns up to tens of meters are connected in series (for example, 60 theoretical plates are required to reduce the boron and phosphorus contents in trichlorosilane from 1ppm to 100 ppb). Boron and phosphorus impurities in trichlorosilane have larger boiling points than that of boron chloride, phosphorus chloride and other boron and phosphorus-free compounds, are relatively easy to separate by rectification, and boron and phosphorus-containing compounds have almost the same boiling points as that of the trichlorosilane, are easy to undergo disproportionation reaction and are difficult to separate by rectification. If impurities in the waste water are further removed to reach ppt level, more rectifying towers are needed to be connected in series for removing impurities only by rectification, so that the investment and the energy consumption are huge, and the waste water can not be realized almost.
The method for removing boron and phosphorus by physical adsorption of active carbon, molecular sieve, resin and the like can further reduce boron and phosphorus impurities, but the adsorbent has high price, huge equipment volume and high investment. In addition, the service life of the adsorbent is relatively short, when the catalyst is replaced after saturation, the replacement difficulty is high and the catalyst can be replaced in a period of several months, so that the production efficiency is low.
The ultra-high purity trichlorosilane used in the semiconductor industry is monopolized abroad, the purity of the domestic produced trichlorosilane is difficult to reach the required purity, the quality is unstable, and the high-end semiconductor industry is difficult to enter.
Disclosure of Invention
The invention aims to solve the technical problems of providing a process for removing impurities of chlorosilane, especially trichlorosilane, which is simple, wherein boron and phosphorus impurities can be controlled at ppt level, the quality is stable, the fluctuation is small, the investment cost of the whole device is low, the monopoly of foreign ultra-high purity trichlorosilane purification technology can be broken, and the requirements of the semiconductor industry are met.
The invention also solves the technical problem of providing a special system for the process.
In order to solve the technical problems, the idea of the invention is as follows: the chlorosilane is purified by combining reaction impurity removal with rectification, taking boron impurity removal as an example.
Firstly, the liquid or the vaporized chlorosilane enters a impurity removal reactor, and the reactive substance in the reactor, namely the oxidizing inorganic salt, oxidizes the hydrogen-containing boron compound with reducibility in the chlorosilane into a boronol compound. The boiling point of the alcohol compounds is greatly increased, and part of the alcohol compounds can continue to undergo oxidation or polymerization reaction, so that the alcohol compounds are converted into substances with higher boiling points;
the corresponding reaction equation for boron is:
B-H- & gtB-O-H oxidation reaction
B-O-H+Si-Cl- & gt, B-O-Si+HCl ≡polymerization reaction;
the corresponding reaction equation for phosphorus is:
oxidation of P-H.fwdarw.P-O-H
P-O-H+Si-Cl- & gt P-O-Si+HCl ≡polymerization reaction;
and secondly, separating heavy component impurities generated by the reaction of the chlorosilane after the reaction in the impurity removal reactor in a heavy component removal rectifying tower. The selected oxidizing inorganic salt does not react with the trichlorosilane, does not release impurities, can be removed easily by rectification after trace dissolution, and does not pollute the trichlorosilane; the reaction product also does not cause pollution.
The invention relates to a process for purifying chlorosilane by reaction impurity removal, which comprises the steps of introducing liquid phase or vaporized chlorosilane into an impurity removal reactor, carrying out reaction impurity removal treatment, introducing the treated material into a rectifying tower to remove heavy components, and obtaining purified chlorosilane;
wherein, the impurity removal reactor is filled with oxidative inorganic salt.
The oxidative inorganic salts include, but are not limited to, any one or more of permanganate, chlorate, hypochlorite, peroxo salt, dichromate and the like.
Further preferably, the oxidizing inorganic salt is a permanganate.
The reaction temperature in the impurity removal reactor is controlled between-70 ℃ and 300 ℃.
Further preferably, the reaction temperature in the impurity removal reactor is controlled to be-40 ℃ to 220 ℃.
The oxidative inorganic salt can be supported on the surface of a carrier, wherein the carrier comprises any one or more of porous silicate, active carbon, porous carbon, diatomite, alumina, pumice, hollow glass spheres and porous ceramic, and the supporting mode is an impregnation method. Further preferably, the support carrying the inorganic salt is a porous silicate.
The chlorosilane preferably comprises, but is not limited to, chlorosilanes such as trichlorosilane, silicon tetrachloride, dichlorosilane or hexachlorodisilane, and preferably trichlorosilane.
The invention relates to a device system for purifying chlorosilane by reaction impurity removal, which comprises at least one impurity removal reactor and at least one rectifying tower, wherein the impurity removal reactor and the rectifying tower are connected in series.
The impurity removal reactor is a fixed bed reactor and can be in a cylindrical shape, a tubular shape or a tubular shape.
The impurity removal reactor is internally provided with a filtering and compacting device, and the oxidative inorganic salt particles are fixed in the impurity removal reactor.
The rectifying tower can be selected from a sieve plate tower, a packed tower or a baffle tower.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1. the invention has simple process flow, small device investment and low operation cost, and can obtain the semiconductor-grade chlorosilane.
2. The process has unique effect on removing boron and phosphorus impurities in the chlorosilane, and also has certain impurity removing effect on other impurities.
3. Compared with the prior art, the method has the advantages that the same purity requirement is achieved, the equipment of a rectifying tower can be reduced, and the investment is reduced by 20%.
4. Compared with an adsorption tower by a physical adsorption method, the method has the advantages of small loading amount of reactive substances, long service life and greatly reduced reactor volume, and can facilitate the transformation of the existing purification device.
5. The reactive substance has low price, easy replacement, high production efficiency and low operation cost by 25 percent.
6. The reaction impurity removal and rectification are combined, the boron and phosphorus impurities can be controlled at ppt level, the quality is stable, the impurity fluctuation is small, and the requirements of the semiconductor industry are met.
Drawings
Fig. 1 is a schematic structural diagram of the present invention, wherein 1 is a impurity removal reactor, and 2 is a rectifying tower.
FIG. 2 is a flow chart of TCS purification according to one embodiment of the invention, wherein 1 is a impurity removal reactor, 2 is a rectifying column, TCS feed is less than 200ppb of boron and phosphorus impurities, and the boron and phosphorus impurities are controlled to less than 50ppt after reaction impurity removal and rectification.
FIG. 3 is a flow chart of TCS purification according to another embodiment of the invention, wherein 1 is a impurity removal reactor, 2 is a rectifying column, TCS feed is less than 10ppb of boron and phosphorus impurities, and the boron and phosphorus impurities are controlled to less than 50ppt through reaction impurity removal and rectification.
Detailed Description
The invention will be better understood from the following examples. However, it will be readily appreciated by those skilled in the art that the description of the embodiments is provided for illustration only and should not limit the invention as described in detail in the claims.
The invention relates to a process for purifying chlorosilane by reaction impurity removal, which comprises the steps of introducing liquid phase or vaporized chlorosilane into an impurity removal reactor, carrying out reaction impurity removal treatment, introducing the treated material into a rectifying tower to remove heavy components, and obtaining purified chlorosilane; the impurity removal reactor is filled with oxidative inorganic salt.
In actual production operation, the reaction temperature in the impurity removal reactor is controlled to be between-70 ℃ and 300 ℃ according to the oxidizing strength of the oxidizing inorganic salt, a jacket or a shell side of a tube can be arranged outside the impurity removal reactor according to the requirement of the reaction temperature, so that energy exchange with cold and heat sources is realized, and further preferably, the reaction temperature in the impurity removal reactor is controlled to be between-40 ℃ and 220 ℃. The oxidizing inorganic salt used in the present invention is mainly selected from one or more of reactive substances such as permanganate, chlorate, hypochlorite, peroxo salt, dichromate and the like, and further preferably the oxidizing inorganic salt is permanganate. The above-mentioned oxidizing inorganic salt is used to react with impurities in chlorosilanes such as trichlorosilane, and the conversion of the impurities into heavy component substances can be realized. In addition, the above-selected oxidizing inorganic salts are easy to prepare, inexpensive, and easy to replace.
In addition to directly loading pure oxidizing inorganic salt particles into the impurity removal reactor, in order to increase the contact area of the reactor or fix active substances and reaction products, the invention preferably loads the oxidizing inorganic salt on the surface of a carrier, and the carrier can be one or more selected from porous silicate, activated carbon, porous carbon, diatomite, alumina, pumice, hollow glass spheres and porous ceramics, and the loading mode can be a common impregnation method. Further preferred support carriers are porous silicates. The chlorosilane is chlorosilane such as trichlorosilane, silicon tetrachloride, dichlorosilane or hexachlorodisilane, and further preferably trichlorosilane.
The invention relates to a device system for purifying chlorosilane by reaction impurity removal, which comprises at least one impurity removal reactor and at least one rectifying tower, wherein the impurity removal reactor and the rectifying tower are connected in series.
The impurity removal reactor is selected from fixed bed reactors, and can be a tubular, tubular or tubular reactor. The feeding mode can be upper inlet and lower outlet, lower inlet and upper outlet, side inlet and upper and lower outlet or upper and lower inlet and side outlet. The interior of the impurity removal reactor is provided with a filtering and compacting device, so that the oxidative inorganic salt particles or the load carrier can be fixed in the reactor.
The rectifying tower can be selected from a sieve plate tower, a packed tower or a baffle tower. The rectifying tower is mainly used for removing heavy components generated by the reaction, the impurity removal reactor and the impurity removal rectifying tower for removing the heavy components generated by the reaction are necessary devices (shown in figure 1), but a proper number of rectifying towers (shown in figure 2 or figure 3) can be configured by a person skilled in the art according to the impurity content condition of raw materials and the requirements on the quality of trichlorosilane products, wherein the rectifying towers are arranged between the impurity removal rectifying tower and the impurity removal reactor, after the rectifying tower and before the impurity removal reactor.
Example 1:
the liquid phase trichlorosilane purified by preliminary rectification contains about 200ppb of boron-phosphorus impurities, the boron-phosphorus impurities are firstly introduced from the bottom of an impurity removal reactor, the reactor is a cylindrical fixed bed reactor, wherein the reaction temperature in the reactor is kept at 200 ℃, in addition, permanganate is loaded on porous silicate and fixed in the reactor, and materials enter from bottom to top. The permanganate oxidizes the reducible boron-containing compound in the trichlorosilane to a boron alcohol compound, and part of alcohol substances continue to undergo oxidation or polymerization reaction, so that the boron-containing compound is converted into heavy components with higher boiling points.
Heavy components are extracted from the top of the impurity removal reactor, then introduced into the middle part of the heavy removal rectifying tower, after rectifying treatment, purified trichlorosilane is extracted from the top of the rectifying tower, and other components are collected from the bottom of the rectifying tower. After the reaction impurity removal and rectification, the boron and phosphorus impurities in the trichlorosilane are controlled to be 50ppt, so that the requirement of polysilicon enterprises for stable production of semiconductor grade trichlorosilane is met.
Example 2:
the gas phase trichlorosilane purified by preliminary rectification contains about 10ppb of boron-phosphorus impurities, the boron-phosphorus impurities are firstly introduced from the bottom of an impurity removal reactor, the reactor is a tube fixed bed reactor, the reaction temperature in the reactor is kept at 170 ℃, in addition, permanganate is loaded on alumina and fixed in the reactor, and materials enter and exit from the bottom. The permanganate oxidizes the reducible boron-containing compound in the trichlorosilane to a boron alcohol compound, and part of alcohol substances continue to undergo oxidation or polymerization reaction, so that the boron-containing compound is converted into heavy components with higher boiling points.
Heavy components are extracted from the top of the impurity removal reactor, then introduced into the middle part of the heavy removal rectifying tower, after rectifying treatment, purified trichlorosilane is extracted from the top of the rectifying tower, and other components are collected from the bottom of the rectifying tower. After the reaction impurity removal and rectification, the boron and phosphorus impurities in the trichlorosilane are controlled to be 50ppt, so that the requirement of polysilicon enterprises for stable production of semiconductor grade trichlorosilane is met.
Example 3:
a rectifying device implemented by a certain company adopts a five-tower process, the yield of high-purity TCS is 20t/h, and the investment is 1.3 hundred million yuan. After one year, a rectifying device is added, a purifying reactor is added, a four-tower process is adopted, the yield is 20t/h, the investment is 1.05 hundred million yuan, and the volume of the purifying reactor is 1m 3 One for each preparation. After the technically improved rectifying device is put into operation, the active substances are replaced once in half a year, the active substances can be replaced in 2 days, the replacement cost is only about 10 ten thousand yuan, one rectifying tower is reduced to operate, and the operation cost is saved by 3000 ten thousand yuan every year.
Claims (7)
1. A process for purifying chlorosilane by reaction impurity removal is characterized by comprising the steps of introducing liquid phase or vaporized chlorosilane into an impurity removal reactor, carrying out reaction impurity removal treatment, introducing the treated material into a rectifying tower to remove heavy components, and obtaining purified chlorosilane;
wherein, the impurity removal reactor is filled with an oxidizing inorganic salt, and the oxidizing inorganic salt is any one or more of permanganate, chlorate, hypochlorite, peroxo salt and dichromate.
2. The process for purifying chlorosilanes as claimed in claim 1 wherein said oxidizing inorganic salt is permanganate.
3. The process for purifying chlorosilane by reaction and impurity removal as claimed in claim 1, wherein the reaction temperature in said impurity removal reactor is controlled to be-70 ℃ to 300 ℃.
4. A process for purifying chlorosilanes as claimed in claim 3 wherein the reaction temperature in said impurity removal reactor is controlled at-40 ℃ to 220 ℃.
5. The process for purifying chlorosilane by reaction impurity removal as in claim 1 or 2 wherein said inorganic salt is carried on the surface of a carrier selected from any one or more of porous silicate, activated carbon, porous carbon, diatomaceous earth, alumina, pumice, hollow glass spheres and porous ceramics, said carrying being by impregnation.
6. The process for purifying chlorosilanes as claimed in claim 5, wherein said carrier is a porous silicate.
7. The process for purifying chlorosilane by removing impurities through reaction according to claim 1, wherein the chlorosilane is trichlorosilane, silicon tetrachloride, dichlorosilane or hexachlorodisilane.
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| EP2689844A1 (en) * | 2007-09-21 | 2014-01-29 | MEMC Electronic Materials, Inc. | Catalysts for purification of silicon tetrafluoride |
| CN103553058A (en) * | 2013-11-11 | 2014-02-05 | 新特能源股份有限公司 | Production process of high-purity refined trichlorosilane |
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| CN106882808A (en) * | 2017-02-28 | 2017-06-23 | 洛阳中硅高科技有限公司 | The purification process and purification system of chlorine silicide |
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