CN109987608A

CN109987608A - Method that is a kind of while producing dichlororosilane eiectronic grade, electron level trichlorosilane and electron level silicon tetrachloride

Info

Publication number: CN109987608A
Application number: CN201910323974.6A
Authority: CN
Inventors: 董立强; 戴帅; 杨志军
Original assignee: Tangshan Sanfu Electronic Materials Co Ltd
Current assignee: Tangshan Sanfu Electronic Materials Co Ltd
Priority date: 2019-04-22
Filing date: 2019-04-22
Publication date: 2019-07-09
Anticipated expiration: 2039-04-22
Also published as: CN109987608B

Abstract

The present invention relates to a kind of methods for producing dichlororosilane eiectronic grade, electron level trichlorosilane and electron level silicon tetrachloride simultaneously, using crude product trichlorosilane as raw material, including primary dedusting, Gas Phase Adsorption, once take off light component, once take off heavy constituent, disproportionation, addition complexing agent, final dusting, first separation, secondary separation processing, the processing of secondary de- light component, secondary de- heavy constituent processing, three times separating treatment, take off light component three times, take off heavy constituent, four de- light components, four de- heavy constituents three times.Present invention process route, it is on the process route of existing manufacture dichlororosilane eiectronic grade, pass through the variation and adjustment of step, raw material purity of trichlorosilane is required to reduce, dichlororosilane eiectronic grade, electron level trichlorosilane and the electron level silicon tetrachloride that can simultaneously obtain, the impurity contents such as metal impurities, chlorosilane impurity and boron are few, and quality is stable and is able to satisfy requirement of the large-scale integrated circuit to product.

Description

It is a kind of to produce dichlororosilane eiectronic grade, electron level trichlorosilane and electron level simultaneously The method of silicon tetrachloride

Technical field

Dichlororosilane eiectronic grade, electron level trichlorosilane and electron level silicon tetrachloride are produced simultaneously the present invention relates to a kind of Method, belong to chlorosilane production technical field.

Background technique

Dichlororosilane eiectronic grade, electron level trichlorosilane and electron level silicon tetrachloride are mainly used for growing epitaxial silicon and big The silicon source of scale integrated circuit.Dichlororosilane eiectronic grade and trichlorosilane are mainly monopolized by Zoomlions such as Japan at present, with China semiconductor industry is fast-developing and the production domesticization demand such as semiconductor material, equipment, break foreign countries to electron level dichloro The monopolization of dihydro silicon and electron level trichlorosilane to China guarantees that China's information industry develops in a healthy way, independent development electron level two Chlorine dihydro silicon and electron level trichlorosilane are imperative.Meanwhile electron level is produced for raw material using dichlororosilane eiectronic grade Perhydropolysilazane is also widely used for defence and military, is at present also that national defence and military is badly in need of.

Instantly the other dichlororosilane eiectronic grade of semiconductor grade, and technique road can just not reached on domestic market really Line or be to be feedstock purification using the dichlorosilane of polysilicon by-product or be with trichlorosilane as waste, but to original Material requirements is very high, some requirement 4N or more, some requirements at least 3N or more, while electronics industry is to dichlororosilane eiectronic grade Required with the metal impurities of trichlorosilane, boron and phosphorus matter and other chlorosilane impurity it is extremely high, domestic electron level dichloro hydrogen silicon Above-mentioned Control of Impurities is unstable；Furthermore the dichloro-dihydro thrown away in high boiling or de- low-boiling-point substance is taken off in dichlorosilane preparation process The extremely bad processing of silicon, industry need that raw material can be made with low-quality trichlorosilane, being capable of stability contorting resultant metal impurity, boron The technique of dichlorosilane is discharged in phosphorus impurities and other chlorosilane impurity, and the fine treating and preparing process of energy.

Summary of the invention

Dichlororosilane eiectronic grade, electron level trichlorine are produced simultaneously technical problem to be solved by the invention is to provide a kind of The method of hydrogen silicon and electron level silicon tetrachloride, solves the above problems.

The technical scheme to solve the above technical problems is that a kind of produce dichlororosilane eiectronic grade, electricity simultaneously The method of sub- grade trichlorosilane and electron level silicon tetrachloride, comprising the following steps:

S1 carries out primary dedusting processing using crude product trichlorosilane as raw material；

Trichlorosilane after primary dedusting is carried out Gas Phase Adsorption processing by S2；

S3 successively carries out the trichlorosilane after Gas Phase Adsorption once to take off light component processing and once de- heavy constituent processing；

Trichlorosilane after de- heavy constituent is carried out disproportionated reaction, obtained comprising dichlorosilane, trichlorosilane and four by S4 First mixture of silicon chloride；

S5 adds complexing agent into the first mixture, and carries out final dusting processing；

The first mixture after final dusting is carried out first separation, obtained containing dichlorosilane and trichlorosilane by S6 The second mixture and third mixture containing trichlorosilane and silicon tetrachloride；

S7 successively carries out the second mixture at secondary separation processing, secondary de- light component processing and secondary de- heavy constituent Reason, obtains dichlororosilane eiectronic grade；Third mixture is subjected to separating treatment three times, it is mixed to obtain the containing trichlorosilane the 4th Object and the 5th mixture containing silicon tetrachloride are closed, the 4th mixture is successively taken off into light component processing three times and is taken off three times Heavy constituent processing, obtains electron level trichlorosilane, and the 5th mixture is successively carried out four de- light component processing and four de- weights Component processing, obtains electron level silicon tetrachloride.

The beneficial effects of the present invention are: present invention process route, is different from existing separately fabricated electron level dichloro-dihydro The technique of silicon or separately fabricated electron level trichlorosilane is the process route in existing manufacture dichlororosilane eiectronic grade On, by the variation and adjustment of step, raw material purity of trichlorosilane is required to reduce, process route has obviously with other techniques Variation and difference, dichlororosilane eiectronic grade, electron level trichlorosilane and electron level silicon tetrachloride, the metal that can simultaneously obtain are miscellaneous The impurity contents such as matter, chlorosilane impurity and boron are few, and quality is stable and is able to satisfy requirement of the large-scale integrated circuit to product.

Based on the above technical solution, the present invention can also be improved as follows.

Further, in step S1, the purity of the crude product trichlorosilane is 2N (99 or more % of content), the primary dedusting Processing carries out in raw material gas wash tower, and tower presses 0.2-0.4MPa, 68-87 DEG C of tower top temperature, inlet amount 1896.2kg/h, tower reactor removing The boiling point impurity higher than tower top temperature, overhead extraction.

The beneficial effect for using above-mentioned further scheme is raw material of the invention for trichlorosilane, is carried out with trichlorosilane Disproportionated reaction, being different from other existing production chlorosilane technique chinese raw materialies is the polysilicon by-product dichlorosilane after purification, It is at least 4N (content 99.99 that also different from the technique that other are disproportionated with trichlorosilane, in other techniques, trichlorosilane, which requires purity, The above %) or 3N (99.9 or more % of content), and the present invention proposes that purity of trichlorosilane is 2N, and existing other are given birth to It produces raw material dichlorosilane, raw material trichlorosilane, raw material silicon tetrachloride in chlorosilane technique and is very likely not from trichlorine hydrogen Silicon is obtained with anionic surface tertiary amine groups exchanger resin, and B, P impurity of product etc. is caused to be difficult or can not remove by rectifying.

Further, in step S2, the Gas Phase Adsorption processing carries out in adsorption tower, is adsorbed using molecular sieve, tower pressure 0.2-0.4MPa, 90 DEG C of tower top temperature, inlet amount 1896.2kg/h.The grain graininess of the molecular sieve is diameter 1-3.5mm, butt Bulk density 0.45-0.78g/cm³, specific surface is greater than 200m²/ g, Kong Rong are more than or equal to 0.4cm³/g。

Beneficial effect using above-mentioned further scheme is that the absorption in other existing techniques is placed in disproportionated reaction Product purification afterwards, adsorbent are active carbon, silica gel etc.；And absorption of the invention is placed in the purification of raw material trichlorosilane raw material Before, adsorbent is molecular sieve.Firstly, all boron and phosphorus matter both is from raw material, if raw material in the technique of production chlorosilane It is not handled properly, and putting reprocessing after the purification is clearly that primary and secondary is inverted, if secondly boron is not handled well in raw material, adsorption effect If bad, when disproportionated reaction, boron chloride can be generated, it is very close with the boiling point of target product dichlorosilane, if Adsorption effect is bad, then is also difficult to be separated by rectifying, causes product to contain impurity more and decline product quality, this Outside, the fine particles such as silica gel of molecular sieve also have the possibility for being broken, taking away in absorption, will affect product purity, stringent next Say that absorption position more front end is better, rather than it is more preferable from finished product end.

Further, step S3, the once de- light component processing carry out in raw material lightness-removing column, and tower presses 0.2-0.4MPa, 68-87 DEG C of tower top temperature, tower top outlet material 240kg/h, tower reactor produce 1656.2kg/h, regurgitant volume 12-16m³/h；It is described primary De- heavy constituent processing carries out in raw material weight-removing column, tower pressure 0.2-0.4MPa, 68-87 DEG C of tower top temperature, tower reactor outlet 240kg/h, Overhead extraction 1416.2kg/h, regurgitant volume 11-15m³/h。

Beneficial effect using above-mentioned further scheme is that raw material trichlorosilane of the invention passes through lightness-removing column and de- weight Tower carries out rectifying, and specifically requires to be different from the prior art in the state modulator of lightness-removing column and weight-removing column, and tower of the present invention is voltage-controlled System gas used is not nitrogen, and is other high-purity gas, because nitrogen is for semicon industry especially present invention back Downstream manufacturers for be foreign gas, doping enters to be unfavorable for the further processings of downstream manufacturers, and therefore, the present invention can adopt With other high-purity gas for not being foreign gas.

Further, in step S4, the disproportionated reaction carries out in disproportionation reactor, disproportionation reactor pressure 0.2- 0.3MPa, 60-70 DEG C of reaction temperature；Disproportionation reactor is double tubesheet tubular heat exchanger, is water in tube side, and shell side is de- weight Simultaneously water content is added in macroreticular weakly base anion exchange tree of 0.3% surface below with tertiary amino in trichlorosilane after component Rouge A21 is as catalyst；First mixture includes 6wt%-7wt% dichlorosilane, 80wt%-81wt% trichlorine hydrogen Silicon, 11wt%-12wt% silicon tetrachloride, remaining is other impurities.

Beneficial effect using above-mentioned further scheme, which is the prior art, obtains trichlorine with doing raw material with industrial metallic silicon Hydrogen silicon purifies again produces electron level trichlorosilane, the boron chloride and phosphorus trichloride contained in raw material trichlorosilane in this technique Deng being difficult to be completely segregated in rectifying, cause the resistivity of the impurity effects product such as B, P in product.And the present invention is selected three Chlorine hydrogen silicon makes the boron chloride and phosphorus trichloride in trichlorosilane by macroreticular weakly base resin anion (R.A.) of the surface with tertiary amino Form BH₃-PH₃Compound, the compound are low-boiling compound.The boiling point of boron chloride is 12 degrees Celsius, the boiling of phosphorus trichloride Point is 76 degrees Celsius, and the silicon tetrachloride boiling point produced after disproportionated reaction is 57 degrees Celsius, and dichlorosilane is 8.2 degrees Celsius.Such as After catalyst, boron chloride and phosphorus trichloride are induced to generate low-boiling PH this trichlorosilane₃-BH₃Compound, relatively It is easy to separate by rectifying in the boiling point of trichlorosilane, is so readily available the very low electron level of boracic phosphorus impurity Trichlorosilane, effect, which is significantly better than, directly obtains electron level trichlorosilane with chlorosilane rectifying.

If catalyst is aqueous in disproportionated reaction, chlorosilane can generate siliceous material with water reaction, and react A large amount of heat is issued in the process, and catalyst surface, blocking catalyst gap can be attached to by reacting silicic acid of generation etc., and reduction is urged Agent reactivity, the heat that simultaneous reactions are released will lead to catalyst overheating inactivation, and therefore, the catalyst of disproportionated reaction needs It is adequately dried, the catalyst water content that the present invention uses reaches 0.3wt% hereinafter, simple nitrogen in being different from the prior art Gas is dry, or enters device and catalyst reaction using silicon tetrachloride or trichlorosilane to take away moisture, this hair in catalyst Bright Catalyst processing method is to handle catalyst with modes such as hot nitrogen, alcohols, arenes, and effect is more preferable, and water content is more It is low.

In addition, material and catalyst are in shell side, opposite tube side is not easy to plug, and tube side is hot water, and the temperature of water can be by changing Hot device precise controlling, while the specific heat capacity of water is big, is capable of providing equilibrium temperature environment, disproportionated reaction not available for other media Device has prevented the possibility of tube side water and the contact of shell side material, there have in terms of safety and quality to be greatly good by the way of double tubesheet Place.

Further, in step S5, add complexing agent the step of carried out in chlorosilane pans, the complexing agent be fragrance Aldehyde or fragrant aldehyde derivatives, additive amount are the 0.08wt%-0.15wt% of the first mixture；The final dusting processing is in chlorine It is carried out in silane gas wash tower, tower presses 0.2-0.4MPa, 70-95 DEG C of tower top temperature, inlet amount 1416.2kg/h, tower reactor removing boiling point ratio Tower top temperature high impurity about 0.1kg/h, overhead extraction 1416.1kg/h mixed chlorosilane.

Beneficial effect using above-mentioned further scheme be the impurity in material is adsorbed with complexing agent, but because The complexing agent of addition is easy to form solid high-polymer with metal chlorides such as iron chloride, causes the blocking of container or pipeline, is Clear up these tampers, it may be necessary to which periodically parking cleaning causes the frequent driving and parking of system, while increasing workload, increases System opens the more impurity of generation and is difficult to replace clean risk.So present invention process is provided with two sets of gas wash towers, after complexing Dust removal step can be very good to get rid of the solid matter that complexing is formed, avoid blocking.

Further, in step S6, the first separation carries out in No. 1 knockout tower, and tower presses 0.2-0.4MPa, tower top temperature 53-73 DEG C, overhead extraction the second mixture 299.1kg/h, tower bottom produces third mixture 1117kg/h, regurgitant volume 7-10m³/ h。

Further, in step S7, the secondary separation processing carries out in No. 2 knockout towers, and tower presses 0.2-0.4MPa, tower top Warm 41-60 DEG C, inlet amount 319.1kg/h, the outer discharge capacity of tower reactor is 200kg/h, and overhead extraction amount is 99.1kg/h, and regurgitant volume is 2-4m³/h；The secondary de- light component processing carries out in DCS lightness-removing column, and tower presses 0.2-0.4MPa, 41-60 DEG C of tower top temperature, tower The DCS 20kg/h of outlet impurity containing heavy constituent is pushed up, tower reactor produces 79.1kg/h, regurgitant volume 2-4m³/h；The secondary de- recombination Processing is divided to carry out in DCS weight-removing column, tower pressure 0.2-0.4MPa, 41-60 DEG C of tower top temperature, tower reactor outlet impurity containing light component DCS 16kg/h, overhead extraction dichlororosilane eiectronic grade 63.1kg/h, regurgitant volume 2-4m³/h。

Further, the material of DCS lightness-removing column tower top outlet material and DCS weight-removing column tower reactor outlet is pumped into anti-disproportionated reaction Device, while the crude product silicon tetrachloride of 10 times of weight of material is added into anti-disproportionation reactor, anti-disproportionation is anti-under the action of catalyst Trichlorosilane should be obtained, the raw material of step S1 is back to；Anti- disproportionation reactor pressure 0.5MPa, temperature 70 C.Feed composition DCS 36kg/h, STC 360kg/h.

Beneficial effect using above-mentioned further scheme is in the existing technique for preparing dichlororosilane eiectronic grade, for Dichlorosilane purification in be discharged containing high boiling or low boiling dichlorosilane, traditional method be neutralizing treatment absorb, on the one hand Increase cost, still further aspect dichlorosilane is relatively active more dangerous, and alkali cleaning is relatively dangerous, and the present invention is miscellaneous by containing for discharge Anti- disproportionation obtains trichlorosilane to the silicon tetrachloride of the dichloro hydrogen silicon common grade of matter again, as a whole the raw materials recovery of technique It utilizes, makes process cycles non-pollution discharge.It should be noted that anti-disproportionation purpose is to consume extra dichlorosilane, keep away Exempt from additional processing and increase cost, can also obtain realizing the recycling of material, and anti-as the trichlorosilane of raw material Disproportionated reaction is not one to one theoretical reaction, needs to increase reactant concentration and reaction is promoted to carry out, four chlorinations finally obtained Silicon can carry out simple rectifying with the mixture of trichlorosilane and separate, and can reuse respectively as the raw material of low-purity.

Further, in step S7, the separating treatment three times carries out in No. 3 knockout towers, and tower presses 0.2-0.4MPa, tower top Warm 68-87 DEG C, the 4th mixture 850kg/h of overhead extraction, tower reactor produces the 5th mixture 267g/h, regurgitant volume 9-11m³/h； The light component processing de- three times carries out in TCS lightness-removing column, and tower presses 0.2-0.4MPa, 68-87 DEG C of tower top temperature, the outer impurities removal of tower top Matter 200kg/h, tower reactor produce 650kg/h, regurgitant volume 8-10m³/h；It is described three times take off heavy constituent processing in TCS weight-removing column into Row, tower press 0.2-0.4MPa, 68-87 DEG C of tower top temperature, the outer impurity removal 190kg/h of tower reactor, overhead extraction electron level trichlorosilane 460kg/h, regurgitant volume 8-10m³/h；Four de- light component processing carry out in STC lightness-removing column, and tower presses 0.2-0.4MPa, 95-117 DEG C of tower top temperature, the outer impurity removal 127kg/h of tower top, tower reactor produce 150kg/h, regurgitant volume 4-6m³/h；Described four times de- weights Component processing carries out in STC weight-removing column, and tower presses 0.2-0.4MPa, 95-117 DEG C of tower top temperature, the outer impurity removal 50kg/h of tower reactor, tower Top extraction electron level silicon tetrachloride 100kg/h, regurgitant volume 4-6m³/h。

Beneficial effect using above-mentioned further scheme is purification of the present invention for chlorosilane using purifying twice, once It is another secondary after disproportionated reaction in feedstock processing part, the purifying twice of chlorosilane is greatly reduced in chlorosilane component The content of metal and boron and phosphorus matter, (production equipment is only needed using 304L or 316L, no for the requirement for reducing to equipment material Need electrobrightening), also reducing the load of equipment, (purification process needs higher tower, more numbers of plates, brings therewith Be the consumption of higher heating agent and refrigerant consumption)

About inlet amount, outer discharge capacity, the produced quantity etc. in above-mentioned technical proposal, it is contemplated that the scale of equipment, it can be with It by changing for corresponding proportion, for example zooms in or out in proportion, in addition, the size requirements of regurgitant volume are to electronic grade product matter Amount influence is very big, although the regurgitant volume of distinct device can change, same equipment designs different regurgitant volumes also can be significantly Product quality is influenced, regurgitant volume can balance in product quality and energy conservation in traditional big chemical industry, but electronic grade product is not necessarily, It needs to be comprehensively considered according to equipment and other correlative factors, and is determined according to experiment.Preferred embodiments are only gived in the present invention, institute It gives an actual example and is served only for explaining the present invention, be not intended to limit the scope of the present invention.

The present invention be it is a kind of in technology controlling and process to the control of the temperature and pressure of lightness-removing column, weight-removing column to solve rectifying Boron-containing compound is difficult to separate the new process route of proposition caused by changing with the variation of temperature, pressure in the process, wherein setting Standby part 316L material, other equal 304L materials do not need electrobrightening, reduce equipment and integrally invest.Filler External import structured packing guarantees resultant metal impurity.

Detailed description of the invention

Fig. 1 is flow chart of the invention.

Specific embodiment

The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit Determine the scope of the present invention.

In the description of the present invention, the material that DCS is referred to is dichlorosilane, and the material that TCS is referred to is trichlorosilane, The material that STC is referred to is silicon tetrachloride, and E- represents electron level, and the reactor in figure is disproportionation reactor.

As shown in Figure 1, producing dichlororosilane eiectronic grade, electron level three simultaneously using trichlorosilane the present invention relates to a kind of The method of chlorine hydrogen silicon and electron level silicon tetrachloride, comprising the following steps:

S1 carries out primary dedusting processing with crude product trichlorosilane (purity 2N) for raw material in raw material gas wash tower；Tower pressure 0.2-0.4MPa, 68-87 DEG C of tower top temperature, inlet amount 1896.2kg/h, tower reactor remove the boiling point impurity higher than tower top temperature, and tower top is adopted Out；It is different from the scheme that feedstock processing in other prior arts is directly entered packed tower, gas wash tower is plate column, to miscellaneous containing particle The material of matter has better adaptability, can significantly reduce the requirement to trichlorine material purity；

Trichlorosilane after primary dedusting is carried out in adsorption tower Gas Phase Adsorption processing, is adsorbed using molecular sieve by S2, is taken off Except the impurity in raw material, tower presses 0.2-0.4MPa, and 90 DEG C of tower top temperature, inlet amount 1896.2kg/h；The particle of the molecular sieve Degree is diameter 1-3.5mm, butt bulk density 0.45-0.78g/cm³, specific surface is greater than 200m²/ g, Kong Rong are more than or equal to 0.4cm³/g；As shown in Figure 1, adsorption tower can be arranged side by side two sets of setting, while Gas Phase Adsorption processing is carried out, it is one of to need When cleaning molecular sieve or maintenance, another still can be run, and whole shutdown are not needed；

Trichlorosilane after Gas Phase Adsorption is first carried out once de- light component processing, tower pressure by S3 in raw material lightness-removing column 0.2-0.4MPa, 68-87 DEG C of tower top temperature, inlet amount 1896.2kg/h, tower top outlet material 240kg/h, tower reactor extraction 1656.2kg/h, regurgitant volume 12-20m³/h；De- heavy constituent processing is carried out once in raw material weight-removing column again, tower presses 0.2- 0.4MPa, 68-87 DEG C of tower top temperature, inlet amount 1656.2kg/h, tower reactor outlet 240kg/h, overhead extraction 1416.2kg/h, reflux Measure 12-20m³/h；

Trichlorosilane after de- heavy constituent is carried out disproportionated reaction by S4 under the effect of the catalyst in disproportionation reactor, Disproportionation reactor pressure 0.2-0.3MPa, obtains comprising dichlorosilane, trichlorosilane and four chlorinations by 60-70 DEG C of reaction temperature First mixture of silicon；Disproportionation reactor is double tubesheet tubular heat exchanger, is water in tube side, and shell side is after taking off heavy constituent Simultaneously water content is added in macroporous weakly basic anion exchange resin A21 work of 0.3% surface below with tertiary amino in trichlorosilane For catalyst, disproportionated reaction carries out in shell side；First mixture includes 6wt%-7wt% dichlorosilane, 80wt%- 81wt% trichlorosilane, 11wt%-12wt% silicon tetrachloride, remaining is other impurities；

First mixture is passed through chlorosilane pans, and adds complexing agent, the complexing by pans feed pipe by S5 Agent is aromatic aldehyde or fragrant aldehyde derivatives, and additive amount is the 0.08wt%-0.15wt% of the first mixture；It is removed again in chlorosilane Final dusting processing is carried out in chimney, tower presses 0.2-0.4MPa, 70-95 DEG C of tower top temperature, inlet amount 1416.2kg/h, tower reactor removing The boiling point impurity about 0.1kg/h higher than tower top temperature, overhead extraction 1416.1kg/h mixed chlorosilane；

S6, by the first mixture (i.e. chlorosilane gas wash tower overhead extraction object in S5) after final dusting in No. 1 knockout tower Middle carry out first separation, tower pressure 0.2-0.4MPa, 53-73 DEG C of tower top temperature, inlet amount 1416.1kg/h, overhead extraction contain two The second mixture (including part TCS and nearly all DCS) 299.1kg/h of chlorine dihydro silicon and trichlorosilane, tower bottom extraction contain There is third mixture (residue major part TCS and nearly all STC) 1117kg/h, regurgitant volume 7- of trichlorosilane and silicon tetrachloride 10m³/h；

Second mixture is successively carried out the secondary separation in No. 2 knockout towers (similar and weight-removing column) and handled by S7, tower pressure 0.2-0.4MPa, 41-60 DEG C of tower top temperature, inlet amount 319.1kg/h, tower reactor outlet (heavy constituent impurity and a small amount of DCS) 200kg/h, overhead extraction 99.1kg/h, regurgitant volume 2-4m³/h；Secondary de- light component processing is carried out in DCS lightness-removing column again, Tower presses 0.2-0.4MPa, 41-60 DEG C of tower top temperature, inlet amount 99.1kg/h, the DCS 20kg/ of tower top outlet impurity containing heavy constituent H, tower reactor produce DCS 79.1kg/h, regurgitant volume 2-4m³/h；Secondary de- heavy constituent processing, tower are finally carried out in DCS weight-removing column Pressure 0.2-0.4MPa, 41-60 DEG C of tower top temperature, inlet amount 79.1kg/h, the DCS 16kg/h of tower reactor outlet impurity containing light component, Overhead extraction dichlororosilane eiectronic grade 63.1kg/h, regurgitant volume 2-4m³/ h, the product of overhead extraction are pumped into electron level dichloro two Hydrogen finished product storage tank；

The material of DCS lightness-removing column tower top outlet material and DCS weight-removing column tower reactor outlet is pumped into anti-disproportionation reactor, simultaneously The crude product silicon tetrachloride of 10 times of weight of material is added into anti-disproportionation reactor, anti-disproportionated reaction obtains three under the action of catalyst Chlorine hydrogen silicon, is back to the raw material of step S1；Anti- disproportionation reactor pressure 0.5MPa, temperature 70 C, feed composition DCS 36kg/h, STC 360kg/h, wherein the conversion ratio of dichlorosilane is 95% or so；

Third mixture is subjected to separating treatment three times in No. 3 knockout towers, tower presses 0.2-0.4MPa, tower top temperature 68-87 DEG C, overhead extraction contains the 4th mixture 850kg/h of trichlorosilane, and tower reactor produces the 5th mixture containing silicon tetrachloride (wherein having a small amount of trichlorosilane) 267g/h, regurgitant volume 9-11m³/h；

4th mixture is taken off into light component processing three times in TCS lightness-removing column, tower presses 0.2-0.4MPa, tower top temperature 68-87 DEG C, inlet amount 850kg/h, tower top outlet TCS200kg/h containing low boiling, tower reactor produces TCS 650kg/h, regurgitant volume 8- 10m³/h；Taken off heavy constituent processing three times in TCS weight-removing column again, tower presses 0.2-0.4MPa, 68-87 DEG C of tower top temperature, charging Amount is 650kg/h, and tower reactor outlet contains high boiling TCS 190kg/h, overhead extraction electron level trichlorosilane 460kg/h, regurgitant volume 8- 10m³/ h, the product of overhead extraction are pumped into electron level trichlorosilane finished product storage tank；

5th mixture is carried out to four de- light component processing in STC lightness-removing column, tower presses 0.2-0.4MPa, tower top temperature 95-117 DEG C, inlet amount 267kg/h, tower top outlet TCS, light component and part STC 127kg/h, tower reactor produces STC 150kg/ H, regurgitant volume 4-6m³/h；Four de- heavy constituent processing are carried out in STC weight-removing column again, tower presses 0.2-0.4MPa, tower top temperature 95- 117 DEG C, inlet amount 150kg/h, tower reactor outlet contains high boiling STC 50kg/h, overhead extraction electron level silicon tetrachloride 100kg/h, returns Flow 4-6m³/ h, the product of overhead extraction are pumped into electron level silicon tetrachloride finished product storage tank.

For production method of the invention, applicant carried out multiple technological experiment, the tower of each tower in above-mentioned technical proposal Pressure and tower top temperature have carried out corresponding confirmatory experiment in limited range and (have carried out different gradients from small to large by data Experiment, since the minimum value of each value range, is gradually increased to maximum value), product of the invention can be obtained, it is preferred that Tower pressure and tower top temperature are the most median in the range recorded in above-mentioned technical proposal.And inlet amount, discharge rate, produced quantity, Regurgitant volume etc., what is recorded in above-mentioned technical proposal is that applicant is obtained using suitable production equipment, certainly, for life Adjustment appropriate can be carried out by producing equipment and its scale those skilled in the art, and related each amount can increase or reduce accordingly. Key to the invention is that in technique although the sequence setting of front and back step and each technical parameter, each production equipment are from this field Common apparatus in select, but be also to have carried out relevant experimental comparison, according to experimental data and interpretation of result from various lifes It produces in equipment and selects equipment the most suitable, and cooperate corresponding step and technical parameter, can achieve best production effect.

In above-mentioned steps, raw material gas wash tower is plate column, and plate column is relative to packed tower, to the object of the impurity containing high-boiling components Material has better adaptability, can significantly reduce this system to the quality requirements of raw material TCS, raw material dedusting tower reboiler be autoclave again Device is boiled, the maintenance of raw material gas wash tower is facilitated to detach；The tower ratio of height to diameter of adsorption tower is about 10:1；Raw material lightness-removing column is packed tower, filler For plate ripple arranged packing, material is 316L stainless steel, and the raw material weight-removing column is packed tower.

The catalyst of the disproportionated reaction will carry out stringent dehydration, detailed process are as follows: purchase stem-based catalyst A- 21, it is desirable that its water content is lower than 0.3wt%, and catalyst is added and is packed into reactor, and the volume needs for being packed into catalyst are true in advance Recognize.After raw material TCS touches catalyst, impurity boron chloride and phosphorus trichloride in TCS will form BH₃-PH₃Compound, the change Conjunction object is low-boiling point material, is easy to separate in distillation system with product.

The present invention tests catalyst by experiment and floats still in alcohols, arene, silicon tetrachloride, trichlorosilane Sinking state and the swelling state in various volumes, expansion rate.

Experimental record is as follows:

Experiment one

One, experiment purpose:

A21 resin is measured in the expansion rate of alcohols.

Two, experiment equipment:

2L graduated cylinder, glass bar, alcohols (99.7%), the basket filter (band strainer) that bore DN50 is transformed, high-purity experiment Room nitrogen, hermetic bag and leather sheath.

Three, experiment content:

1, it takes about 500ML resin, hands over lab analysis personnel to be placed in baking oven and dries, baking oven is arranged 70 DEG C and (be sure not is more than 90 DEG C) three hours of drying, weighing places into 70 DEG C of baking oven drying, weighs again after half an hour, until being spaced half an hour quality Variation is taken out afterwards less than 0.2% (0.001g of poor quality).

2, the A21 resin for taking out laboratory drying, being poured slowly into and measuring the stacking volume of resin in 2L graduated cylinder is 560ML (barrel slightly adsorbs resin, stands a period of time resin and falls).

3, be poured slowly into 2L graduated cylinder 99.7% alcohols make resin be immersed in alcohol solution (resin by white gradually Become faint yellow), bubble out is shaken, volume is 730ML after resin expansion, and after mouth sealing and standing 24 hours, resin volume is still 730ML。

4, resin alcohol mixture is poured into the basket with strainer and filters alcohols, basket is then put into basket filter In, capping is logical to be dried with nitrogen and (arranges into side at bottom), and the raffinate alcohols filtered, which is put into waste liquid bottle, to be stored, to subsequent by lab assistant Processing.

5, A21 resin, which is placed in basket filter, continuously blows two days, takes out bottling, send laboratory constant temperature drying.

6, dried A21 resin is repeated into 2,3,4,5 steps again, entirety in triplicate, records experimental data.

Four, Experiment Data Records:

Five, experimental calculation result

Six, conclusion

Swelling volume of the A21 resin in the alcohols is 33.2%.

Experiment two:

One, experiment purpose:

Measure expansion rate of the A21 resin in arene.

Two, experiment equipment:

2L graduated cylinder, glass bar, aromatic hydrocarbon (99.5%), basket filter (band strainer), the Gao Chunshi that bore DN50 is transformed Test room nitrogen, hermetic bag and leather sheath, gas mask, rubber gloves.

Three, experiment content:

2, the A21 resin for taking out laboratory drying, being poured slowly into and measuring the stacking volume of resin in 2L graduated cylinder is 525ML (barrel seriously adsorbs resin, stands longer period of time resin and falls).

3, be poured slowly into 2L graduated cylinder 99.5% aromatic hydrocarbon be immersed in resin in arene solution (resin is by white Color gradually becomes crocus), bubble out is shaken, volume is 660ML after resin expansion, after mouth sealing and standing 24 hours, resinite Product is still 660ML.

4, resin aromatic hydrocarbon mixture is poured into the basket with strainer and filters arene, basket is then put into basket In formula filter, capping is logical to be dried with nitrogen and (arranges into side at bottom), and the raffinate arene filtered is put into waste liquid bottle, and hermetic bag is close Envelope, is handled to subsequent by lab assistant.

Four, Experiment Data Records:

Five, experimental calculation result

Six, conclusion

A21 resin in aromatic hydrocarbon in swelling volume be 23.7%.

Experiment three:

One, experiment purpose:

Measure expansion rate of the A21 resin in silicon tetrachloride.

Two, experiment equipment:

2L graduated cylinder, glass bar, silicon tetrachloride, basket filter (band strainer), the high-purity laboratory nitrogen that bore DN50 is transformed Gas, hermetic bag and leather sheath, gas mask, rubber gloves, exhaust gas processing device, PH test paper etc..

Three, experiment content:

2, the A21 resin for taking out laboratory drying, being poured slowly into and measuring the stacking volume of resin in 2L graduated cylinder is 505ML (barrel adsorbs resin, stands a period of time resin and falls).

3, be poured slowly into 2L graduated cylinder silicon tetrachloride make resin be immersed in silicon tetrachloride solution (resin by white gradually Become dark-brown, graduated cylinder mouth has a large amount of white smokes to generate, gradually floats with the addition resin of silicon tetrachloride), it shakes out Bubble, volume is 540ML after resin expansion, and after mouth sealing and standing 24 hours, resin volume is still 540ML.

4, resin silicon tetrachloride mixture is poured into the basket with strainer and filters silicon tetrachloride, then basket is put into In basket filter, capping is logical to be dried with nitrogen (bottom is arranged into side, and whether there is or not sour gas with PH test paper detection tail gas), the raffinate filtered Silicon tetrachloride is put into high-purity laboratory waste liquid tank, and hermetic bag sealing is handled to subsequent by lab assistant.

5, A21 resin, which is placed in basket filter, continuously blows two days, and the detection of PH test paper is unchanged, takes out bottling, carries out down Step experiment.

6, dried A21 resin is repeated into 2,3,4,5 steps again, is integrally repeated twice, experimental data is recorded.

Four, Experiment Data Records:

Five, experimental calculation result

Six, conclusion

Swelling volume of the A21 resin in silicon tetrachloride is 7.3%.

Experiment four:

One, experiment purpose:

Measure expansion rate of the A21 resin in trichlorosilane.

Two, experiment equipment:

2L graduated cylinder, glass bar, trichlorosilane, basket filter (band strainer), the high-purity laboratory nitrogen that bore DN50 is transformed Gas, hermetic bag and leather sheath, gas mask, rubber gloves.

Three, experiment content:

1, the A21 resin dried in withdrawing device, being poured slowly into and measuring the stacking volume of resin in 2L graduated cylinder is 525ML (barrel adsorbs resin, stands a period of time resin and falls).

2, be poured slowly into 2L graduated cylinder trichlorosilane make resin be immersed in trichlorosilane solution (resin by white gradually Become dark-brown, graduated cylinder mouth has a small amount of white smoke to generate, gradually floats with the addition resin of silicon tetrachloride), resin is swollen Volume is 560ML after swollen, and then toward nitrogen tube is accessed in graduated cylinder, graduated cylinder mouth is fixed with rubber band.Prevent gas accumulation from generating dangerous. (it can find that resin and trichlorosilane gradually react after standing more than ten minutes, have bubble generation inside resin, over time Under bubble is gradually moved up by bottom, internal to generate new bubble, repetitive cycling until top ruptures, and liquid level is slow Drop.)

3, after two hours, air entrapment out is shaken, volume is that (inside might have 570ML after reading again resin expansion Certain bubble occupies a part of volume).

4, collate the minutes experimental data.

Four, Experiment Data Records:

Five, experimental calculation result

Six, conclusion

Swelling volume of the A21 resin in trichlorosilane is 7.7%.

The quality for the product that production technology of the invention is produced in A-21 catalyst aqueous treatment and pretreatment Closely related, the prior art only individually produces various electron level chlorosilanes, the requirement to A-21 catalyst do not need it is too high, A-21 catalyst is not handled or only simple heat treatment, water content basically reaches production and want even if slightly higher It asks, and the present invention is the method for producing dichlororosilane eiectronic grade, electron level trichlorosilane and electron level silicon tetrachloride simultaneously, by It is in requiring to obtain three kinds of products, very high for the performance requirement of A-21 catalyst so process is complex, especially water content It is required that, it is necessary to below 3%.If catalyst water content is relatively high, have a great impact to production technology of the invention, the One: will lead to the dichlorosilane yield decline in product；Second: will lead to one chlorine of low boiling product, three hydrogen silicon even monosilane etc. Impurity generates, these impurity all influence electronic gas used in semicon industry very big；Third: catalyst treatment is bad, can lead It causes catalyst expansion broken or reacts with water to generate silica or silica type precipitating, occupying catalyst pores causes to be catalyzed Agent inactivation etc..

Above-mentioned experiment obtains expansion rate of the A21 resin in alcohols, arene, silicon tetrachloride, trichlorosilane why It obtains each expansion rate, is on the one hand to the open addition volume etc. for calculating catalyst, protection equipment etc., be on the other hand also public affairs Open the expansion data with various solvents such as alcohols or arene because have to handle using these solvents catalyst with Guarantee catalyst performance, in using these solvents processing catalyst process, different expansion rates requires processing catalyst addition Measure it is different, not so exist expansion top bad equipment possibility.

It is first in disproportionation reactor, Catalyst packing is good before carrying out disproportionated reaction in production technology of the invention (expansion rate being incorporated in each solvent determines loadings) afterwards, it is dry to resin with hot nitrogen (70-80 DEG C), it is added after 24 hours The alcohol solution (such as ethanol solution) of 99.5wt%, is dried up after 24 hours with hot nitrogen；The alcohols for adding 99.5wt% is molten Liquid is dried up after 24 hours with hot nitrogen, and so water content of the circulation in total three times only into detection alcohols is lower than 500ppm；Then It is added into resin and analyzes pure rank aromatic hydrocarbon solution (such as benzene), dried up after 24 hours with hot nitrogen, add the pure grade of analysis It is low to dry up the alcohol content for so recycling and being detected three times in arene in total with hot nitrogen for other arene solution after 24 hours Chlorosilane can be passed through in the side 0.3wt%.

Chlorosilane gas wash tower is plate column, and chlorosilane dedusting tower reboiler is kettle type reboiler, facilitates chlorosilane gas wash tower Maintenance detaches.The present invention uses two sets plate column dedustings, and after complexing agent is added in material, complexing agent is easy and iron chloride etc. Metal chloride forms solid high-polymer, and the blocking of equipment or pipeline, the present invention are be easy to cause when separating using conventional fillers tower It selects gas wash tower to separate high polymer, and regular outlet, reduces the risk that system is influenced by high polymer.

No. 1 knockout tower is packed tower, mainly for separating of DCS, TCS and STC.No. 2 knockout towers, DCS are de- light Tower, DCS weight-removing column, No. 3 knockout towers, TCS lightness-removing column, TCS weight-removing column, STC lightness-removing column and STC weight-removing column are packed tower.

In anti-disproportionation reactor, the DCS being discharged inside and outside distillation system is converted to TCS with the STC of general quality, is saved The expense of processing DCS, avoids the security risk in DCS treatment process, while the TCS of output can be used for photovoltaic or circulation It utilizes.

Using production method of the invention, finally obtained dichlororosilane eiectronic grade, electron level trichlorosilane and electronics Grade silicon tetrachloride product, detects it, as a result as follows:

Dichlororosilane eiectronic grade testing result is as follows:

Project	Unit	Index	Project	Unit	Index
						Purity	Vol%	≥99.99	Aluminium	ppbw	≤0.1
Other chlorosilanes	ppmw	≤1000	Calcium	ppbw	≤0.1
						Carbon	ppmw	≤1	Cobalt	ppbw	≤0.1
Phosphorus+arsenic	ppba	≤0.03	Copper	ppbw	≤0.1
						Boron+aluminium	ppba	≤0.01	Resistivity	Ω.cm	≥1000
Iron	ppbw	≤0.1	One chlorine hydrogen silicon	Vol%	≤0.01
						Nickel	ppbw	≤0.1	Trichlorosilane	Vol%	≤0.001
Chromium	ppbw	≤0.1	Silicon tetrachloride	Vol%	≤0.001

Electron level trichlorosilane testing result is as follows:

Project	Unit	Index	Project	Unit	Index
						Purity	Wt%	≥99.999	Aluminium	ppbw	≤0.1
Other chlorosilanes	ppmw	≤100	Calcium	ppbw	≤0.1
						Carbon	ppmw	≤1	Cobalt	ppbw	≤0.1
Phosphorus+arsenic	ppba	≤0.03	Copper	ppbw	≤0.1
						Boron+aluminium	ppba	≤0.01	Resistivity	Ω.cm	≥500
Iron	ppbw	≤0.1	One chlorine hydrogen silicon	Wt%	≤0.001
						Nickel	ppbw	≤0.1	Dichlorosilane	Wt%	≤0.01
Chromium	ppbw	≤0.1	Silicon tetrachloride	Wt%	≤0.01

Electron level silicon tetrachloride testing result is as follows:

Project	Unit	Index	Project	Unit	Index
						Purity	Wt%	≥99.999	Aluminium	ppbw	≤0.1
Other chlorosilanes	ppmw	≤100	Calcium	ppbw	≤0.1
						Carbon	ppmw	≤1	Cobalt	ppbw	≤0.1
Phosphorus+arsenic	ppba	≤0.03	Copper	ppbw	≤0.1
						Boron+aluminium	ppba	≤0.01	Resistivity	Ω.cm	≥1000
Iron	ppbw	≤0.1	One chlorine hydrogen silicon	Wt%	≤0.001
						Nickel	ppbw	≤0.1	Dichlorosilane	Wt%	≤0.001
Chromium	ppbw	≤0.1	Trichlorosilane	Wt%	≤0.01

The present invention dichlororosilane eiectronic grade, electron level trichlorosilane and electron level silicon tetrachloride produced can expire The demand of foot modern times large scale integrated circuit, no matter product metal impurities or alms giver's acceptor impurity for semiconductor and Other chlorosilane impurity can meet electron level requirement.It is detected using the epitaxial film of electron level chlorosilane produced by the invention growth Its intrinsic resistivity can completely even remote super semicon industry demand.Using production method of the invention, according to object used Material conservation is calculated, and the yield of completed electronic grade dichlorosilane can reach about 6%, and completed electronic grade trichlorosilane yield can Reach about 25%, completed electronic grade silicon tetrachloride yield can be of about 8%.The final output extension of the dichlororosilane eiectronic grade of production The intrinsic resistivity of film can achieve 3000 Ω cm, and the basic dichloro-dihydro without by-product low-purity in process of production Silicon generates because in process of production the dichlorosilane of high boiling low boiling discharge by last anti-disproportionated reaction all at Reason is fallen, and obtained trichlorosilane is also used as raw materials recovery of the invention and recycles；The present invention is high boiling in process of production There are also the mixtures containing trichlorosilane and silicon tetrachloride for the by-product of low boiling discharge, are passing through rectifying separating step of the invention Afterwards, the trichlorosilane of production can be used as the raw material of photovoltaic polysilicon, on the one hand the silicon tetrachloride of production can be used to produce to receive Meter level gas-phase silica, still further aspect can be used as the raw material of optical fiber rank silicon tetrachloride.

In addition, term " first ", " second " etc. and " primary ", " secondary " etc. are used for description purposes only, and should not be understood as Indication or suggestion relative importance or the quantity for implicitly indicating indicated technical characteristic." first ", " are defined as a result, Two " etc. and the feature of " primary ", " secondary " etc. can explicitly or implicitly include at least one of the features.

Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned Embodiment is changed, modifies, replacement and variant.

Claims

1. a kind of method for producing dichlororosilane eiectronic grade, electron level trichlorosilane and electron level silicon tetrachloride simultaneously, special Sign is, comprising the following steps:

Trichlorosilane after de- heavy constituent is carried out disproportionated reaction, obtained comprising dichlorosilane, trichlorosilane and four chlorinations by S4 First mixture of silicon；

The first mixture after final dusting is carried out first separation by S6, obtains the containing dichlorosilane and trichlorosilane Two mixtures and third mixture containing trichlorosilane and silicon tetrachloride；

Second mixture is successively carried out secondary separation processing, secondary de- light component processing and secondary de- heavy constituent processing, obtained by S7 To dichlororosilane eiectronic grade；Third mixture is subjected to separating treatment three times, obtains the 4th mixture containing trichlorosilane And the 5th mixture containing silicon tetrachloride, the 4th mixture is successively taken off into light component processing three times and takes off recombination three times Divide processing, obtain electron level trichlorosilane, the 5th mixture is successively subjected to four de- light components processing and four de- heavy constituents Processing, obtains electron level silicon tetrachloride.

2. a kind of according to claim 1 produce dichlororosilane eiectronic grade, electron level trichlorosilane and electron level four simultaneously The method of silicon chloride, which is characterized in that in step S1, the purity of the crude product trichlorosilane is 2N, the primary dedusting processing It being carried out in raw material gas wash tower, tower presses 0.2-0.4MPa, 68-87 DEG C of tower top temperature, and tower reactor removes the boiling point impurity higher than tower top temperature, Overhead extraction.

3. a kind of according to claim 1 produce dichlororosilane eiectronic grade, electron level trichlorosilane and electron level four simultaneously The method of silicon chloride, which is characterized in that in step S2, the Gas Phase Adsorption processing carries out in adsorption tower, is inhaled using molecular sieve It is attached, tower press 0.2-0.4MPa, 90 DEG C of tower top temperature.

4. a kind of according to claim 1 produce dichlororosilane eiectronic grade, electron level trichlorosilane and electron level four simultaneously The method of silicon chloride, which is characterized in that step S3, the once de- light component processing carry out in raw material lightness-removing column, tower pressure 0.2-0.4MPa, 68-87 DEG C of tower top temperature, tower top outlet, tower reactor extraction；The once de- heavy constituent processing is in raw material weight-removing column It carries out, tower presses 0.2-0.4MPa, 68-87 DEG C of tower top temperature, tower reactor outlet, overhead extraction.

5. a kind of according to claim 1 produce dichlororosilane eiectronic grade, electron level trichlorosilane and electron level four simultaneously The method of silicon chloride, which is characterized in that in step S4, the disproportionated reaction carries out in disproportionation reactor, disproportionation reactor pressure Power 0.2-0.3MPa, 60-70 DEG C of reaction temperature；Disproportionation reactor is double tubesheet tubular heat exchanger, is water, shell side in tube side To take off the trichlorosilane after heavy constituent and water content being added in macroreticular weakly base anion of 0.3% surface below with tertiary amino Exchanger resin A21 is as catalyst；First mixture includes 6wt%-7wt% dichlorosilane, 80wt%-81wt% tri- Chlorine hydrogen silicon, 11wt%-12wt% silicon tetrachloride.

6. a kind of according to claim 1 produce dichlororosilane eiectronic grade, electron level trichlorosilane and electron level four simultaneously The method of silicon chloride, which is characterized in that in step S5, add complexing agent the step of carried out in chlorosilane pans, the network Mixture is aromatic aldehyde or fragrant aldehyde derivatives, and additive amount is the 0.08wt%-0.15wt% of the first mixture；It is described secondary to remove Dirt processing carries out in chlorosilane gas wash tower, and tower presses 0.2-0.4MPa, 70-95 DEG C of tower top temperature, and tower reactor removes boiling point than tower top temperature High impurity, overhead extraction.

7. according to claim 1 to any one of 6 it is described it is a kind of produce simultaneously dichlororosilane eiectronic grade, electron level trichlorosilane and The method of electron level silicon tetrachloride, which is characterized in that in step S6, the first separation carries out in No. 1 knockout tower, tower pressure 0.2-0.4MPa, 53-73 DEG C of tower top temperature, the second mixture of overhead extraction, tower bottom produce third mixture.

8. a kind of according to claim 7 produce dichlororosilane eiectronic grade, electron level trichlorosilane and electron level four simultaneously The method of silicon chloride, which is characterized in that in step S7, the secondary separation processing carries out in No. 2 knockout towers, and tower presses 0.2- 0.4MPa, 41-60 DEG C of tower top temperature, tower reactor outlet, overhead extraction；The secondary de- light component processing carries out in DCS lightness-removing column, Tower presses 0.2-0.4MPa, 41-60 DEG C of tower top temperature, tower top outlet, tower reactor extraction；The secondary de- heavy constituent processing is in the de- weight of DCS It is carried out in tower, tower presses 0.2-0.4MPa, 41-60 DEG C of tower top temperature, tower reactor outlet, overhead extraction dichlororosilane eiectronic grade.

9. a kind of according to claim 8 produce dichlororosilane eiectronic grade, electron level trichlorosilane and electron level four simultaneously The method of silicon chloride, which is characterized in that be pumped into the material of DCS lightness-removing column tower top outlet material and DCS weight-removing column tower reactor outlet Anti- disproportionation reactor, at the same into anti-disproportionation reactor be added 10 times of weight of material crude product silicon tetrachloride, in catalyst action Under anti-disproportionated reaction obtain trichlorosilane, be back to the raw material of step S1；Anti- disproportionation reactor pressure 0.5MPa, temperature 70 C.

10. a kind of according to claim 7 produce dichlororosilane eiectronic grade, electron level trichlorosilane and electron level four simultaneously The method of silicon chloride, which is characterized in that in step S7, the separating treatment three times carries out in No. 3 knockout towers, and tower presses 0.2- 0.4MPa, 68-87 DEG C of tower top temperature, the 4th mixture of overhead extraction, tower reactor produce the 5th mixture；It is described to take off at light component three times Reason carries out in TCS lightness-removing column, and tower presses 0.2-0.4MPa, 68-87 DEG C of tower top temperature, tower top outlet, tower reactor extraction；It is described to take off three times Heavy constituent processing carries out in TCS weight-removing column, and tower presses 0.2-0.4MPa, 68-87 DEG C of tower top temperature, tower reactor outlet, overhead extraction electricity Sub- grade trichlorosilane；Four de- light component processing carry out in STC lightness-removing column, and tower presses 0.2-0.4MPa, tower top temperature 95- 117 DEG C, tower top outlet, tower reactor extraction；Four de- heavy constituent processing carry out in STC weight-removing column, and tower presses 0.2-0.4MPa, 95-117 DEG C of tower top temperature, tower reactor outlet, overhead extraction electron level silicon tetrachloride.