CN103112858B - Liquid-phase chlorination method of dichlorosilane in polysilicon byproduct - Google Patents
Liquid-phase chlorination method of dichlorosilane in polysilicon byproduct Download PDFInfo
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- CN103112858B CN103112858B CN201310014605.1A CN201310014605A CN103112858B CN 103112858 B CN103112858 B CN 103112858B CN 201310014605 A CN201310014605 A CN 201310014605A CN 103112858 B CN103112858 B CN 103112858B
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- silicon tetrachloride
- dichlorosilane
- chlorine
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Abstract
The invention discloses a liquid-phase chlorination method of dichlorosilane in a polysilicon byproduct, which is characterized by performing liquid-phase chlorination reaction on dichlorosilane and chlorine in a silicon tetrachloride solution, wherein the reaction temperature is (-50)-50 DEG C, the reaction pressure is 0.5 MPa or above, and silicon tetrachloride and hydrogen chloride are generated after the reaction. The invention has the following advantages: the method is safe and controllable, the dichlorosilane conversion rate can be up to 99.9% or above, the silicon tetrachloride yield can be up to 98.5% or above, the treatment process of dichlorosilane in a polysilicon byproduct is effectively simplifies, the energy consumption is lowered, and a feasible route is provided for the treatment of the dichlorosilane byproduct in polysilicon factories.
Description
Technical field
The present invention relates to process for liquid phase chlorination, be specifically related to the process for liquid phase chlorination of dichlorosilane in a kind of polysilicon by-product.
Background technology
The molecular formula of dichlorosilane is H
2siCl
2, another name dichlorosilane, English abbreviation DCS is one of by product important in addition to silicon tetrachloride in improved Siemens polysilicon production process.
Dichlorosilane to be suffocated smell and corrosive colourless toxic gas for having pungency at normal temperatures and pressures.The mode of current domestic production of polysilicon producer process dichlorosilane generally has two kinds: one to be incorporated in silicon tetrachloride waste liquid, is processed by specialized factory; Two are sent into vent gas treatment workshop section, and be hydrolyzed process under alkali lye effect.Adopt these processing modes, cost is high, easily causes the waste of resource and the pollution of environment.U.S. combinating carbide company develops anti-disproportionation processes, and this technique, under the katalysis of organic amine or organic amine resin, makes dichlorosilane and silicon tetrachloride reaction generate trichlorosilane, achieves the resource utilization of dichlorosilane, and obtain industrial applications.Studies in China personnel disclose a kind of technique dichlorosilane being converted into trichlorosilane in Chinese patent CN102068829A, its know-why and American Association Carbide basically identical.But anti-disproportionation processes per pass conversion is low, rectifying energy consumption for separating of reaction product is high, and the existing rectifying tower of polysilicon factory cannot be used, and be necessary for the special rectifying tower of anti-disproportionation coordinative composition of equipments, this adds the complicacy of facility investment and process undoubtedly.
Summary of the invention
Technical problem to be solved by this invention is the process for liquid phase chlorination of dichlorosilane in the polysilicon by-product providing a kind of safety controlled for the deficiencies in the prior art.
The present invention solves the problems of the technologies described above adopted technical scheme: the process for liquid phase chlorination of dichlorosilane in a kind of polysilicon by-product, liquid phase chlorination is there is and reacts in dichlorosilane and chlorine in silicon tetrachloride solution, temperature of reaction is-50 ~ 50 DEG C, reaction pressure is more than 0.5MPa, generates silicon tetrachloride and hydrogenchloride after reaction.Its reaction formula is as follows:
H
2SiCl
2+2Cl
2→SiCl
4+2HCl
Due to dichlorosilane and oxygenant, the mixed gas as air, oxygen, chlorine etc. are formed has the limits of explosion of non-constant width, the flash-point extremely low (being-37 DEG C) of dichlorosilane simultaneously, again because above-mentioned reaction is strong exothermal reaction, the directly contact between chlorine and dichlorosilane can quick explosion caused property reaction.Utilize silicon tetrachloride as the inert solvent of circulating reaction system and thinner, make dichlorosilane and chlorine that liquid phase chlorination occur in silicon tetrachloride solution to react, microcosmic reduces the probability of collision of dichlorosilane and chlorine, the liquid phase chlorination of dichlorosilane carries out under the condition that safety is controlled, does not have risk of explosion.
Preferably, described reaction pressure is 0.5 ~ 5MPa.
Preferably, concrete steps are: in the circulating reaction system being full of silicon tetrachloride, inject the silicon tetrachloride solution of dichlorosilane and the silicon tetrachloride solution of chlorine continuously, make dichlorosilane and chlorine that continuous print liquid phase chlorination occur in silicon tetrachloride solution and react; Reacted material not cracked ends separator decompression separation is gas-liquid two-phase, gas phase is by the saturated hydrogen chloride gas of silicon tetrachloride, liquid phase is chlorinated the saturated silicon tetrachloride of hydrogen, hydrogen chloride gas is discharged circulating reaction system, the part overflow from circulating reaction system being chlorinated the saturated silicon tetrachloride of hydrogen is flowed out, and remaining part turns back to circulating reaction system again and recycles.
Preferably, in the silicon tetrachloride solution of described dichlorosilane, the mol ratio of dichlorosilane and silicon tetrachloride is 1:20 ~ 200; In the silicon tetrachloride solution of described chlorine, the mol ratio of chlorine and silicon tetrachloride is 1:20 ~ 200.
Preferably, when the silicon tetrachloride solution of described dichlorosilane and the silicon tetrachloride solution of chlorine inject circulating reaction system continuously, dichlorosilane is 1:1.95 ~ 2.05 with the molar flow rate ratio of chlorine.
Preferably, the pressure-controlling of the material after separator decompression separation is at 0.05 ~ 1MPa.
Compared with prior art, the invention has the advantages that:
(1) process for liquid phase chlorination of dichlorosilane in polysilicon by-product of the present invention, its principle utilizes silicon tetrachloride as the inert solvent of circulating reaction system and thinner, make dichlorosilane and chlorine that liquid phase chlorination occur in silicon tetrachloride solution to react, microcosmic reduces the probability of collision of dichlorosilane and chlorine, the liquid phase chlorination of dichlorosilane carries out under the condition that safety is controlled, does not have risk of explosion;
(2) using silicon tetrachloride as inert solvent, dichlorosilane and chlorine are dissolved wherein before reaction, one of reacted target product is silicon tetrachloride, with reaction before solvent be same material, ensure that the heat and mass efficiency of circulating reaction system the best, target product silicon tetrachloride after simultaneous reactions can turn back to circulating reaction system and recycle, greatly simplifie follow-up lock out operation, reduce separating energy consumption, make technical process become simple;
(3) silicon tetrachloride of liquid phase can absorb expeditiously and conduct reaction heat, simultaneously by the ratio that controls reaction mass and solvent just can the temperature rise of convenient, reliable controlled circulation reactive system in the scope of safety, thus completely avoid because heat of reaction Rapid Accumulation causes the generation of runaway reaction phenomenon;
(4) control the reaction conditionss such as suitable reaction pressure and guarantee that the material in circulating reaction system is in homogeneous liquid phase all the time, and the hydrogen chloride gas that reaction generates also is dissolved in this liquid phase, ensure that circulating reaction system can be in homogeneous state, thus avoid formation gas-liquid two-phase in circulating reaction system and cause gas phase to dodge the possibility of quick-fried reaction generation;
(5) after polysilicon factory adopts the inventive method, the silicon tetrachloride that overflow is flowed out from circulating reaction system can be delivered directly in existing rectifying tower and carry out later separation operation, need not other supporting special rectifying tower, and existing polysilicon factory all establishes for being the hot hydrogenation of trichlorosilane or cold hydrogenation apparatus by converting silicon tetrachloride, visible, from at utmost utilizing polysilicon factory existing apparatus and flow process, reduction Operating Complexity angle, dichlorosilane being converted into silicon tetrachloride and realizing one of optimal path of dichlorosilane resource utilization beyond doubt.
Therefore, the inventive method safety is controlled, the transformation efficiency of its dichlorosilane can reach more than 99.9%, the yield of silicon tetrachloride can reach more than 98.5%, effectively simplify the treatment scheme of dichlorosilane in polysilicon by-product, reduce energy consumption, for polysilicon factory processes dichlorosilane by product provides a practicable approach.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the circulating reaction system that embodiment adopts.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
As shown in Figure 1, the circulating reaction system that embodiment adopts comprises recycle pump 1, recycle pump 2, mixing tank 3, mixing tank 4, tubular reactor 5 and separator 6.Recycle pump 1 can control and regulate the flow of the material flowing into mixing tank 4, recycle pump 2 can control and regulate the flow of the material flowing into mixing tank 3, material is injected into tubular reactor 5 from mixing tank 3 and mixing tank 4, and the separator 6 of carry potential overflow function can carry out decompression separation to reacted material.
Embodiment 1, as shown in Figure 1:
The silicon tetrachloride of purity more than 99.9% is filled with, until silicon tetrachloride is full of circulating reaction system and overflow from separator 6 in circulating reaction system, open and regulate recycle pump 1 and recycle pump 2, the mass rate making the silicon tetrachloride entering mixing tank 4 is 50kmol/h, makes the mass rate of the silicon tetrachloride entering mixing tank 3 be 50kmol/h, the silicon tetrachloride solution that dichlorosilane forms dichlorosilane is injected continuously in mixing tank 4, the silicon tetrachloride solution of liquid chlorine or chlorine formation chlorine is injected continuously in mixing tank 3, the molar flow rate making the dichlorosilane entering mixing tank 4 is 1kmol/h, and the molar flow rate entering the chlorine of mixing tank 3 is 2kmol/h, through the mixing effect of mixing tank 4, the mol ratio going out dichlorosilane and silicon tetrachloride in the silicon tetrachloride solution of the dichlorosilane of mixing tank 4 is 1:50, through the mixing effect of mixing tank 3, the mol ratio going out chlorine and silicon tetrachloride in the silicon tetrachloride solution of the chlorine of mixing tank 3 is 1:25, the silicon tetrachloride solution of the silicon tetrachloride solution going out the dichlorosilane of mixing tank 4 and the chlorine going out mixing tank 3 is injected continuously in tubular reactor 5, continuous print liquid phase chlorination is there is and reacts in dichlorosilane and chlorine in silicon tetrachloride solution, reaction pressure controls at 4.5MPa, temperature of reaction controls at 45 ± 2.5 DEG C, reaction time is 10s, reacted material not cracked ends separator 6 decompression separation is gas-liquid two-phase, post-decompression pressure is 0.5MPa, gas phase is by the saturated hydrogen chloride gas of silicon tetrachloride, liquid phase is chlorinated the saturated silicon tetrachloride of hydrogen, hydrogen chloride gas is discharged circulating reaction system, the part overflow from separator 6 being chlorinated the saturated silicon tetrachloride of hydrogen is flowed out, remaining part turns back to tubular reactor 5 again and recycles.
At tubular reactor 5 end sampling analysis after this circulating reaction system steady running 6h, result shows that the transformation efficiency of dichlorosilane is 99.9%, and the yield of silicon tetrachloride is 99.5%.
Embodiment 2, as shown in Figure 1:
The silicon tetrachloride of purity more than 99.9% is filled with, until silicon tetrachloride is full of circulating reaction system and overflow from separator 6 in circulating reaction system, open and regulate recycle pump 1 and recycle pump 2, the mass rate making the silicon tetrachloride entering mixing tank 4 is 50kmol/h, makes the mass rate of the silicon tetrachloride entering mixing tank 3 be 395kmol/h, the silicon tetrachloride solution that dichlorosilane forms dichlorosilane is injected continuously in mixing tank 4, the silicon tetrachloride solution of liquid chlorine or chlorine formation chlorine is injected continuously in mixing tank 3, the molar flow rate making the dichlorosilane entering mixing tank 4 is 2kmol/h, and the molar flow rate entering the chlorine of mixing tank 3 is 3.95kmol/h, through the mixing effect of mixing tank 4, the mol ratio going out dichlorosilane and silicon tetrachloride in the silicon tetrachloride solution of the dichlorosilane of mixing tank 4 is 1:25, through the mixing effect of mixing tank 3, the mol ratio going out chlorine and silicon tetrachloride in the silicon tetrachloride solution of the chlorine of mixing tank 3 is 1:100, the silicon tetrachloride solution of the silicon tetrachloride solution going out the dichlorosilane of mixing tank 4 and the chlorine going out mixing tank 3 is injected continuously in tubular reactor 5, continuous print liquid phase chlorination is there is and reacts in dichlorosilane and chlorine in silicon tetrachloride solution, reaction pressure controls at 2MPa, temperature of reaction controls at 0 ± 2.5 DEG C, reaction time is 15s, reacted material not cracked ends separator 6 decompression separation is gas-liquid two-phase, post-decompression pressure is 0.15MPa, gas phase is by the saturated hydrogen chloride gas of silicon tetrachloride, liquid phase is chlorinated the saturated silicon tetrachloride of hydrogen, hydrogen chloride gas is discharged circulating reaction system, the part overflow from separator 6 being chlorinated the saturated silicon tetrachloride of hydrogen is flowed out, remaining part turns back to tubular reactor 5 again and recycles.
At tubular reactor 5 end sampling analysis after this circulating reaction system steady running 12h, result shows that the transformation efficiency of dichlorosilane is 99.95%, and the yield of silicon tetrachloride is 98.5%.
Embodiment 3, as shown in Figure 1:
The silicon tetrachloride of purity more than 99.9% is filled with, until silicon tetrachloride is full of circulating reaction system and overflow from separator 6 in circulating reaction system, open and regulate recycle pump 1 and recycle pump 2, the mass rate making the silicon tetrachloride entering mixing tank 4 is 98kmol/h, makes the mass rate of the silicon tetrachloride entering mixing tank 3 be 50.5kmol/h, the silicon tetrachloride solution that dichlorosilane forms dichlorosilane is injected continuously in mixing tank 4, the silicon tetrachloride solution of liquid chlorine or chlorine formation chlorine is injected continuously in mixing tank 3, the molar flow rate making the dichlorosilane entering mixing tank 4 is 0.5kmol/h, and the molar flow rate entering the chlorine of mixing tank 3 is 1.01kmol/h, through the mixing effect of mixing tank 4, the mol ratio going out dichlorosilane and silicon tetrachloride in the silicon tetrachloride solution of the dichlorosilane of mixing tank 4 is 1:196, through the mixing effect of mixing tank 3, the mol ratio going out chlorine and silicon tetrachloride in the silicon tetrachloride solution of the chlorine of mixing tank 3 is 1:50, the silicon tetrachloride solution of the silicon tetrachloride solution going out the dichlorosilane of mixing tank 4 and the chlorine going out mixing tank 3 is injected continuously in tubular reactor 5, continuous print liquid phase chlorination is there is and reacts in dichlorosilane and chlorine in silicon tetrachloride solution, reaction pressure controls at 0.8MPa, temperature of reaction controls at-35 ± 2.5 DEG C, reaction time is 30s, reacted material not cracked ends separator 6 decompression separation is gas-liquid two-phase, post-decompression pressure is 0.06MPa, gas phase is by the saturated hydrogen chloride gas of silicon tetrachloride, liquid phase is chlorinated the saturated silicon tetrachloride of hydrogen, hydrogen chloride gas is discharged circulating reaction system, the part overflow from separator 6 being chlorinated the saturated silicon tetrachloride of hydrogen is flowed out, remaining part turns back to tubular reactor 5 again and recycles.
At tubular reactor 5 end sampling analysis after this circulating reaction system steady running 12h, result shows that the transformation efficiency of dichlorosilane is 99.9%, and the yield of silicon tetrachloride is 99.2%.
Claims (5)
1. the process for liquid phase chlorination of dichlorosilane in a polysilicon by-product, it is characterized in that dichlorosilane and chlorine liquid phase chlorination occur in silicon tetrachloride solution and reacts, temperature of reaction is-50 ~ 50 DEG C, reaction pressure is more than 0.5MPa, silicon tetrachloride and hydrogenchloride is generated after reaction, concrete steps are: in the circulating reaction system being full of silicon tetrachloride, the continuous silicon tetrachloride solution of injection dichlorosilane and the silicon tetrachloride solution of chlorine, make dichlorosilane and chlorine that continuous print liquid phase chlorination occur in silicon tetrachloride solution and react; Reacted material not cracked ends separator decompression separation is gas-liquid two-phase, gas phase is by the saturated hydrogen chloride gas of silicon tetrachloride, liquid phase is chlorinated the saturated silicon tetrachloride of hydrogen, hydrogen chloride gas is discharged circulating reaction system, the part overflow from circulating reaction system being chlorinated the saturated silicon tetrachloride of hydrogen is flowed out, and remaining part turns back to circulating reaction system again and recycles.
2. the process for liquid phase chlorination of dichlorosilane in a kind of polysilicon by-product according to claim 1, is characterized in that described reaction pressure is 0.5 ~ 5MPa.
3. the process for liquid phase chlorination of dichlorosilane in a kind of polysilicon by-product according to claim 1, it is characterized in that in the silicon tetrachloride solution of described dichlorosilane, the mol ratio of dichlorosilane and silicon tetrachloride is 1:20 ~ 200; In the silicon tetrachloride solution of described chlorine, the mol ratio of chlorine and silicon tetrachloride is 1:20 ~ 200.
4. the process for liquid phase chlorination of dichlorosilane in a kind of polysilicon by-product according to claim 1, when it is characterized in that the silicon tetrachloride solution of described dichlorosilane and the silicon tetrachloride solution of chlorine inject circulating reaction system continuously, dichlorosilane is 1:1.95 ~ 2.05 with the molar flow rate ratio of chlorine.
5. the process for liquid phase chlorination of dichlorosilane in a kind of polysilicon by-product according to claim 1, is characterized in that the pressure-controlling of the material after separator decompression separation is at 0.05 ~ 1MPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310014605.1A CN103112858B (en) | 2013-01-15 | 2013-01-15 | Liquid-phase chlorination method of dichlorosilane in polysilicon byproduct |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357286A (en) * | 2007-07-31 | 2009-02-04 | 中国恩菲工程技术有限公司 | Method for recovering dichloro-dihydro silicon from off-gas generated from the production of polycrystalline silicon |
| CN102068829A (en) * | 2010-11-24 | 2011-05-25 | 天津大学 | Baffle reaction-rectification equipment and anti-disproportionation reaction between dichlorosilane and silicon tetrachloride |
| CN102791630A (en) * | 2010-03-10 | 2012-11-21 | 信越化学工业株式会社 | Method for producing trichlorosilane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9067338B2 (en) * | 2008-08-04 | 2015-06-30 | Semlux Technologies, Inc. | Method to convert waste silicon to high purity silicon |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357286A (en) * | 2007-07-31 | 2009-02-04 | 中国恩菲工程技术有限公司 | Method for recovering dichloro-dihydro silicon from off-gas generated from the production of polycrystalline silicon |
| CN102791630A (en) * | 2010-03-10 | 2012-11-21 | 信越化学工业株式会社 | Method for producing trichlorosilane |
| CN102068829A (en) * | 2010-11-24 | 2011-05-25 | 天津大学 | Baffle reaction-rectification equipment and anti-disproportionation reaction between dichlorosilane and silicon tetrachloride |
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