CN116534864A - Chlorosilane rectifying and impurity removing process and system in polysilicon production - Google Patents
Chlorosilane rectifying and impurity removing process and system in polysilicon production Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 75
- 239000012535 impurity Substances 0.000 title claims abstract description 71
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000005046 Chlorosilane Substances 0.000 title claims abstract description 45
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 37
- 229920005591 polysilicon Polymers 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 159
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 110
- 239000002994 raw material Substances 0.000 claims abstract description 55
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 50
- 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 abstract description 45
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000605 extraction Methods 0.000 claims description 86
- 238000010992 reflux Methods 0.000 claims description 29
- 238000011084 recovery Methods 0.000 claims description 11
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000007791 liquid phase Substances 0.000 description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229910003902 SiCl 4 Inorganic materials 0.000 description 5
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
Description
技术领域technical field
本发明属于多晶硅生产领域，具体涉及一种多晶硅生产中氯硅烷精馏除杂工艺及系统。The invention belongs to the field of polysilicon production, and in particular relates to a chlorosilane rectification and impurity removal process and system in polysilicon production.
背景技术Background technique
三氯氢硅精馏是多晶硅生产工艺的核心技术之一，三氯氢硅提纯的程度直接影响最终产品多晶硅的纯度，而多晶硅的纯度又影响到下游太阳能电池的发电效果。多晶硅生产的原料硅粉、氢气、氯化氢以及各道工序在化学反应中产生的中间产物含有影响多晶硅质量的磷、硼以及金属杂质等。Trichlorosilane rectification is one of the core technologies of the polysilicon production process. The degree of trichlorosilane purification directly affects the purity of the final product polysilicon, and the purity of polysilicon affects the power generation effect of downstream solar cells. The raw material silicon powder, hydrogen, hydrogen chloride and the intermediate products produced in the chemical reaction of each process in the production of polysilicon contain phosphorus, boron and metal impurities that affect the quality of polysilicon.
现有电子级多晶硅生产大部分采用改良西门子法，均采用四级或五级精馏塔串联的精馏系统,且三氯氢硅产品采出率不高，部分氯硅烷原料不能完全回收利用。通常无法达到满足电子级多晶硅生产的需求，同时能耗较高、物料利用率低等问题。Most of the existing electronic-grade polysilicon production adopts the improved Siemens method, and a rectification system with four or five rectification towers connected in series is used, and the recovery rate of trichlorosilane products is not high, and some chlorosilane raw materials cannot be completely recycled. Usually it cannot meet the demand of electronic grade polysilicon production, and at the same time there are problems such as high energy consumption and low material utilization rate.
目前大多数的多晶硅生产企业所采用的精馏提纯多为多塔精馏，通常采用5级精馏工艺，流程为：粗分塔→脱轻塔→脱重塔→脱轻塔→脱重塔。此工艺存在问题如下：①多级精馏设备投资较大；②各精馏塔分离效果不好，易造成塔切除较大，产品采出率低、能耗高，还易造成产品不合格；③物料高，回收利用率低；④受原料杂质的影响，产品品质不稳定。At present, the rectification and purification adopted by most polysilicon production enterprises are mostly multi-tower rectification, usually adopting a 5-stage rectification process, and the process is: crude fractionation tower→light removal tower→heaviness removal tower→light removal tower→heaviness removal tower . The problems of this process are as follows: ①Multi-stage rectification equipment has a large investment; ②The separation effect of each rectification tower is not good, which may easily lead to large tower removal, low product recovery rate, high energy consumption, and easily lead to unqualified products; ③The material is high and the recycling rate is low; ④Because of the influence of raw material impurities, the product quality is unstable.
发明内容Contents of the invention
发明目的：本发明所要解决的技术问题是针对现有技术的不足，提供一种多晶硅生产中氯硅烷精馏除杂工艺及系统，实现同产能的设备投资减少20％以上，有效降低生产能耗；实现精馏系统的闭路循环，实现物料回收利用；稳定三氯氢硅品质，满足电子级多晶硅生产的需求。Purpose of the invention: The technical problem to be solved by the present invention is to provide a chlorosilane rectification and impurity removal process and system in polysilicon production, which can reduce the equipment investment of the same production capacity by more than 20%, and effectively reduce production energy consumption. ;Realize the closed-circuit circulation of the rectification system to realize material recycling; stabilize the quality of trichlorosilane to meet the needs of electronic-grade polysilicon production.
为了实现上述目的，本发明采取的技术方案如下：In order to achieve the above object, the technical scheme that the present invention takes is as follows:
一种多晶硅生产中氯硅烷精馏除杂工艺，包括如下步骤：A chlorosilane rectification and impurity removal process in polysilicon production, comprising the following steps:
上游原料氯硅烷通入原料吸附塔除杂，去除原料氯硅烷中大部分磷、硼以及金属杂质；The upstream raw material chlorosilane is passed into the raw material adsorption tower to remove impurities, and most of the phosphorus, boron and metal impurities in the raw material chlorosilane are removed;
除杂后的所述氯硅烷送入粗分塔，所述粗分塔被配置为具有至少粗分塔塔顶采出管、粗分塔塔釜采出管、粗分塔塔中侧线采出管三个出口；从塔顶切除二氯二氢硅及轻杂，从塔釜切除四氯化硅及重杂，从塔中侧线采出三氯氢硅；The chlorosilane after impurity removal is sent into the rough fractionation tower, and the rough fractionation tower is configured to have at least the extraction pipe at the top of the rough fractionation tower, the extraction pipe at the bottom of the crude fractionation tower, and the side line extraction in the rough fractionation tower. Pipe three outlets; remove dichlorodihydrosilane and light impurities from the top of the tower, remove silicon tetrachloride and heavy impurities from the bottom of the tower, and extract trichlorosilane from the side line of the tower;
所述粗分塔塔中侧线采出管采出的物料送入脱轻塔和脱重塔，所述脱轻塔至少具有脱轻塔上塔顶采出管和脱轻塔下塔釜采出管两个出口，通过脱轻塔的上塔顶切除轻杂(轻杂中还混合有部分二氯二氢硅DCS)；所述脱轻塔下塔釜采出管采出的物料送入所述脱重塔；所述脱重塔具有脱重塔上塔顶采出管和脱重塔下塔釜采出管两个出口，脱重塔下塔釜切除重杂(重杂中还混合有部分四氯化硅STC)，所述脱重塔上塔顶采出管采出合格三氯氢硅产品；The material extracted from the side line extraction pipe in the rough separation tower is sent to the light removal tower and the weight removal tower. Two outlets, light impurities are removed through the upper tower top of the light removal tower (parts of dichlorodihydrosilane DCS are also mixed in the light impurities); the material extracted from the lower tower still extraction pipe of the light removal tower is sent into the Heavy tower; the heavy removal tower has two outlets of the upper tower extraction pipe on the heavy removal tower and the lower tower still extraction pipe of the heavy removal tower, and the lower tower still of the heavy removal tower removes heavy impurities (partial tetrachloride is also mixed in the heavy impurities) Silicon STC), the top extraction pipe on the de-weighting tower extracts qualified trichlorosilane product;
所述粗分塔塔顶采出管、粗分塔塔釜采出管、脱轻塔上塔顶、脱重塔下塔釜采出管采出的物料送入反歧化后分离塔内进行组分分离；所述反歧化后分离塔被配置为具有至少反歧化后分离塔塔顶采出管、反歧化后分离塔塔釜采出管、反歧化后分离塔塔中侧线采出管三个出口，所述反歧化后分离塔塔顶采出管、反歧化后分离塔塔釜采出管采出的物料送入反歧化反应器内进行反歧化反应后重新送入反歧化后分离塔；反歧化后分离塔分离出的二氯二氢硅和四氯化硅送入反歧化反应器内进行反歧化反应生成三氯氢硅，产生的三氯氢硅与未反应的二氯二氢硅、四氯化硅重新进入反歧化后分离塔进行组分分离；The materials extracted from the top production pipe of the crude separation tower, the production pipe of the crude separation tower tower kettle, the upper tower top of the light removal tower, and the lower tower kettle production pipe of the heavy separation tower are sent into the separation tower after dedisproportionation for composition Separation; after the dedisproportionation, the separation tower is configured to have at least three outlets of the separation tower top production pipe after the dedisproportionation, the separation tower bottom production pipe after the dedisproportionation, and the sideline production pipe in the separation tower tower after the dedisproportionation , after the dedisproportionation, the material extracted from the top extraction pipe of the separation tower and the extraction pipe of the separation tower tower tank after the dedisproportionation is sent into the dedisproportionation reactor to carry out the dedisproportionation reaction, and then re-enter the separation tower after the dedisproportionation; After the disproportionation, the dichlorodihydrosilane and silicon tetrachloride separated from the separation tower are sent to the anti-disproportionation reactor for anti-disproportionation reaction to generate trichlorosilane, and the produced trichlorosilane is combined with unreacted dichlorodihydrosilane, Silicon tetrachloride re-enters the separation tower after dedisproportionation for component separation;
所述反歧化后分离塔塔中侧线采出管采出的物料与上游原料氯硅烷重新送入所述原料吸附塔，循环上述步骤，最终从脱重塔的上塔顶采出合格三氯氢硅产品。After the dedisproportionation, the material extracted from the side line extraction pipe of the separation tower tower and the upstream raw material chlorosilane are re-sent to the raw material adsorption tower, and the above steps are circulated, and finally qualified trichlorohydrogen is extracted from the upper tower top of the de-weighting tower. Silicon products.
进一步地，反歧化后分离塔顶分离出的二氯二氢硅，和反歧化后分离塔釜分离出的四氯化硅，在混合前进行配料计算，并从外部补入四氯化硅，将二氯二氢硅反应完全，反应式：SiH2Cl2+SiCl4→SiHCl3。Further, the dichlorodihydrosilane separated from the top of the separation tower after the anti-disproportionation, and the silicon tetrachloride separated from the bottom of the separation tower after the anti-disproportionation, the ingredients are calculated before mixing, and silicon tetrachloride is added from the outside, Complete reaction of dichlorodihydrosilane, reaction formula: SiH 2 Cl 2 +SiCl 4 →SiHCl 3 .
更进一步地，本发明还提供一种多晶硅生产中氯硅烷精馏除杂系统，包括原料缓冲罐、粗分塔、脱轻塔、脱重塔、反歧化后分离塔以及反歧化反应器；所述原料缓冲罐粗分塔、脱轻塔、脱重塔通过管线依次连接；Furthermore, the present invention also provides a chlorosilane rectification and impurity removal system in polysilicon production, which includes a raw material buffer tank, a crude fractionation tower, a light removal tower, a weight removal tower, a separation tower after deproportionation, and a deproportionation reactor; The crude fractionation tower, light removal tower, and weight removal tower of the raw material buffer tank are sequentially connected through pipelines;
所述粗分塔的塔侧通过管道连接至脱轻塔，所述脱轻塔的下塔釜通过管线连接至脱重塔，所述脱重塔的上塔顶通过管线采出合格三氯氢硅产品；The tower side of described crude fractionation tower is connected to light removal tower by pipeline, and the lower tower still of described light removal tower is connected to weight removal tower by pipeline, and the upper tower top of described weight removal tower is produced qualified trichlorohydrogen by pipeline. silicon products;
所述粗分塔的塔顶和塔釜、所述脱轻塔的上塔顶、以及脱重塔的下塔釜，分别通过采出管线一同连接至反歧化后分离塔；所述反歧化后分离塔的塔顶和塔釜分别通过采出管线连接至反歧化反应器，反歧化后分离塔的塔侧通过采出管线重新连接至原料缓冲罐；所述反歧化反应器通过采出管线返回反歧化后分离塔，将反应产生的混合气体重新进行分离。The tower top and the tower still of the described crude fractionation tower, the upper tower top of the described light removal tower, and the lower tower still of the heavy removal tower are respectively connected to the separation tower after the anti-disproportionation through the production pipeline; The top and bottom of the separation tower are respectively connected to the anti-disproportionation reactor through the production pipeline, and the side of the separation tower is reconnected to the raw material buffer tank through the production pipeline after dedisproportionation; After deproportionation, the separation tower re-separates the mixed gas generated by the reaction.
进一步地，所述反歧化后分离塔和反歧化反应器之间设有混合器；所述反歧化后分离塔的塔顶和塔釜分别通过采出管线连接至混合器，经混合后再送入反歧化反应器内。Further, a mixer is provided between the separation tower after the dedisproportionation and the dedisproportionation reactor; the top and bottom of the separation tower after the dedisproportionation are respectively connected to the mixer through the production pipeline, and then sent into the in the antiproportionation reactor.
进一步地，所述混合器的进料侧，还连接有四氯化硅补料管。Further, the feed side of the mixer is also connected with a silicon tetrachloride feeding pipe.
进一步地，该系统还包括反歧化后分离塔进料缓冲罐；所述反歧化后分离塔进料缓冲罐设置在反歧化后分离塔前端，用于缓存粗分塔、脱轻塔、脱重塔内采出的含杂物料；粗分塔的塔顶和塔釜、所述脱轻塔的上塔顶、以及脱重塔的下塔釜，分别通过采出管线一同连接至反歧化后分离塔进料缓冲罐内经缓存后再送入反歧化后分离塔；所述反歧化反应器通过采出管线连接至反歧化后分离塔进料缓冲罐。Further, the system also includes a feed buffer tank for the separation tower after the dedisproportionation; the feed buffer tank for the separation tower after the dedisproportionation is arranged at the front end of the separation tower after the dedisproportionation, and is used for buffering the crude fractionation tower, light removal tower, weight removal The impurity-containing material extracted in the tower; the top and bottom of the crude fractionation tower, the upper top of the light removal tower, and the lower bottom bottom of the weight removal tower are respectively connected to the post-disproportionation through the production pipeline. The feed buffer tank of the separation tower is buffered and then sent to the separation tower after dedisproportionation; the dedisproportionation reactor is connected to the feed buffer tank of the separation tower after dedisproportionation through a production pipeline.
进一步地，所述原料缓冲罐与粗分塔之间设有原料吸附塔；所述反歧化后分离塔进料缓冲罐的进料侧前端设有回收料吸附塔；所述粗分塔的塔顶和塔釜、所述脱轻塔的上塔顶、以及脱重塔的下塔釜，分别通过采出管线一同连接至回收料吸附塔内。通过原料吸附塔、回收料吸附塔去除原料中大部分磷、硼以及金属杂质。Further, a raw material adsorption tower is arranged between the raw material buffer tank and the rough separation tower; a recycled material adsorption tower is arranged at the front end of the feed side of the separation tower feed buffer tank after the dedisproportionation; the tower of the rough separation tower The top and the tower bottom, the upper tower top of the light removal tower, and the lower tower bottom of the weight removal tower are respectively connected to the recycled material adsorption tower through the production pipeline. Most of the phosphorus, boron and metal impurities in the raw material are removed through the raw material adsorption tower and the recycled material adsorption tower.
具体地，所述粗分塔的塔顶设有粗分塔塔顶回流管，所述粗分塔塔顶回流管上设有冷凝器以及粗分塔塔顶采出管；所述粗分塔的下塔釜设有粗分塔塔釜回流管，所述粗分塔塔釜回流管上设有再沸器以及粗分塔塔釜采出管；所述粗分塔的塔侧设有粗分塔塔中侧线采出管，通过粗分塔塔中侧线采出管连接至脱轻塔。Specifically, the top of the crude fractionation tower is provided with a crude fractionation tower top return pipe, and the crude fractionation tower top return pipe is provided with a condenser and a crude fractionation tower top recovery pipe; the rough fractionation tower The lower tower kettle is provided with a crude fractionation tower reactor reflux pipe, which is provided with a reboiler and a crude fractionation tower reactor recovery pipe on the crude fractionation tower reactor reflux pipe; The side line production pipe in the sub-column is connected to the light removal tower through the side line production tube in the coarse sub-column.
具体地，所述的脱轻塔包括依次串联的脱轻塔上塔和脱轻塔下塔；所述脱轻塔上塔的塔顶设有脱轻塔上塔顶回流管；所述脱轻塔上塔顶回流管上设有冷凝器以及脱轻塔上塔顶采出管；所述脱轻塔上塔的底部通过脱轻塔上塔底部采出管连接至脱轻塔下塔；Specifically, the light removal tower includes an upper tower of the light removal tower and a lower tower of the light removal tower connected in series; The upper tower top reflux pipe is provided with a condenser and the upper tower top extraction pipe of the light removal tower; the bottom of the upper tower of the light removal tower is connected to the lower tower of the light removal tower through the extraction pipe at the bottom of the upper tower of the light removal tower;
所述脱轻塔下塔的塔顶设有脱轻塔下塔顶气相管，通过脱轻塔下塔顶气相管重新连接至脱轻塔上塔；所述脱轻塔下塔的底部设有脱轻塔下塔釜回流管，所述脱轻塔下塔釜回流管上设有再沸器以及脱轻塔下塔釜采出管，通过脱轻塔下塔釜采出管连接至脱重塔。The top of the lower tower of the light removal tower is provided with a gas phase pipe at the top of the light removal tower, which is reconnected to the upper tower of the light removal tower through the gas phase pipe at the top of the lower tower of the light removal tower; the bottom of the lower tower of the light removal tower is provided with a lower tower of the light removal tower A kettle return pipe, the lower tower kettle return pipe of the light removal tower is provided with a reboiler and a lower tower kettle extraction pipe of the light removal tower, and is connected to the heavy weight removal tower through the lower tower kettle extraction pipe of the light removal tower.
具体地，所述的脱重塔包括依次串联的脱重塔下塔和脱重塔上塔；所述脱重塔下塔的塔顶设有脱重塔下塔顶气相管，通过脱重塔下塔顶气相管连接至脱重塔上塔；所述脱重塔下塔底部设有脱重塔下塔釜回流管，所述脱重塔下塔釜回流管上设有再沸器以及脱重塔下塔釜采出管；Specifically, the weight-removing tower includes a weight-removing tower lower tower and a weight-removing tower upper tower connected in series; The pipe is connected to the upper tower of the weight removal tower; the bottom of the lower tower of the weight removal tower is provided with a return pipe of the lower tower kettle of the weight removal tower, and a reboiler and a recovery pipe of the lower tower kettle of the weight removal tower are arranged on the return pipe of the lower tower kettle of the weight removal tower ;
所述脱重塔上塔的塔顶设有脱重塔上塔顶回流管，所述脱重塔上塔顶回流管上设有冷凝器以及脱重塔上塔顶采出管，通过脱重塔上塔顶采出管采出合格三氯氢硅产品；所述脱重塔上塔的底部设有脱重塔上塔釜底部采出管，通过脱重塔上塔釜底部采出管重新连接至脱重塔下塔。The tower top of the upper tower of the weight removal tower is provided with a top return pipe on the weight removal tower. Qualified trichlorosilane product is extracted from the tower top extraction pipe on the tower; the bottom of the upper tower of the weight removal tower is provided with an extraction pipe at the bottom of the upper tower kettle of the weight removal tower, and the outlet pipe at the bottom of the upper tower kettle of the weight removal tower is re- Connected to the lower tower of the de-weighting tower.
具体地，所述反歧化后分离塔的塔顶设有反歧化后分离塔塔顶回流管，所述反歧化后分离塔塔顶回流管上设有冷凝器以及反歧化后分离塔塔顶采出管；所述反歧化后分离塔的下塔釜设有反歧化后分离塔塔釜回流管，所述反歧化后分离塔塔釜回流管上设有再沸器以及反歧化后分离塔塔釜采出管；所述反歧化后分离塔的塔侧设有反歧化后分离塔塔中侧线采出管，通过反歧化后分离塔塔中侧线采出管重新连接至原料缓冲罐；所述反歧化后分离塔塔顶采出管和反歧化后分离塔塔釜采出管一同连接至混合器。Specifically, the top of the separation tower after the dedisproportionation is provided with a separation tower top return pipe after the dedisproportionation, and the separation tower top return pipe after the dedisproportionation is provided with a condenser and a separation tower top recovery pipe after the dedisproportionation. Out of the pipe; the lower tower kettle of the separation tower after the anti-disproportionation is provided with a separation tower tower kettle reflux pipe after the anti-disproportionation, and a reboiler and a separation tower tower tower after the anti-disproportionation are arranged on the separation tower tower kettle reflux pipe after the described anti-disproportionation still extraction pipe; the tower side of the separation tower after the dedisproportionation is provided with the side line extraction pipe in the separation tower tower after the dedisproportionation, and the side line extraction pipe in the separation tower tower after the dedisproportionation is reconnected to the raw material buffer tank; The extraction pipe at the top of the separation tower after the anti-disproportionation and the extraction pipe at the bottom of the separation tower after the anti-disproportionation are connected to the mixer together.
具体地，所述反歧化反应器的底部设有反歧化反应器采出管，通过反歧化反应器采出管重新连接至反歧化后分离塔进料缓冲罐。Specifically, the bottom of the anti-disproportionation reactor is provided with an extraction pipe of the anti-disproportionation reactor, which is reconnected to the feed buffer tank of the separation tower after the anti-disproportionation through the extraction pipe of the anti-disproportionation reactor.
有益效果：Beneficial effect:
(1)本发明利用吸附+精馏耦合的结合，通过两级吸附除杂和高效耦合精馏，有效解决多晶硅生产中精馏工艺水平，产品三氯氢硅满足电子级多晶硅生产的需求，且生产能耗、物耗实现大幅降低。(1) The present invention utilizes the combination of adsorption + rectification coupling, through two-stage adsorption impurity removal and high-efficiency coupling rectification, effectively solves the rectification process level in polysilicon production, and the product trichlorosilane meets the needs of electronic grade polysilicon production, and Production energy consumption and material consumption have been greatly reduced.
(2)本发明各精馏塔切除料经过二级吸附除杂后，通过反歧化系统回收利用，反歧化反应后生产的三氯氢硅补充到氯硅烷原料中，二氯二氢硅及四氯化硅得到回收利用，实现物料全部循环。(2) After the removal of impurities from each rectification tower of the present invention, it is recycled through the anti-disproportionation system after secondary adsorption and impurity removal, and the trichlorosilane produced after the anti-disproportionation reaction is added to the chlorosilane raw material, dichlorodihydrosilane and tetrahydrosilane Silicon chloride is recycled to realize full material circulation.
(3)本发明用于三氯氢硅精馏提纯的装置，包括原料吸附塔、粗分塔(隔板塔)、脱轻塔(串塔)、脱重塔(串塔)、回收吸附塔、反歧化反应器、反歧化后分离塔(隔板塔)等关键设备构成，在保证精馏质量下又可以将各种沸点的组分区别开来实现资源的有效利用。(3) The present invention is used for the device of rectification purification of trichlorosilane, comprises raw material adsorption tower, crude fractionation tower (partition tower), light removal tower (string tower), weight removal tower (string tower), recovery adsorption tower , anti-disproportionation reactor, separation tower after anti-disproportionation (baffle tower) and other key equipment, while ensuring the quality of rectification, it can distinguish components with various boiling points to realize the effective utilization of resources.
附图说明Description of drawings
下面结合附图和具体实施方式对本发明做更进一步的具体说明，本发明的上述和/或其他方面的优点将会变得更加清楚。The advantages of the above and/or other aspects of the present invention will become clearer as the present invention will be further described in detail in conjunction with the accompanying drawings and specific embodiments.
图1是该多晶硅生产中氯硅烷精馏除杂系统的整体结构示意图。Figure 1 is a schematic diagram of the overall structure of the chlorosilane rectification and impurity removal system in the polysilicon production.
其中，各附图标记分别代表：Wherein, each reference sign represents respectively:
10原料缓冲罐；101氯硅烷原料引管；102氯硅烷原料输送管；20原料吸附塔；30粗分塔；301粗分塔塔顶回流管；302粗分塔塔釜回流管；303粗分塔塔中侧线采出管；304粗分塔塔顶采出管；305粗分塔塔釜采出管；40脱轻塔上塔；401脱轻塔上塔顶回流管；402脱轻塔上塔底部采出管；403脱轻塔上塔顶采出管；50脱轻塔下塔；501脱轻塔下塔顶气相管；502脱轻塔下塔釜回流管；503脱轻塔下塔釜采出管；60脱重塔下塔；601脱重塔下塔顶气相管；602脱重塔下塔釜回流管；603脱重塔下塔釜采出管；70脱重塔上塔；701脱重塔上塔顶回流管；702脱重塔上塔釜底部采出管；703脱重塔上塔顶采出管；80回收料吸附塔；90反歧化后分离塔进料缓冲罐；100反歧化后分离塔；1001反歧化后分离塔塔顶回流管；1002反歧化后分离塔塔釜回流管；1003反歧化后分离塔塔中侧线采出管；1004反歧化后分离塔塔顶采出管；1005反歧化后分离塔塔釜采出管；110混合器；1101四氯化硅补料管；120反歧化反应器；1201反歧化反应器采出管。10 Raw material buffer tank; 101 Chlorosilane raw material introduction pipe; 102 Chlorosilane raw material delivery pipe; 20 Raw material adsorption tower; Production pipe in the side line of the tower; 304 production pipe at the top of the crude separation tower; 305 production pipe at the bottom of the crude separation tower; 40 upper tower of the light removal tower; 401 top return pipe of the upper tower of the light removal tower; Production pipe at the bottom of the tower; 403 production pipe at the top of the light removal tower; 50 lower tower of the light removal tower; 501 gas phase pipe at the top of the lower tower of the light removal tower; ;60 Lower Tower of Weight-removing Tower; 601 Gas Phase Pipe of Lower Tower of Weight-removing Tower; 602 Return Pipe of Lower Tower Kettle of Weight-removing Tower; Pipe; 702 production pipe at the bottom of the upper tank of the weight removal tower; 703 production pipe at the top of the upper tower of the weight removal tower; 80 recovery material adsorption tower; Separation tower top reflux pipe after anti-disproportionation; 1002 Separation tower tank reflux pipe after anti-disproportionation; 1003 Separation tower middle side line production pipe after anti-disproportionation; 1004 Separation tower top production pipe after anti-disproportionation; 1005 After anti-disproportionation 110 mixer; 1101 silicon tetrachloride feeding pipe; 120 anti-disproportionation reactor; 1201 anti-disproportionation reactor output pipe.
DCS为二氯二氢硅；TCS为三氯氢硅(液相)；STC为四氯化硅；LI为轻杂(lightimpurity)；HI为重杂(heavy impurity)。DCS is dichlorodihydrosilane; TCS is trichlorosilane (liquid phase); STC is silicon tetrachloride; LI is light impurity; HI is heavy impurity.
具体实施方式Detailed ways
根据下述实施例，可以更好地理解本发明。The present invention can be better understood from the following examples.
如图1所示，该多晶硅生产中氯硅烷精馏除杂系统，包括原料缓冲罐10、原料吸附塔20、粗分塔30、脱轻塔、脱重塔、反歧化后分离塔进料缓冲罐90、反歧化后分离塔100、混合器110以及反歧化反应器120；所述原料缓冲罐10、原料吸附塔20、粗分塔30、脱轻塔、脱重塔通过管线依次连接。As shown in Figure 1, the chlorosilane rectification and impurity removal system in polysilicon production includes a raw material buffer tank 10, a raw material adsorption tower 20, a crude fractionation tower 30, a light removal tower, a weight removal tower, and a separation tower feed buffer after dedisproportionation The tank 90, the separation tower after deproportionation 100, the mixer 110, and the deproportionation reactor 120; the raw material buffer tank 10, the raw material adsorption tower 20, the crude fractionation tower 30, the light removal tower, and the weight removal tower are connected in sequence through pipelines.
粗分塔30的塔侧通过管道连接至脱轻塔，将侧线采出的较纯三氯氢硅(TCS)送入脱轻塔进一步脱轻杂(LI)。脱轻塔的下塔釜通过管线连接至脱重塔进行进一步脱重杂(HI)。脱重塔的上塔顶通过管线采出合格三氯氢硅产品。The tower side of the crude separation tower 30 is connected to the light removal tower through pipelines, and the relatively pure trichlorosilane (TCS) extracted from the side line is sent to the light removal tower for further removal of light impurities (LI). The lower still of the light removal tower is connected to the weight removal tower through a pipeline for further removal of heavy impurities (HI). Qualified trichlorosilane products are extracted from the upper tower top of the weight-removing tower through pipelines.
粗分塔30的塔顶和塔釜、所述脱轻塔的上塔顶、以及脱重塔的下塔釜，分别通过采出管线一同连接至反歧化后分离塔进料缓冲罐90，将切出的原料杂质进行全部回收。The tower top and the tower still of the crude separation tower 30, the upper tower top of the described light removal tower, and the lower tower still of the heavy weight removal tower are respectively connected to the separation tower feed buffer tank 90 after the deproportionation through the production pipeline, and the The raw material impurities cut out are all recovered.
反歧化后分离塔进料缓冲罐90和反歧化后分离塔100通过管道依次连接；所述反歧化后分离塔100的塔顶和塔釜分别通过采出管线连接至混合器110，塔顶采出二氯二氢硅(DCS)，塔釜采出四氯化硅(STC)。反歧化后分离塔100的塔侧通过采出管线重新连接至原料缓冲罐10，将采出的三氯氢硅(TCS)重新作为原料进行精馏除杂。混合器110、反歧化反应器120通过管道依次连接，反歧化反应器120内主要发生SiH2Cl2+SiCl4→SiHCl3这一反应，通过采出管线重新连接至反歧化后分离塔进料缓冲罐90，将反应产生的三氯氢硅(TCS)，以及未反应的二氯二氢硅(DCS)和四氯化硅(STC)，重新返回进行分离。After the anti-disproportionation, the separation tower feed buffer tank 90 and the separation tower 100 after the anti-disproportionation are connected successively through pipelines; Dichlorodihydrosilane (DCS) is produced, and silicon tetrachloride (STC) is produced from the tower kettle. After dedisproportionation, the side of the separation tower 100 is reconnected to the raw material buffer tank 10 through the production pipeline, and the produced trichlorosilane (TCS) is used as a raw material for rectification and impurity removal. The mixer 110 and the anti-disproportionation reactor 120 are connected sequentially through pipelines, and the reaction of SiH 2 Cl 2 +SiCl 4 →SiHCl 3 mainly occurs in the anti-disproportionation reactor 120, which is reconnected to the separation tower after the anti-disproportionation through the production pipeline. The buffer tank 90 returns the trichlorosilane (TCS) produced by the reaction, as well as the unreacted dichlorodihydrosilane (DCS) and silicon tetrachloride (STC), to be separated again.
原料氯硅烷中二氯二氢硅含量比四氯化硅含量高，反歧化反应为确保二氯二氢硅完全消耗。因此混合器110的进料侧，还连接有四氯化硅补料管1101，通过补入足够的四氯化硅(STC)，让二氯二氢硅(DCS)尽量反应完全。The content of dichlorodihydrosilane in the raw material chlorosilane is higher than that of silicon tetrachloride, and the anti-disproportionation reaction is to ensure the complete consumption of dichlorodihydrosilane. Therefore, the feeding side of the mixer 110 is also connected with a silicon tetrachloride feeding pipe 1101, and by adding enough silicon tetrachloride (STC), the dichlorodihydrosilane (DCS) is allowed to react as completely as possible.
粗分塔30为隔板塔，塔顶设有粗分塔塔顶回流管301，所述粗分塔塔顶回流管301上设有冷凝器以及粗分塔塔顶采出管304，通过设置回流比，将塔顶轻杂(LI)和二氯二氢硅(DCS)采出。粗分塔塔顶回流管301位于冷凝器前段为气相管，位于冷凝器后段为液相管，通过冷凝器将粗分塔塔顶出来的气相冷凝为液相，液相一部分循环进入粗分塔30，另一部分从粗分塔塔顶采出管304采出。粗分塔30的下塔釜设有粗分塔塔釜回流管302，所述粗分塔塔釜回流管302上设有再沸器以及粗分塔塔釜采出管305，将塔釜重杂(HI)和四氯化硅(STC)采出。粗分塔塔釜回流管302位于再沸器的前段为液相管，位于再沸器的后段为气相管，通过再沸器将粗分塔塔釜出来的液相一部分送入再沸器气化后重新返回粗分塔30，另一部分液相从粗分塔塔釜采出管305采出。粗分塔30的塔侧设有粗分塔塔中侧线采出管303采出较纯的三氯氢硅(TCS)，通过粗分塔塔中侧线采出管303连接至脱轻塔。The coarse fractionation tower 30 is a partition tower, and the top of the tower is provided with a coarse fractionation tower top return pipe 301, and the crude fractionation tower top return pipe 301 is provided with a condenser and a coarse fractionation tower top extraction pipe 304, by setting Reflux ratio, the overhead light impurity (LI) and dichlorodihydrosilane (DCS) are taken out. The top reflux pipe 301 of the crude separation tower is located in the front section of the condenser and is a gas phase pipe, and the rear section of the condenser is a liquid phase pipe. Tower 30, the other part is extracted from the extraction pipe 304 at the top of the crude fractionation column. The lower tower still of coarse fractionation tower 30 is provided with thick fractionation tower tower still reflux pipe 302, is provided with reboiler and coarse fractionation tower tower still extraction pipe 305 on the described coarse fractionation tower tower still return pipe 302, the tower still is weighed Miscellaneous (HI) and silicon tetrachloride (STC) are mined. The reflux pipe 302 of the crude fractionation tower kettle is located in the front section of the reboiler and is a liquid phase pipe, and the rear section of the reboiler is a gas phase pipe, and a part of the liquid phase from the crude fractionation tower kettle is sent to the reboiler through the reboiler After being vaporized, return to the crude separation tower 30, and another part of the liquid phase is extracted from the extraction pipe 305 of the bottom of the crude separation tower. The tower side of the rough fractionation tower 30 is provided with a side line extraction pipe 303 in the rough fractionation tower to extract relatively pure trichlorosilane (TCS), and is connected to the light removal tower through the side line extraction pipe 303 in the rough fractionation tower.
脱轻塔为串塔，包括依次串联的脱轻塔上塔40和脱轻塔下塔50；所述脱轻塔上塔40的塔顶设有脱轻塔上塔顶回流管401；所述脱轻塔上塔顶回流管401上设有冷凝器以及脱轻塔上塔顶采出管403，通过设置回流比，将塔顶轻杂(LI)和混合其中的二氯二氢硅(DCS)采出。脱轻塔上塔顶回流管401位于冷凝器前段为气相管，位于冷凝器后段为液相管，通过冷凝器将塔顶出来的气相冷凝为液相，液相一部分循环进入脱轻塔上塔40，另一部分从脱轻塔上塔顶采出管403采出。脱轻塔上塔40的底部通过脱轻塔上塔底部采出管402连接至脱轻塔下塔50。The light removal tower is a string tower, including the upper tower 40 of the light removal tower and the lower tower 50 of the light removal tower connected in series; The top reflux pipe 401 on the light tower is provided with a condenser and the top extraction pipe 403 on the light removal tower. By setting the reflux ratio, the light impurities (LI) on the top of the tower and the dichlorodihydrosilane (DCS) mixed therein mining. The top return pipe 401 on the light removal tower is located in the front section of the condenser as a gas phase pipe, and in the rear section of the condenser is a liquid phase pipe. The gas phase from the top of the tower is condensed into a liquid phase through the condenser, and a part of the liquid phase is circulated into the light removal tower. Tower 40, the other part is extracted from the top extraction pipe 403 on the stripping tower. The bottom of the upper tower 40 of the light removal tower is connected to the lower tower 50 of the light removal tower through a production pipe 402 at the bottom of the upper tower of the light removal tower.
脱轻塔下塔50的塔顶设有脱轻塔下塔顶气相管501，通过脱轻塔下塔顶气相管501重新连接至脱轻塔上塔40；所述脱轻塔下塔50的底部设有脱轻塔下塔釜回流管502，所述脱轻塔下塔釜回流管502上设有再沸器以及脱轻塔下塔釜采出管503，通过脱轻塔下塔釜采出管503连接至脱重塔进一步脱重。脱轻塔下塔釜回流管502位于再沸器的前段为液相管，位于再沸器的后段为气相管，通过再沸器将脱轻塔下塔釜出来的液相一部分送入再沸器气化后重新返回脱轻塔下塔50，另一部分液相从脱轻塔下塔釜采出管503采出送入脱重塔。The top of the light removal tower lower tower 50 is provided with a light removal tower lower tower top gas phase pipe 501, which is reconnected to the light removal tower upper tower 40 through the light removal tower lower tower top gas phase pipe 501; the bottom of the light removal tower lower tower 50 is provided with a light removal tower. The lower tower kettle return pipe 502 of the light tower, the lower tower kettle return pipe 502 of the light removal tower is provided with a reboiler and the lower tower kettle extraction pipe 503 of the light removal tower, and is connected to the heavy removal tower through the lower tower kettle extraction pipe 503 of the light removal tower Further weight loss. The reflux pipe 502 of the lower tower kettle of the light removal tower is located in the front section of the reboiler as a liquid phase pipe, and the rear section of the reboiler is a gas phase pipe, and a part of the liquid phase from the lower tower kettle of the light removal tower is sent to the reboiler through the reboiler After gasification, return to the lower tower 50 of the light removal tower, and another part of the liquid phase is extracted from the lower tower kettle extraction pipe 503 of the light removal tower and sent to the weight removal tower.
脱重塔同样为串塔，包括依次串联的脱重塔下塔60和脱重塔上塔70；所述脱重塔下塔60的塔顶设有脱重塔下塔顶气相管601，通过脱重塔下塔顶气相管601连接至脱重塔上塔70；所述脱重塔下塔60底部设有脱重塔下塔釜回流管602，所述脱重塔下塔釜回流管602上设有再沸器以及脱重塔下塔釜采出管603，将塔釜重杂(HI)和混合其中的四氯化硅(STC)采出。The weight-removing tower is also a series of towers, including the lower tower 60 of the weight-removing tower and the upper tower 70 of the weight-removing tower connected in series; The gas phase pipe 601 at the top of the tower is connected to the upper tower 70 of the weight-removing tower; the bottom of the lower tower 60 of the weight-removing tower is provided with a return pipe 602 for the lower tower still of the weight-removing tower, and the lower tower still return pipe 602 of the weight-removing tower is provided with a reboiler and The extraction pipe 603 at the bottom of the heavy removal tower is used to extract the heavy impurities (HI) and silicon tetrachloride (STC) mixed therein.
脱重塔上塔70的塔顶设有脱重塔上塔顶回流管701，所述脱重塔上塔顶回流管701上设有冷凝器以及脱重塔上塔顶采出管703，通过脱重塔上塔顶采出管703采出合格三氯氢硅产品；所述脱重塔上塔70的底部设有脱重塔上塔釜底部采出管702，通过脱重塔上塔釜底部采出管702重新连接至脱重塔下塔60。The tower top of the upper tower 70 of the weight-removing tower is provided with a top return pipe 701 on the weight-removing tower. The top extraction pipe 703 on the weight removal tower extracts qualified trichlorosilane products; the bottom of the upper tower 70 of the weight removal tower is provided with an extraction pipe 702 at the bottom of the upper tower kettle of the weight removal tower, and passes through the upper tower kettle of the weight removal tower. The bottom production pipe 702 is reconnected to the lower tower 60 of the weight removal tower.
反歧化后分离塔进料缓冲罐90的进料侧前端设有回收料吸附塔80，其与原料吸附塔20作用相同，用于去除原料中的磷、硼以及金属杂质。粗分塔30的塔顶和塔釜、所述脱轻塔的上塔顶、以及脱重塔的下塔釜，分别通过采出管线一同连接至回收料吸附塔80内。After deproportionation, the front end of the feed side of the separation tower feed buffer tank 90 is provided with a recycled material adsorption tower 80, which has the same function as the raw material adsorption tower 20, and is used to remove phosphorus, boron and metal impurities in the raw material. The tower top and tower bottom of the crude fractionation tower 30, the upper tower top of the light removal tower, and the lower tower bottom of the weight removal tower are respectively connected to the recycling material adsorption tower 80 through production pipelines.
反歧化后分离塔100的塔顶设有反歧化后分离塔塔顶回流管1001，所述反歧化后分离塔塔顶回流管1001上设有冷凝器以及反歧化后分离塔塔顶采出管1004，通过设置回流比，将二氯二氢硅(DCS)采出。反歧化后分离塔100的下塔釜设有反歧化后分离塔塔釜回流管1002，所述反歧化后分离塔塔釜回流管1002上设有再沸器以及反歧化后分离塔塔釜采出管1005，将四氯化硅(STC)采出。反歧化后分离塔100的塔侧设有反歧化后分离塔塔中侧线采出管1003用于采出三氯氢硅(TCS)，通过反歧化后分离塔塔中侧线采出管1003重新连接至原料缓冲罐10。反歧化后分离塔塔顶采出管1004和反歧化后分离塔塔釜采出管1005一同连接至混合器110，将采出的二氯二氢硅(DCS)和四氯化硅(STC)进行混合后送入反歧化反应器120内进行反应，反应式：SiH2Cl2+SiCl4→SiHCl3。The top of the separation tower 100 after the anti-disproportionation is provided with a separation tower top return pipe 1001 after the anti-disproportionation, and the separation tower top return pipe 1001 after the anti-disproportionation is provided with a condenser and a separation tower top extraction pipe after the anti-disproportionation 1004, by setting the reflux ratio, dichlorodihydrosilane (DCS) is extracted. The lower tower kettle of the separation tower 100 after dedisproportionation is provided with the separation tower tower kettle reflux pipe 1002 after the antidisproportionation, and the separation tower tower kettle reflux pipe 1002 after the dedisproportionation is provided with a reboiler and a separation tower tower kettle recovery pipe after the antidisproportionation. Out of the pipe 1005, silicon tetrachloride (STC) is extracted. The tower side of the separation tower 100 after anti-disproportionation is provided with a side line extraction pipe 1003 in the separation tower tower after the anti-disproportionation, which is used to extract trichlorosilane (TCS). To the raw material buffer tank 10. After the anti-disproportionation, the extraction pipe 1004 at the top of the separation tower and the extraction pipe 1005 at the bottom of the separation tower after the anti-disproportionation are connected to the mixer 110 together, and the produced dichlorodihydrosilane (DCS) and silicon tetrachloride (STC) After mixing, they are sent to the anti-disproportionation reactor 120 for reaction. The reaction formula is: SiH 2 Cl 2 +SiCl 4 →SiHCl 3 .
反歧化反应器120的底部设有反歧化反应器采出管1201，通过反歧化反应器采出管1201重新连接至反歧化后分离塔进料缓冲罐90，将反应产生的三氯氢硅(TCS)，以及未反应的二氯二氢硅(DCS)和四氯化硅(STC)，重新返回进行分离。The bottom of the anti-disproportionation reactor 120 is provided with an anti-disproportionation reactor extraction pipe 1201, which is reconnected to the separation tower feed buffer tank 90 after the anti-disproportionation by the anti-disproportionation reactor extraction pipe 1201, and the trichlorosilane ( TCS), as well as unreacted dichlorodihydrosilane (DCS) and silicon tetrachloride (STC), are returned for separation.
本发明多晶硅生产中氯硅烷精馏除杂工艺流程主要为：The process flow of chlorosilane rectification and impurity removal in polycrystalline silicon production of the present invention mainly includes:
上游原料氯硅烷通过氯硅烷原料引管101送入原料缓冲罐10内，然后经氯硅烷原料输送管102首先经过原料吸附塔20，去除原料氯硅烷中大部分磷、硼以及金属杂质。进入粗分塔30(隔板塔)，粗分塔30可同时从塔顶切除二氯二氢硅及轻杂，从塔釜切除四氯化硅及重杂，从塔中侧线采出99.99％的三氯氢硅，达到了传统多晶硅合成料精馏流程中前两级塔的脱轻和脱重功能，侧线采出的三氯氢硅中硼、磷含量均能＜10ppbw。侧线采出的三氯氢硅进入脱轻塔(串塔)，脱轻塔上塔40主要切除轻杂，脱轻塔下塔50采出料进入脱重塔(串塔)，脱重塔下塔60主要切除一些重杂。脱重塔上塔70采出合格三氯氢硅产品。The upstream raw material chlorosilane is sent into the raw material buffer tank 10 through the chlorosilane raw material introduction pipe 101, and then first passes through the raw material adsorption tower 20 through the chlorosilane raw material delivery pipe 102 to remove most of the phosphorus, boron and metal impurities in the raw material chlorosilane. Enter the rough fractionation tower 30 (partition tower), the rough fractionation tower 30 can simultaneously remove dichlorodihydrosilane and light impurities from the top of the tower, remove silicon tetrachloride and heavy impurities from the bottom of the tower, and extract 99.99% from the side line of the tower The trichlorosilane has achieved the delight and weight removal functions of the first two towers in the traditional polysilicon synthetic material rectification process, and the content of boron and phosphorus in the trichlorosilane extracted from the side line can both be less than 10ppbw. The trichlorosilane extracted from the side line enters the light removal tower (string tower), and the upper tower 40 of the light removal tower mainly removes light impurities, and the mined material from the lower tower 50 of the light removal tower enters the weight removal tower (string tower), and the lower tower 60 of the weight removal tower Mainly remove some heavy impurities. The upper tower 70 of the weight-removing tower produces qualified trichlorosilane products.
各塔切除全部回收，经回收料吸附塔80回收吸附塔进行除杂处理，处理后的氯硅烷(含二氯氢硅、三氯氢硅、四氯化硅)经反歧化进料缓冲罐90后送至反歧化后分离塔100(隔板塔)进行组分分离。反歧化后分离塔100塔顶采出二氯二氢硅，反歧化后分离塔100塔釜采用四氯化硅全部回收利用，一定配比的二氯二氢硅及四氯化硅经过混合器110后，在反歧化反应器120内进行反歧化反应(反应式：SiH2Cl2+SiCl4→SiHCl3)，生成三氯氢硅，此部分三氯氢硅供精馏三氯氢硅原料使用，因二氯二氢硅(DCS)配比较大，必要时需通过四氯化硅补料管1101另外补充新鲜四氯化硅STC，使得二氯二氢硅(DCS)尽量反应完全，生成三氯氢硅(TCS)。反歧化反应在催化剂床层中进行，STC/DCS的反应配比在3-5之间，反应温度一般控制在40-50℃之间，反应压力控制约为0.2Mpa。All towers are excised and recovered, and the adsorption tower is recovered through the recovery material adsorption tower 80 for impurity removal treatment, and the treated chlorosilane (containing dichlorosilane, trichlorosilane, and silicon tetrachloride) is fed into the buffer tank 90 through antiproportionation Afterwards, it is sent to the separation column 100 (partition column) after deproportionation for component separation. After anti-disproportionation, dichlorodihydrosilane is extracted from the top of the separation tower 100, and after anti-disproportionation, the bottom of the separation tower 100 is fully recycled with silicon tetrachloride, and a certain proportion of dichlorodihydrosilane and silicon tetrachloride passes through the mixer After 110, the anti-disproportionation reaction (reaction formula: SiH 2 Cl 2 +SiCl 4 → SiHCl 3 ) is carried out in the anti-disproportionation reactor 120 to generate trichlorosilane, and this part of trichlorosilane is used as the raw material for rectifying trichlorosilane Use, because dichlorodihydrosilane (DCS) ratio is bigger, need to supplement fresh silicon tetrachloride STC in addition through silicon tetrachloride feeding pipe 1101 when necessary, make dichlorodihydrosilane (DCS) react completely as far as possible, generate Trichlorosilane (TCS). The anti-disproportionation reaction is carried out in the catalyst bed, the reaction ratio of STC/DCS is between 3-5, the reaction temperature is generally controlled between 40-50°C, and the reaction pressure is controlled at about 0.2Mpa.
本发明中，上游原料氯硅烷为二氯二氢硅SiH2Cl2、三氯氢硅SiHCl3、四氯化硅SiCl4以及杂质的混合物。氯硅烷原料组分相对质量含量：DCS～3％，TCS～96％，STC～1％，生产过程中各组分会略有波动。硼、磷杂质等杂质为BCl3、PCl3、BCl5、PH3、B2H6、甲基二氯硅烷、二甲基一氯硅烷等其他金属杂质。脱轻塔、脱重塔为串塔，分上下塔，该塔再沸器、冷凝器只有一个，其附属设备均为单塔的配备量，上下塔通过一个气相管和一个回流管相连，实现能量传递。采用该除杂工艺及系统，能够实现同产能的设备投资减少20％以上，有效降低生产能耗；实现精馏系统的闭路循环，实现物料回收利用；稳定三氯氢硅品质，满足电子级多晶硅生产的需求。In the present invention, the upstream raw material chlorosilane is a mixture of dichlorodihydrosilane SiH 2 Cl 2 , trichlorosilane SiHCl 3 , silicon tetrachloride SiCl 4 and impurities. The relative mass content of chlorosilane raw material components: DCS ~ 3%, TCS ~ 96%, STC ~ 1%, each component will fluctuate slightly during the production process. Impurities such as boron and phosphorus impurities are BCl 3 , PCl 3 , BCl 5 , PH 3 , B 2 H 6 , methyldichlorosilane, dimethylmonochlorosilane and other metal impurities. The light removal tower and the weight removal tower are series towers, which are divided into upper and lower towers. There is only one reboiler and condenser in this tower, and its auxiliary equipment is equipped with a single tower. The upper and lower towers are connected by a gas phase pipe and a reflux pipe to realize energy transfer. Using this impurity removal process and system can reduce equipment investment of the same production capacity by more than 20%, effectively reducing production energy consumption; realize closed-circuit circulation of the rectification system, realize material recycling; stabilize the quality of trichlorosilane to meet the requirements of electronic grade polysilicon production needs.
实施例1Example 1
三氯氢硅原料以50t/h的流量经进料泵送至粗分塔，通过检测进料杂质、过程杂质及产品杂质含量，从数据及实际生产过程中，三氯氢硅产品杂质含量满足电子级多晶硅生产要求，具体数据见表1过程氯硅烷杂质检测数据。The trichlorosilane raw material is pumped to the crude separation tower through the feed flow rate of 50t/h. By detecting the impurities in the feed, process impurities and product impurities, from the data and the actual production process, the impurity content of the trichlorosilane product satisfies Electronic grade polysilicon production requirements, specific data see Table 1 process chlorosilane impurity detection data.
表1过程氯硅烷杂质检测数据Table 1 process chlorosilane impurity detection data
实施例2Example 2
二氯二氢硅(DCS)和四氯化硅(STC)以反应质量比1:3的比例，反应温度压力为0.2Mpa，反应温度为45℃，以5t/h的流量进入反歧化反应器进行反应，检测过程运行数据。通过数据检测，DCS转化率能达到90％以上，有效解决了DCS的循环利用，见表2反歧化反应器出料组分数据。Dichlorodihydrosilane (DCS) and silicon tetrachloride (STC) enter the antiproportionation reactor at a flow rate of 5t/h at a reaction mass ratio of 1:3, a reaction temperature and pressure of 0.2Mpa, and a reaction temperature of 45°C. Perform reactions and detect process run data. Through data detection, the conversion rate of DCS can reach more than 90%, which effectively solves the recycling of DCS. See Table 2 for the output component data of the anti-disproportionation reactor.
表2反歧化反应器出料组分数据Table 2 Disproportionation reactor discharge component data
本发明提供了一种多晶硅生产中氯硅烷精馏除杂工艺及系统的思路及方法，具体实现该技术方案的方法和途径很多，以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。The present invention provides an idea and method of a chlorosilane rectification and impurity removal process and system in the production of polysilicon. There are many methods and approaches to specifically realize the technical solution. The above description is only a preferred embodiment of the present invention. It should be pointed out that for Those of ordinary skill in the art may make some improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention. All components that are not specified in this embodiment can be realized by existing technologies.
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