CN103253676B - Preparation method of trichlorosilane - Google Patents
Preparation method of trichlorosilane Download PDFInfo
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- CN103253676B CN103253676B CN201310169960.6A CN201310169960A CN103253676B CN 103253676 B CN103253676 B CN 103253676B CN 201310169960 A CN201310169960 A CN 201310169960A CN 103253676 B CN103253676 B CN 103253676B
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- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000005052 trichlorosilane Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 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 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 70
- 238000010521 absorption reaction Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 8
- 238000012856 packing Methods 0.000 claims abstract description 7
- 239000012071 phase Substances 0.000 claims description 45
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 29
- 238000010992 reflux Methods 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 230000000630 rising effect Effects 0.000 claims description 7
- 230000008016 vaporization Effects 0.000 claims 6
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 239000000945 filler Substances 0.000 claims 3
- 230000009466 transformation Effects 0.000 claims 3
- 238000009834 vaporization Methods 0.000 claims 3
- 230000008878 coupling Effects 0.000 abstract description 11
- 238000010168 coupling process Methods 0.000 abstract description 11
- 238000005859 coupling reaction Methods 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 9
- 239000007789 gas Substances 0.000 description 22
- 238000006555 catalytic reaction Methods 0.000 description 14
- 238000004821 distillation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 229920005591 polysilicon Polymers 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明公开一种三氯氢硅的制备方法，该制备方法采用以下设备和工艺：该生产设备主要由耦合塔、再沸器和冷凝器构成，所述耦合塔由汽提段、汽提反应段、吸收反应段和精馏段构成；在汽提反应段和吸收反应段内安装新型微分反应精馏装置，汽提段和精馏段内安装塔内件，塔内件是塔板或者填料；三氯氢硅制备工艺为：原料二氯二氢硅从汽提反应段和吸收反应段之间进入塔内，原料四氯化硅从吸收反应段和精馏段之间进入塔内；实现三氯氢硅与四氯化硅的分离；在微分反应精馏装置的作用下，实现三氯氢硅的合成，并将三氯氢硅与反应物分离到气相当中，从吸收反应段得到的富含三氯氢硅的气相最后进入精馏段；实现对三氯氢硅的提纯。
The invention discloses a method for preparing trichlorosilane. The preparation method adopts the following equipment and process: the production equipment is mainly composed of a coupling tower, a reboiler and a condenser, and the coupling tower is composed of a stripping section, a stripping reaction section, absorption reaction section and rectification section; a new type of differential reaction rectification device is installed in the stripping reaction section and absorption reaction section, and column internals are installed in the stripping section and rectification section, and the column internals are trays or packing The preparation process of trichlorosilane is: the raw material dichlorodihydrosilane enters the tower from between the stripping reaction section and the absorption reaction section, and the raw material silicon tetrachloride enters the tower from between the absorption reaction section and the rectifying section; Separation of trichlorosilane and silicon tetrachloride; under the action of the differential reaction rectification device, the synthesis of trichlorosilane is realized, and trichlorosilane and reactants are separated into the gas phase, and obtained from the absorption reaction section The gas phase rich in trichlorosilane finally enters the rectification section; realizing the purification of trichlorosilane.
Description
技术领域technical field
本发明涉及从冶金级多晶硅提纯至太阳能级多晶硅生产过程中副产品二氯二氢硅反歧化转化工艺技术，具体为一种三氯氢硅的制备方法。该方法是利用一种新型的微分反应精馏设备实现精馏、吸收、反应与汽提过程的耦合，将二氯二氢硅反歧化转化为三氯氢硅的制备方法。The invention relates to a process technology of deproportionation conversion of by-product dichlorodihydrogen silicon in the production process from the purification of metallurgical grade polysilicon to solar grade polysilicon, in particular to a preparation method of trichlorohydrogen silicon. The method uses a novel differential reaction rectification equipment to realize the coupling of rectification, absorption, reaction and stripping process, and converts dichlorodihydrosilane into trichlorosilane by deproportionation.
背景技术Background technique
在多晶硅产品生产中，改良西门子法由于工艺成熟而被广泛采用。此工艺以三氯氢硅为原料，在还原炉内通过氢还原而得到多晶硅产品。但是在三氯氢硅的合成和还原工段，会生成四氯化硅和二氯二氢硅等氯硅烷副产品，这严重影响了产品收率和生产成本。目前，对于四氯化硅可以采用冷氢化技术使其转化为三氯氢硅，但同时也会生成一部分二氯二氢硅。对于二氯二氢硅，虽然国际上已有以其为原料制备多晶硅的技术，但是其技术难度和生产成本都较高。所以大多数企业采用固定床反应器，利用反歧化技术原理，实现二氯二氢硅与四氯化硅的反歧化反应，使其转化为三氯氢硅，但是为了将二氯二氢硅尽可能转化完全，采用了四氯化硅过量反应，使得反应器出口浓度三氯氢硅只有10%左右，这直接导致后续分离能耗较高。In the production of polysilicon products, the improved Siemens method is widely used due to its mature technology. This process uses trichlorosilane as raw material to obtain polysilicon products through hydrogen reduction in a reduction furnace. However, in the synthesis and reduction section of trichlorosilane, chlorosilane by-products such as silicon tetrachloride and dichlorodihydrosilane will be generated, which seriously affects the product yield and production cost. At present, silicon tetrachloride can be converted into trichlorosilane by cold hydrogenation technology, but a part of dichlorodihydrosilane will also be generated at the same time. As for dichlorodihydrogensilane, although the technology of preparing polysilicon by using it as a raw material already exists in the world, its technical difficulty and production cost are relatively high. Therefore, most enterprises use fixed-bed reactors and use the principle of anti-disproportionation technology to realize the anti-disproportionation reaction of dichlorodihydrosilane and silicon tetrachloride to convert them into trichlorosilane. The conversion may be complete, and the excessive reaction of silicon tetrachloride is used, so that the concentration of trichlorosilane at the outlet of the reactor is only about 10%, which directly leads to higher energy consumption for subsequent separation.
中国专利CN101955187A公开了一种利用反歧化反应通过反应精馏制三氯氢硅方法和设备。该发明通过三塔工艺流程，可以实现二氯二氢硅和四氯化硅转化为三氯氢硅，而且理论转化率可以达到100%，但是其发明中却没有公开能耗和第一反应精馏塔塔底出口三氯氢硅浓度及实现的产品单程转化率，只是笼统的说通过物料的分离与再循环理论反应转化率可以达到100%。另外，目的产物三氯氢硅沸点介于二氯二氢硅和四氯化硅之间，而且此反应为液相反应，所以在采用单一反应精馏技术转化时，一次转化很难实现反应物的高转化率，只能通过后续分离使过量未反应物循环的方法实现转化率的提高。Chinese patent CN101955187A discloses a method and equipment for producing trichlorosilane through reactive distillation using anti-disproportionation reaction. This invention can realize the conversion of dichlorodihydrosilane and silicon tetrachloride into trichlorosilane through the three-tower process flow, and the theoretical conversion rate can reach 100%, but the invention does not disclose the energy consumption and the first reaction essence. The concentration of trichlorosilane at the bottom outlet of the distillation tower and the single-pass conversion rate of the product are only generally speaking that the theoretical reaction conversion rate can reach 100% through the separation and recycling of materials. In addition, the boiling point of the target product trichlorosilane is between dichlorodihydrosilane and silicon tetrachloride, and this reaction is a liquid phase reaction, so it is difficult to realize the reactant in one conversion when the single reaction distillation technology is used for conversion. The high conversion rate can only be achieved by subsequent separation to recycle excess unreacted substances.
中国专利CN102516036A公开了一种微分反应蒸馏设备，通过该设备实现了MTBE催化蒸馏合成。该发明实现了塔板微分化，催化单元与传质单元交错排列，避免了催化反应与分离传质过程分区进行，提高了反应转化率和分离效率。另外该发明还实现了一种微分化的催化剂装填方式，实现了固定床反应器的微分化。由于该技术为最新发明，对其实验研究较少，其缺点未见报道。Chinese patent CN102516036A discloses a differential reaction distillation equipment, through which MTBE catalytic distillation synthesis is realized. The invention realizes micro-differentiation of trays, staggered arrangement of catalytic units and mass transfer units, avoids partitioning of catalytic reaction and separation and mass transfer process, and improves reaction conversion rate and separation efficiency. In addition, the invention also realizes a micro-differentiation catalyst loading method, and realizes the micro-differentiation of the fixed-bed reactor. Because this technology is the latest invention, its experimental research is less, and its shortcomings have not been reported.
发明内容Contents of the invention
针对现有二氯二氢硅固定床转化技术不足，本发明拟解决的技术问题是，提供一种三氯氢硅的制备方法，该制备方法利用微分催化反应精馏塔板，采用集成设计方法，将吸收、反应、精馏和汽提四个过程耦合在同一个塔器设备内，实现二氯二氢硅与四氯化硅高转化率与耦合塔的节能高效运行。Aiming at the deficiency of existing dichlorodihydrosilane fixed-bed conversion technology, the technical problem to be solved by the present invention is to provide a preparation method of trichlorosilane, which uses differential catalytic reaction rectification trays and adopts an integrated design method , the four processes of absorption, reaction, rectification and stripping are coupled in the same tower equipment to realize the high conversion rate of dichlorodihydrosilane and silicon tetrachloride and the energy-saving and efficient operation of the coupling tower.
本发明解决所述技术问题的技术方案是，设计一种三氯氢硅的制备方法，该制备方法，该制备方法采用以下设备和工艺：The technical scheme that the present invention solves described technical problem is, design a kind of preparation method of trichlorosilane, this preparation method, this preparation method adopts following equipment and technology:
该生产设备主要由耦合塔、再沸器和冷凝器构成，所述耦合塔由汽提段、汽提反应段、吸收反应段和精馏段构成；在汽提反应段和吸收反应段内安装微分催化反应精馏塔板，汽提段和精馏段内安装塔内件，塔内件是塔板或者填料；The production equipment is mainly composed of a coupling tower, a reboiler and a condenser. The coupling tower is composed of a stripping section, a stripping reaction section, an absorption reaction section and a rectification section; Differential catalytic reaction rectification trays, column internals are installed in the stripping section and rectification section, and the column internals are trays or packing;
三氯氢硅制备工艺为：原料二氯二氢硅从汽提反应段和吸收反应段之间进入塔内，原料四氯化硅从吸收反应段和精馏段之间进入塔内；进到塔内的二氯二氢硅马上就会发生部分汽化，没汽化的二氯二氢硅向下进入汽提反应段和汽提段上升来的四氯化硅发生反应，由于温度较高，反应得到的三氯氢硅会和二氯二氢硅一起被汽化，实现三氯氢硅与四氯化硅的分离，从而提高转化率；汽化二氯二氢硅直接进入了吸收反应段，由于在气相当中没有催化剂，所以必须将气相中的二氯二氢硅吸收到液相中才能反应，从上部进入吸收反应段的四氯化硅就起到吸收剂的作用，将气相当中的二氯二氢硅吸收到四氯化硅中，在微分反应精馏装置的作用下，实现三氯氢硅的合成，并将三氯氢硅与反应物分离到气相当中，从吸收反应段得到的富含三氯氢硅的气相最后进入精馏段；进入精馏段的气相，在塔顶回流的作用下，实现对三氯氢硅的提纯，在塔顶得到浓度较高的三氯氢硅产品；塔下部汽提段的作用是将汽提反应段没有汽化脱除的三氯氢硅进一步脱除到气相，使得塔釜间歇排出的釜残液不含有三氯氢硅。The preparation process of trichlorosilane is as follows: the raw material dichlorodihydrosilane enters the tower from between the stripping reaction section and the absorption reaction section, and the raw material silicon tetrachloride enters the tower from between the absorption reaction section and the rectifying section; The dichlorodihydrosilane in the tower will be partially vaporized immediately, and the non-vaporized dichlorodihydrosilane enters the stripping reaction section downward and reacts with the silicon tetrachloride rising from the stripping section. Due to the higher temperature, the reaction The obtained trichlorosilane will be vaporized together with dichlorodihydrosilane to realize the separation of trichlorosilane and silicon tetrachloride, thereby improving the conversion rate; vaporized dichlorosilane directly enters the absorption reaction section, due to the There is no catalyst in the gas phase, so the dichlorodihydrosilane in the gas phase must be absorbed into the liquid phase to react, and the silicon tetrachloride entering the absorption reaction section from the upper part acts as an absorbent, and the dichlorodihydrogen silicon in the gas phase is absorbed into the liquid phase. Chlorodihydrosilane is absorbed into silicon tetrachloride, and under the action of the differential reaction rectification device, the synthesis of trichlorosilane is realized, and trichlorosilane and reactants are separated into the gas phase, and obtained from the absorption reaction section The gas phase rich in trichlorosilane finally enters the rectification section; the gas phase entering the rectification section realizes the purification of trichlorosilane under the action of reflux at the top of the tower, and obtains trichlorohydrogen with a higher concentration at the top of the tower Silicon product: The function of the stripping section in the lower part of the tower is to further remove the trichlorosilane that has not been vaporized and removed in the stripping reaction section to the gas phase, so that the residual liquid intermittently discharged from the tower still does not contain trichlorosilane.
本发明制备方法的条件为：操作压力0.1-0.4MPa；操作温度为10-130℃；操作回流比为1.0-3.0；二氯二氢硅与四氯化硅摩尔比为1-1:1.2。The conditions of the preparation method of the present invention are: operating pressure 0.1-0.4 MPa; operating temperature 10-130° C.; operating reflux ratio 1.0-3.0; molar ratio of dichlorodihydrosilane to silicon tetrachloride 1-1:1.2.
与现有技术相比，本发明制备方法因为利用微分催化反应精馏塔板（新型微分反应精馏装置），实现了微分化反应、吸收、精馏和汽提过程的耦合，并且只在一个耦合塔内完成，实现了二氯二氢硅和四氯化硅的高反应转化率，因而具有工艺路线短，操作能耗低，反应效率高等特点。Compared with the prior art, the preparation method of the present invention realizes the coupling of differential reaction, absorption, rectification and stripping process by using the differential catalytic reaction rectification tray (new differential reaction rectification device), and only in one It is completed in the coupling tower to achieve a high reaction conversion rate of dichlorodihydrosilane and silicon tetrachloride, so it has the characteristics of short process route, low operating energy consumption, and high reaction efficiency.
附图说明Description of drawings
图1是本发明三氯氢硅制备方法一种实施例的生产设备和工艺过程示意图。Fig. 1 is a schematic diagram of the production equipment and process of an embodiment of the trichlorosilane preparation method of the present invention.
具体实施方式Detailed ways
下面结合实施例及其附图进一步描述本发明。The present invention is further described below in conjunction with embodiment and accompanying drawing.
本发明设计的三氯氢硅制备方法（简称制备方法，参见图1），该制备方法采用以下生产设备和工艺：The preparation method of trichlorosilane designed by the present invention (referred to as the preparation method, see Fig. 1), the preparation method adopts the following production equipment and technology:
该生产设备主要由耦合塔1、再沸器2和冷凝器7构成。所述的耦合塔1由汽提段3、汽提反应段4、吸收反应段5和精馏段6构成；在汽提反应段4和吸收反应段5内安装微分催化反应精馏塔板，汽提段3和精馏段6内安装塔内件，塔内件可以是塔板或者填料。The production equipment is mainly composed of a coupling column 1, a reboiler 2 and a condenser 7. Described coupling tower 1 is made of stripping section 3, stripping reaction section 4, absorption reaction section 5 and rectifying section 6; Differential catalytic reaction rectification tray is installed in stripping reaction section 4 and absorption reaction section 5, Column internals are installed in the stripping section 3 and the rectifying section 6, and the column internals may be trays or packings.
三氯氢硅（TCS）制备工艺为：原料二氯二氢硅（DCS）从汽提反应段4和吸收反应段5之间进入塔内，原料四氯化硅（STC）从吸收反应段5和精馏段6之间进入塔内。进到塔内的二氯二氢硅马上就会发生部分汽化，没汽化的二氯二氢硅向下进入汽提反应段4和汽提段3上升来的四氯化硅（STC）发生反应，由于温度较高，反应得到的三氯氢硅会和二氯二氢硅一起被汽化，实现三氯氢硅与四氯化硅的分离，从而提高转化率；汽化二氯二氢硅直接进入了吸收反应段5，由于在气相当中没有催化剂，所以必须将气相中的二氯二氢硅吸收到液相中才能反应，从上部进入吸收反应段5的四氯化硅就起到吸收剂的作用，将气相当中的二氯二氢硅吸收到四氯化硅中，在微分反应精馏装置的作用下，实现三氯氢硅的合成，并将三氯氢硅与反应物分离到气相当中，从吸收反应段5得到的富含三氯氢硅的气相最后进入精馏段。进入精馏段的气相，在塔顶回流的作用下，实现对三氯氢硅的提纯。塔下部汽提段3的作用是将汽提反应段4没有汽化脱除的三氯氢硅进一步脱除到气相，使得塔釜间歇排出的釜残液不含有三氯氢硅。再沸器2提供汽提段3气相回流，冷凝器7提供精馏段6的液相回流。The preparation process of trichlorosilane (TCS) is as follows: the raw material dichlorodihydrosilane (DCS) enters the tower between the stripping reaction section 4 and the absorption reaction section 5, and the raw material silicon tetrachloride (STC) enters the tower from the absorption reaction section 5 and rectifying section 6 into the tower. The dichlorodihydrosilane entering the tower will be partially vaporized immediately, and the non-vaporized dichlorodihydrosilane enters the stripping reaction section 4 and reacts with the silicon tetrachloride (STC) rising from the stripping section 3 , due to the high temperature, the trichlorosilane obtained by the reaction will be vaporized together with dichlorodihydrosilane to realize the separation of trichlorosilane and silicon tetrachloride, thereby increasing the conversion rate; vaporized dichlorosilane directly enters In addition to the absorption reaction section 5, since there is no catalyst in the gas phase, the dichlorodihydrosilane in the gas phase must be absorbed into the liquid phase to react, and the silicon tetrachloride entering the absorption reaction section 5 from the upper part just acts as an absorbent The effect of absorbing the dichlorodihydrosilane in the gas phase into silicon tetrachloride, and under the action of the differential reaction rectification device, the synthesis of trichlorosilane is realized, and the trichlorosilane and the reactant are separated into In the gas phase, the gas phase rich in trichlorosilane obtained from the absorption reaction section 5 finally enters the rectification section. The gas phase entering the rectification section realizes the purification of trichlorosilane under the action of the top reflux. The role of the stripping section 3 in the lower part of the tower is to further remove the trichlorosilane that has not been vaporized and removed in the stripping reaction section 4 to the gas phase, so that the residual liquid intermittently discharged from the tower still does not contain trichlorosilane. The reboiler 2 provides the gas phase reflux of the stripping section 3, and the condenser 7 provides the liquid phase reflux of the rectifying section 6.
本发明合成过程的操作条件为：操作压力0.1-0.4MPa；操作温度为10-130℃；操作回流比为1.0-3.0；二氯二氢硅与四氯化硅摩尔比为1-1:1.2。The operating conditions of the synthesis process of the present invention are: operating pressure 0.1-0.4MPa; operating temperature 10-130°C; operating reflux ratio 1.0-3.0; molar ratio of dichlorodihydrosilane to silicon tetrachloride 1-1:1.2 .
本发明所涉及的化学反应主要是： The chemical reactions involved in the present invention are mainly:
本发明生产工艺原理和过程是：由上一工段送来的二氯二氢硅原料，从汽提反应段4和吸收反应段5之间进入塔内；由于塔内温度较高，进到塔内的二氯二氢硅马上发生部分汽化，汽化的二氯二氢硅直接进入了吸收反应段5，另一原料四氯化硅则从吸收反应段5和精馏段6之间进入塔内；由于其沸点较高，会直接进入反应吸收段5，作为吸收剂吸收气相中的二氯二氢硅DCS，在液相中与催化剂接触反应生成三氯氢硅，在微分反应精馏设备的作用下，实现三氯氢硅的合成，并将三氯氢硅与反应物分离到气相当中；从吸收反应段5得到的富含三氯氢硅的气相最后进入精馏段6；进入精馏段的气相，在冷凝器7提供的塔顶液相回流作用下，实现对三氯氢硅）的提纯，在塔顶即得到浓度较高的三氯氢硅产品。The principle and process of the production process of the present invention are: the dichlorodihydrosilane raw material sent from the previous section enters the tower from between the stripping reaction section 4 and the absorption reaction section 5; due to the high temperature in the tower, it enters the tower Part of the dichlorodihydrosilane inside is vaporized immediately, and the vaporized dichlorodihydrosilane directly enters the absorption reaction section 5, and another raw material, silicon tetrachloride, enters the tower from between the absorption reaction section 5 and the rectification section 6. ; Because its boiling point is higher, it will directly enter the reaction absorption section 5, as the absorbent absorbs the dichlorodihydrosilane DCS in the gas phase, and reacts with the catalyst in the liquid phase to generate trichlorosilane. Under the action, the synthesis of trichlorosilane is realized, and the trichlorosilane and the reactants are separated into the gas phase; the gas phase rich in trichlorosilane obtained from the absorption reaction section 5 finally enters the rectification section 6; enters the rectification section 6; The gas phase in the distillation section, under the action of the top liquid phase reflux provided by the condenser 7, realizes the purification of trichlorosilane), and obtains a higher concentration of trichlorosilane product at the top of the tower.
没有汽化的二氯二氢硅则直接向下进入汽提反应段4，它会与汽提段3上升气中的四氯化硅发生反应，而且由于此段温度较高，反应得到的三氯氢硅会和二氯二氢硅一起被汽化，并转移到气相当中，实现三氯氢硅与四氯化硅的分离，从而提高转化率。另外，塔下部汽提段3在塔底再沸器2提供的上升蒸汽的作用下，可将汽提反应段没有汽化脱除的三氯氢硅进一步脱除到气相，最后塔釜得到不含有三氯氢硅和二氯二氢硅的釜液，富含四氯化硅和杂质的釜残液间歇排出耦合塔外。The dichlorodihydrosilane that does not evaporate directly enters the stripping reaction section 4 downwards, and it will react with the silicon tetrachloride in the rising gas of the stripping section 3, and because the temperature of this section is relatively high, the trichlorosilane obtained by the reaction Hydrogen silicon will be vaporized together with dichlorodihydrosilane and transferred to the gas phase to realize the separation of trichlorosilane and silicon tetrachloride, thereby increasing the conversion rate. In addition, under the action of the rising steam provided by the bottom reboiler 2, the stripping section 3 in the lower part of the tower can further remove the trichlorosilane that has not been vaporized and removed in the stripping reaction section to the gas phase, and finally the tower still can obtain The still liquor of trichlorosilane and dichlorodihydrosilane, and the still raffinate rich in silicon tetrachloride and impurities are discharged out of the coupling tower intermittently.
以下是本发明的具体实施例。所述的实施例仅是用于具体描述本发明，而不是限制本申请的权利要求。The following are specific embodiments of the present invention. The described embodiments are only used to specifically describe the present invention, not to limit the claims of the present application.
实施例1Example 1
二氯二氢硅（DCS）与四氯化硅（STC）的摩尔比例：1：1.2；The molar ratio of dichlorodihydrosilane (DCS) to silicon tetrachloride (STC): 1:1.2;
催化反应精馏塔操作压力：0.15MPa；Catalytic reaction distillation column operating pressure: 0.15MPa;
操作温度：10-85℃；Operating temperature: 10-85°C;
塔结构型式自上而下是：3m高效规整填料（精馏段）+20层微分催化反应精馏塔板（吸收反应段）+10层微分催化反应精馏塔板（汽提反应段）+3m高效规整填料（汽提段）；The tower structure type from top to bottom is: 3m high-efficiency structured packing (rectification section) + 20 layers of differential catalytic reaction rectification trays (absorption reaction section) + 10 layers of differential catalytic reaction rectification trays (stripping reaction section) + 3m efficient structured packing (stripping section);
塔顶组成（m%）：三氯氢硅（TCS）：80%，二氯二氢硅（DCS）：0.5%，四氯化硅（STC）：19.5%；Top composition (m%): trichlorosilane (TCS): 80%, dichlorodihydrosilane (DCS): 0.5%, silicon tetrachloride (STC): 19.5%;
塔底组成（m%）：三氯氢硅（TCS）：0.0%，二氯二氢硅（DCS）：0.0%，四氯化硅（STC）：98%，其它2%。Bottom composition (m%): trichlorosilane (TCS): 0.0%, dichlorodihydrosilane (DCS): 0.0%, silicon tetrachloride (STC): 98%, other 2%.
实施例2Example 2
二氯二氢硅（DCS）与四氯化硅（STC）摩尔比例：1：1.05；The molar ratio of dichlorodihydrosilane (DCS) to silicon tetrachloride (STC): 1:1.05;
催化反应精馏塔操作压力：0.2MPa；Catalytic reaction distillation column operating pressure: 0.2MPa;
操作温度：50-105℃；Operating temperature: 50-105°C;
塔结构型式自上而下是：10层塔板（精馏段）+35层微分催化反应精馏塔板（吸收反应段）+10层微分催化反应精馏塔板（汽提反应段）+15层塔板（汽提段）；The tower structure type from top to bottom is: 10 layers of trays (rectification section) + 35 layers of differential catalytic reaction rectification trays (absorption reaction section) + 10 layers of differential catalytic reaction rectification trays (stripping reaction section) + 15 trays (stripping section);
塔顶组成（m%）：三氯氢硅（TCS）：97.5%，二氯二氢硅（DCS）：0.5%，四氯化硅（STC）：2%；Top composition (m%): trichlorosilane (TCS): 97.5%, dichlorodihydrosilane (DCS): 0.5%, silicon tetrachloride (STC): 2%;
塔底组成（m%）：三氯氢硅（TCS）：0.0%，二氯二氢硅（DCS）：0.0%，四氯化硅（STC）：98%，其它：2%。Bottom composition (m%): trichlorosilane (TCS): 0.0%, dichlorodihydrosilane (DCS): 0.0%, silicon tetrachloride (STC): 98%, others: 2%.
实施例3Example 3
二氯二氢硅（DCS）与四氯化硅（STC）摩尔比例：1：1；The molar ratio of dichlorodihydrosilane (DCS) to silicon tetrachloride (STC): 1:1;
催化反应精馏塔操作压力：0.4MPa；Catalytic reaction distillation column operating pressure: 0.4MPa;
操作温度：60-115℃；Operating temperature: 60-115°C;
塔结构型式自上而下是：10层塔板（精馏段）+35层微分催化反应精馏塔板（吸收反应段）+10层微分催化反应精馏塔板（汽提反应段）+15层塔板（汽提段）；The tower structure type from top to bottom is: 10 layers of trays (rectification section) + 35 layers of differential catalytic reaction rectification trays (absorption reaction section) + 10 layers of differential catalytic reaction rectification trays (stripping reaction section) + 15 trays (stripping section);
塔顶组成（m%）：三氯氢硅（TCS）：97.0%，二氯二氢硅（DCS）：1.0%，四氯化硅（STC）：2%；Top composition (m%): trichlorosilane (TCS): 97.0%, dichlorodihydrosilane (DCS): 1.0%, silicon tetrachloride (STC): 2%;
塔底组成（m%）：三氯氢硅（TCS）：0.0%，二氯二氢硅（DCS）：0.0%，四氯化硅（STC）：98%，其它：2%。Bottom composition (m%): trichlorosilane (TCS): 0.0%, dichlorodihydrosilane (DCS): 0.0%, silicon tetrachloride (STC): 98%, others: 2%.
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