WO2011009390A1

WO2011009390A1 - Reactor and method for converting silicon gas

Info

Publication number: WO2011009390A1
Application number: PCT/CN2010/075252
Authority: WO
Inventors: 储晞
Original assignee: Chu Xi
Priority date: 2009-07-19
Filing date: 2010-07-19
Publication date: 2011-01-27

Abstract

The reactor and method for converting silicon gas are provided. The reactor includes a chamber, wherein a solid inlet, a tail gas outlet, a feed-gas inlet, a slag outlet and an inside or outside heat-exchanger are arranged. There is at least one packed bed reaction stage inside said reactor chamber and the packed bed reaction stage comprises the densely packed mixture of silicon particles and/or catalyst particles as the bed layer. When the feed-gas is passed through said packed bed reaction stage, the contacting time of the reactant is increased and the dust is removed from the tail gas. Also the removed dust can be recycled to the reactor chamber for reuse. The large scale production and low cost of the process for converting silicon gas can be achieved.

Description

硅气转化的反应器和方法技术领域 Silicon gas conversion reactor and method

本发明涉及硅气转化技术，尤其涉及一种硅气转化的反应器和方法。背景技术 The present invention relates to silicon gas conversion technology, and more particularly to a reactor and method for silicon gas conversion. Background technique

硅气转化过程是将金属硅（纯度 95%以上 )或者一种含硅气体，通过化学方法与反应气体在高温高压下进行反应生成另一含有硅的化合物的过程；其中上述反应气体例如可以为： 1¾素、 [¾化氢以及其他 [¾素化合物 (如 CC1₄、 CH₃C1等）。在硅气转化过程中通常加入催化剂以加速反应，提高转换效率。常见的催化剂有过渡金属 Cu、 Ni、 Pt和碱金属以及它们的氢化物、氯化物、特殊树脂等。 The silicon gas conversion process is a process of reacting metal silicon (purity of more than 95%) or a silicon-containing gas by chemical reaction with a reaction gas under high temperature and high pressure to form another silicon-containing compound; wherein the above reaction gas can be, for example, : 13⁄4素, [3⁄4 hydrogen and other [ _3⁄4 prime compounds (such as CC1 ₄ , CH ₃ C1, etc.). Catalyst is usually added during the conversion of silicon gas to accelerate the reaction and improve the conversion efficiency. Common catalysts are transition metals Cu, Ni, Pt and alkali metals and their hydrides, chlorides, special resins and the like.

一种常见的硅气转化过程为金属硅与四氯化硅气体、氢气进行反应生成三氯氢硅的过程。现有的该过程通常采用传统的流化床，将硅粉与催化剂机械混合或者通过溶液浸泡烘干后，加入到流化床中，然后通过四氯化硅和氢气进行反应。 A common silicon gas conversion process is a process in which metal silicon is reacted with silicon tetrachloride gas or hydrogen to form trichlorosilane. The prior art process typically employs a conventional fluidized bed in which the silica fume is mechanically mixed with the catalyst or dried by solution soaking, added to the fluidized bed, and then reacted by silicon tetrachloride and hydrogen.

但是在该现有的采用流化床进行硅气转化的过程中，主要存在如下问题： However, in the existing process of converting silicon gas by using a fluidized bed, the following problems mainly exist:

( 1 )反应过程中硅料加入反应器时阀门磨损严重； (1) The valve is seriously worn when the silicon material is added to the reactor during the reaction;

( 2 ) 由于流化床内的硅粒相互碰撞，使得反应器内部磨损严重； (2) The internal friction of the reactor is severe due to the collision of silicon particles in the fluidized bed;

( 3 )反应尾气中易夹带粉末，从而导致下游管道堵塞。发明内容 (3) The reaction tail gas is easily entrained with powder, which causes blockage of the downstream pipeline. Summary of the invention

本发明的目的在于提供一种硅气转化的反应器和方法，用于实现大规模、低成本的硅气转化生产过程。 It is an object of the present invention to provide a silicon gas conversion reactor and method for achieving a large scale, low cost silicon gas conversion production process.

为了实现上述目的，本发明提供硅气转化的反应器，包括反应器腔体，其中： In order to achieve the above object, the present invention provides a reactor for the conversion of silicon gas, including a reactor chamber, among them:

所述反应器腔体设置有固体加料口、尾气出口、原料气体入口和排渣口； The reactor chamber is provided with a solid feed port, an exhaust gas outlet, a raw material gas inlet and a slag discharge port;

所述反应器腔体内部包括至少一段堆积床反应段；所述堆积床反应段包括密集堆积的作为床层的硅粒和 /或催化剂颗粒的混合物； The interior of the reactor chamber includes at least one stage of packed bed reaction section; the packed bed reaction section comprises a mixture of densely packed silicon particles and/or catalyst particles as a bed;

所述反应器腔体设有内置或外置的换热机构。 The reactor chamber is provided with a built-in or external heat exchange mechanism.

进一步，所述反应器腔体还设有外置的尾气处理机构；所述尾气处理机构包括处于动态的或密集堆积的硅粒和 /或催化剂颗粒形成的床层，用于除去反应尾气中携带的粉尘。 Further, the reactor chamber is further provided with an external exhaust gas treatment mechanism; the exhaust gas treatment mechanism comprises a bed formed of dynamic or densely packed silicon particles and/or catalyst particles for removing the reaction exhaust gas Dust.

进一步，所述尾气处理机构分别与所述反应器腔体的尾气出口和固体加料口相连，用以除去所述尾气出口排出的反应尾气中携带的粉尘，并将所述硅粒和 /或催化剂颗粒形成的床层中被所述反应尾气加热的硅粒和 /或催化剂颗粒传输到所述固体加料口。 Further, the exhaust gas treatment mechanism is respectively connected to the exhaust gas outlet of the reactor chamber and the solid feed port for removing dust carried in the reaction tail gas discharged from the exhaust gas outlet, and the silicon particles and/or the catalyst The silicon particles and/or catalyst particles heated by the reaction off-gas in the bed formed by the particles are transported to the solid feed port.

优选的，所述尾气处理机构还包括换热装置，用于通过所述反应尾气对待通过所述原料气体入口进入所述反应器腔体的原料气体进行加热。 Preferably, the exhaust gas treatment mechanism further comprises a heat exchange device for heating the material gas to be introduced into the reactor chamber through the raw material gas inlet by the reaction tail gas.

进一步，所述反应器腔体内部还包括位于所述堆积床反应段下方的至少一段流化床反应段或喷动床反应段或移动床反应段；所述流化床反应段包括处于流化状态的硅粒和 /或催化剂颗粒的混合物，所述喷动床反应段包括处于喷动状态的硅粒和 /或催化剂颗粒的混合物，所述移动床反应段包括处于移动状态的硅粒和 /或催化剂颗粒的混合物。 Further, the reactor chamber further includes at least one fluidized bed reaction section or a spouted bed reaction section or a moving bed reaction section below the packed bed reaction section; the fluidized bed reaction section includes fluidization a mixture of silicon particles and/or catalyst particles comprising a mixture of silicon particles and/or catalyst particles in a spouted state, the moving bed reaction section comprising silicon particles in a moving state and/or Or a mixture of catalyst particles.

进一步，所述反应器腔体还设置有远离所述原料气体入口的辅助气体进行反应。 Further, the reactor chamber is further provided with an auxiliary gas remote from the inlet of the raw material gas for reaction.

为了实现上述目的，本发明还提供一种根据本发明提供的反应器进行硅气转化的方法，包括：原料气体与所述反应器腔体内已加热的、由硅粒和 /或催化剂颗粒的混合物形成的堆积床层进行反应；除去粉尘后的所述反应尾气经分离、吸附和蒸馏得到含硅气体。 In order to achieve the above object, the present invention also provides a method for performing silicon gas conversion in a reactor provided according to the present invention, comprising: The feed gas is reacted with a heated packed bed formed by a mixture of silicon particles and/or catalyst particles in the reactor chamber; the reaction tail gas after the dust removal is separated, adsorbed and distilled to obtain a silicon-containing gas.

本发明提供的硅气转化的反应器和方法，使原料气体通过位于反应器腔体内的由硅粒和 /或催化剂颗粒形成的堆积床，增加了反应物的接触时间，并可以通过反应器中的堆积床除去反应尾气中的粉尘，使除去的粉尘返回反应器腔体中重新进行反应，从而实现了大规模、低成本的硅气转化生产过程。附图说明 The silicon gas conversion reactor and method provided by the invention allows the raw material gas to pass through a packed bed formed of silicon particles and/or catalyst particles located in the reactor cavity, increasing the contact time of the reactants, and passing through the reactor. The stacked bed removes the dust in the reaction tail gas, and the removed dust is returned to the reactor chamber for re-reaction, thereby realizing a large-scale, low-cost silicon gas conversion production process. DRAWINGS

图 1为本发明一硅气转化的反应器实施例的示意图； Figure 1 is a schematic view of an embodiment of a silicon gas conversion reactor of the present invention;

图 2为本发明另一硅气转化的反应器实施例的示意图； 2 is a schematic view of another embodiment of a silicon gas conversion reactor of the present invention;

图 3为本发明硅气转化的反应器实施例中一反应器腔体的示意图；图 4为本发明硅气转化的反应器实施例中另一反应器腔体的示意图；图 5为本发明硅气转化的反应器实施例中一尾气处理机构的示意图。具体实施方式 3 is a schematic view of a reactor chamber in a reactor for the conversion of silicon gas according to the present invention; FIG. 4 is a schematic view showing another reactor chamber in the embodiment of a reactor for conversion of silicon gas according to the present invention; A schematic of a tail gas treatment mechanism in a reactor for the conversion of silicon gas. detailed description

下面结合附图和具体实施例进一步说明本发明实施例的技术方案。硅气转化的反应器实施例 The technical solutions of the embodiments of the present invention are further described below with reference to the accompanying drawings and specific embodiments. Silicon gas conversion reactor embodiment

图 1为本发明一硅气转化的反应器实施例的示意图，如图 1所示，该反应器可以包括：反应器腔体 100、堆积床反应段 4和换热机构（图中未示出）。 1 is a schematic view of an embodiment of a silicon gas conversion reactor of the present invention. As shown in FIG. 1, the reactor may include: a reactor chamber 100, a packed bed reaction section 4, and a heat exchange mechanism (not shown in the drawings). ).

其中，反应器腔体 100上部设置有固体加料口 1和尾气出口 2, 下部设置有原料气体入口 3和排渣口 5。 The upper portion of the reactor chamber 100 is provided with a solid feed port 1 and an exhaust gas outlet 2, and a lower portion is provided with a raw material gas inlet 3 and a slag discharge port 5.

堆积床反应段 4设置在反应器腔体 100内部。堆积床反应段可以包括密集堆积的作为床层的硅粒和 /或催化剂颗粒的混合物；其中该堆积床可以是移动堆积床，也可以是固定堆积床；当该堆积床是固定堆积床时，在床层中的颗粒经反应变小后，会从分布板的孔中落到反应器腔体的下部。与流化床相比，使用堆积床进行反应时，每次加料的数量较多，由此加料的次数就大大减少，从而减少了固体加料口的阀门打开的次数，由此可以减少阀门的磨损。并且，与流化床相比，堆积床中各颗粒之间的相对运动较小，从而可以减少反应器内部的磨损。 The packed bed reaction section 4 is disposed inside the reactor chamber 100. The packed bed reaction section can include a densely packed mixture of silicon particles and/or catalyst particles as a bed; wherein the packed bed may be a moving packed bed or a fixed packed bed; when the packed bed is a fixed packed bed, particles in the bed After the reaction becomes smaller, it falls from the pores of the distribution plate to the lower portion of the reactor chamber. Compared with the fluidized bed, when the packed bed is used for the reaction, the amount of each feeding is large, and the number of feedings is greatly reduced, thereby reducing the number of times the valve of the solid feeding port is opened, thereby reducing the wear of the valve. . Also, the relative motion between the particles in the packed bed is small compared to the fluidized bed, so that the wear inside the reactor can be reduced.

其中，堆积床反应段除了用作反应以外，还可以用作尾气处理，以除去反应尾气中的粉尘。反应器腔体中的气体在经过堆积床层的过程中，气体中的粉尘会被密集堆积的床层过滤掉，尤其是被床层最上方的一段过滤掉，由此反应尾气在从反应器腔体的尾气出口排出之前，其中的粉尘也会被堆积床层过滤掉，被过滤掉的粉尘大部分是硅粒和 /或催化剂颗粒，被过滤掉的粉尘还留在反应器腔体内，以进一步进行反应。 Among them, the packed bed reaction section can be used as an exhaust gas treatment in addition to the reaction to remove dust in the reaction tail gas. During the passage of the gas in the reactor chamber, the dust in the gas is filtered by the densely packed bed, especially by the uppermost section of the bed, whereby the reaction tail gas is in the reactor. Before the exhaust outlet of the chamber is discharged, the dust therein is also filtered by the packed bed. Most of the filtered dust is silicon particles and/or catalyst particles, and the filtered dust remains in the reactor chamber. The reaction was further carried out.

需要说明的是，为了进一步对反应尾气进行除尘处理，并充分利用反应尾气中携带的热量，可以在反应器腔体外部再设置一尾气处理机构。该尾气处理机构分别与反应器腔体的尾气出口和固体加料口相连，反应尾气从尾气出口排出反应器腔体之后，经过尾气处理机构将其中的粉尘过滤掉，被过滤掉的粉尘返回反应器腔体内重新参与反应。经过尾气处理机构的除尘后，大大减少了反应尾气中携带的粉尘，有效的避免了下游管道的堵塞。 It should be noted that in order to further perform the dust removal treatment on the reaction tail gas and make full use of the heat carried in the reaction tail gas, an exhaust gas treatment mechanism may be disposed outside the reactor chamber. The exhaust gas treatment mechanism is respectively connected with the exhaust gas outlet of the reactor chamber and the solid feed port, and after the reaction tail gas is discharged from the exhaust gas outlet into the reactor chamber, the dust is filtered out by the exhaust gas treatment mechanism, and the filtered dust is returned to the reactor. The chamber re-participates in the reaction. After the dust removal by the exhaust gas treatment mechanism, the dust carried in the reaction tail gas is greatly reduced, and the blockage of the downstream pipeline is effectively avoided.

尾气处理机构可以包含一含硅颗粒和 /催化剂颗粒的床层，该床层具体可以为处于动态的或密集堆积的硅粒和 /催化剂颗粒形成的床层，当反应尾气通过该尾气处理机构时，动态的或密集堆积的硅粒和 /催化剂颗粒能够将反应尾气中携带的粉尘除去，并且在除去反应尾气中粉尘的同时，反应尾气与该床层中的硅粒和 /催化剂颗粒进行热交换，即对该床层中的硅粒和 / 催化剂颗粒进行加热，该被加热后的硅粒和 /催化剂颗粒被传输到反应腔体中参与反应，从而可以在除尘的同时充分利用反应尾气的余热。进一步的，尾气处理机构除了用于除尘以外，还可以是余热利用机构，进行加热以外，还可以在尾气处理机构中设置换热装置，以通过该换热装反应器腔体 100设有内置或外置的换热机构。该换热机构用于对反应器腔体中的反应物进行加热或释热，以将反应器腔体内维持在反应所需的温度。 The exhaust gas treatment mechanism may comprise a bed of silicon-containing particles and/or catalyst particles, which may in particular be a bed formed of dynamic or densely packed silicon particles and/or catalyst particles, when the reaction off-gas passes through the exhaust gas treatment mechanism The dynamic or densely packed silicon particles and/or catalyst particles are capable of removing the dust carried in the reaction off-gas, and the reaction off-gas exchanges heat with the silicon particles and/or catalyst particles in the bed while removing the dust in the reaction off-gas. That is, the silicon particles and/or catalyst particles in the bed are heated, and the heated silicon particles and/or catalyst particles are transferred to the reaction chamber. Participate in the reaction, so that the waste heat of the reaction tail gas can be fully utilized while removing dust. Further, in addition to being used for dust removal, the exhaust gas treatment mechanism may be a waste heat utilization mechanism for heating, or a heat exchange device may be disposed in the exhaust gas treatment mechanism to be provided with a built-in or through the heat exchange reactor chamber 100. External heat exchange mechanism. The heat exchange mechanism is used to heat or liberate the reactants in the reactor chamber to maintain the reactor chamber at the temperature required for the reaction.

更进一步，在反应器腔体内部可以包括一段堆积床反应段，也可以包括多段堆积床反应段，还可以在包括堆积床反应段的基础上，包括位于堆积床反应段的下方其他反应段，其他反应段例如可以为多级单一移动床、流化床、固定床、沸腾床、喷动床、旋动床、熔融床或者是它们的任意组合。其中，流化床反应段包括处于流化状态的硅粒和 /或催化剂颗粒的混合物；喷动床反应段包括处于喷动状态的硅粒和 /或催化剂颗粒的混合物；移动床反应段包括处于移动状态的硅粒和 /或催化剂颗粒的混合物。也就是说，原料气体进入反应器腔体之后，先经过流化床或喷动床反应，然后再经过堆积床进行反应。如：若硅粒中已经包含了一部分可以作为催化剂的杂质，则可以只包含硅粒而不包含其他的催化剂，也可以包含硅粒和催化剂颗粒；若某个硅气转化反应不需硅粒参与反应（例：四氯化硅和氢气生成三氯氢硅）时，可以只包含催化剂颗粒。 Further, a reactor bed reaction section may be included in the reactor chamber, or may include a multi-stage packed bed reaction section, or may be included on the basis of the packed bed reaction section, including other reaction sections below the packed bed reaction section. Other reaction stages can be, for example, a multi-stage single moving bed, a fluidized bed, a fixed bed, a bubbling bed, a spouted bed, a rotating bed, a molten bed, or any combination thereof. Wherein the fluidized bed reaction section comprises a mixture of silicon particles and/or catalyst particles in a fluidized state; the spouted bed reaction section comprises a mixture of silicon particles and/or catalyst particles in a spouted state; A mixture of silicon particles and/or catalyst particles in a moving state. That is, after the feed gas enters the reactor chamber, it is first reacted through a fluidized bed or a spouted bed, and then passed through a packed bed for reaction. For example, if the silicon particles already contain a part of impurities which can be used as a catalyst, they may contain only silicon particles and no other catalysts, and may also contain silicon particles and catalyst particles; if a silicon gas conversion reaction does not require silicon particles to participate The reaction (for example, silicon tetrachloride and hydrogen to form trichlorosilane) may contain only catalyst particles.

在反应器腔体上远离原料气体入口的位置，例如反应器腔体的上部，还可以设置有辅助气体入口，通过该辅助气体入口通入辅助气体，以使辅助气体与位于反应器腔体上部的反应物进行反应，进一步生成含硅气体。例如：在由四氯化硅、氢气和硅粉进行反应生成三氯氢硅的过程中，四氯化硅和氢气作为原料气体从反应器腔体下方的原料气体入口加入，然后在向上运动的过程与硅粒进行反应，整个反应为吸热反应；在该反应过程中，可以在反应器腔体的上部通入氯化氢气体，使得氯化氢气体和硅粒反应生成三氯氢硅，该过程为放热过程，可以补充反应所需热量。 At a location on the reactor chamber remote from the feed gas inlet, such as the upper portion of the reactor chamber, an auxiliary gas inlet may be provided through which the auxiliary gas is passed to provide an auxiliary gas and an upper portion of the reactor chamber. The reactants are reacted to further generate a silicon-containing gas. For example: in the process of reacting silicon tetrachloride, hydrogen and silicon powder to form trichlorosilane, tetrachloro Silicon and hydrogen are fed as raw material gases from the inlet of the raw material gas below the reactor chamber, and then reacted with the silicon particles during the upward movement, the whole reaction is an endothermic reaction; during the reaction, it can be in the reactor chamber The upper part is supplied with hydrogen chloride gas, which causes hydrogen chloride gas and silicon particles to react to form trichlorosilane. This process is an exothermic process and can supplement the heat required for the reaction.

本发明实施例提供的反应器，可以用于进行硅气转化反应。反应的过程可以为：将经过预热的硅粒和催化剂颗粒的混合物通过固体加料口加入反应器腔体中，并处于堆积床状态；原料气体通过原料气体入口通入反应器腔体中，与处于堆积床状态的硅粒发生反应，生成产物含硅气体（即反应尾气）；反应尾气经过堆积床的上部或尾气处理机构进行除尘，并将除掉的粉尘返回反应器腔体中进一步参与反应；然后对进行过除尘的反应尾气进行分离、吸附和蒸馏之后得到纯净的含硅气体。 The reactor provided by the embodiment of the invention can be used for performing a silicon gas conversion reaction. The reaction may be carried out by: adding a mixture of preheated silicon particles and catalyst particles through a solid feed port to the reactor chamber and in a packed bed state; the feed gas is introduced into the reactor chamber through the feed gas inlet, and The silicon particles in the state of the packed bed react to form a product containing silicon gas (ie, reaction tail gas); the reaction tail gas is dedusted through the upper part of the deposition bed or the exhaust gas treatment mechanism, and the removed dust is returned to the reactor cavity to further participate in the reaction. Then, the separated tail gas of the dedusting reaction is separated, adsorbed and distilled to obtain a pure silicon-containing gas.

本发明各实施例中提供的反应器可以应用于硅气转化过程，硅气转化过程中的反应原料包括硅粒和原料气体；其中原料气体可以为高纯含硅气体和还原气体 H₂; 催化剂可以包括过渡金属 Cu、 Ni、 Pt和碱金属以及它们的氢化物、氯化物等。例如四氯化硅和氢气在铜的催化剂下，在上述反应中生成三氯氢硅。三氯氢硅在树脂催化剂下，在上述反应中生成二氯二氢硅和四氯化硅。本发明中使用的所有气体的纯度在 90%以上。 The reactor provided in each embodiment of the present invention can be applied to a silicon gas conversion process, and the reaction raw materials in the silicon gas conversion process include silicon particles and a raw material gas; wherein the raw material gas can be a high-purity silicon-containing gas and a reducing gas H ₂ ; Transition metals Cu, Ni, Pt, and alkali metals, as well as their hydrides, chlorides, and the like, may be included. For example, silicon tetrachloride and hydrogen are produced under a copper catalyst to form trichlorosilane in the above reaction. Trichlorosilane produces dichlorodihydrosilane and silicon tetrachloride in the above reaction under a resin catalyst. All of the gases used in the present invention have a purity of 90% or more.

本发明提供的硅气转化的反应器，使原料气体通过位于反应器腔体内的由硅粒和催化剂颗粒形成的堆积床，增加了反应物的接触时间，并通过堆积床和 /或尾气处理机构除去反应尾气中的粉尘，使除去的粉尘返回反应器腔体中重新进行反应，从而实现了大规模、低成本的硅气转化生产过程。 The silicon gas conversion reactor provided by the invention allows the raw material gas to pass through a packed bed of silicon particles and catalyst particles located in the reactor chamber, increasing the contact time of the reactants, and passing through the deposition bed and/or the exhaust gas treatment mechanism. The dust in the reaction tail gas is removed, and the removed dust is returned to the reactor chamber for re-reaction, thereby realizing a large-scale, low-cost silicon gas conversion production process.

图 2为本发明另一硅气转化的反应器实施例的示意图。在图 1所示的反应器的基础上，如图 2所示，该反应器包括：反应器腔体 100、硅粒与催化剂颗粒混合器 101 (具体可以为混合研磨器）、换热机构 102、预热器 104、硅斗 105、尾气处理机构 107、硅粒和渣料循环机构 106、氢气储存罐 108、尾气分离机构 109、尾气吸附机构 110、 4青馏机构 111和四氯化硅储存罐 118。 2 is a schematic diagram of another embodiment of a silicon gas conversion reactor of the present invention. On the basis of the reactor shown in FIG. 1, as shown in FIG. 2, the reactor comprises: a reactor chamber 100, a silicon particle and catalyst particle mixer 101 (specifically, a hybrid mill), and a heat exchange mechanism 102. , preheater 104, silicon hopper 105, exhaust gas treatment mechanism 107, silicon particle and slag circulation mechanism 106, hydrogen storage tank 108, exhaust gas separation mechanism 109, exhaust gas adsorption mechanism 110, 4 greening mechanism 111, and tetrachlorination Silicon storage tank 118.

其中，硅斗 105分别与混合器 101和尾气处理机构 107的相连；混合器 101与反应器腔体 100的固体加料口相连； Wherein, the silicon hopper 105 is connected to the mixer 101 and the exhaust gas treatment mechanism 107 respectively; the mixer 101 is connected to the solid feed port of the reactor chamber 100;

反应器腔体 100的渣料排出口（排渣口）通过硅粒和渣料循环机构 106 与混合器 101相连，反应器腔体 100的尾气出口与尾气处理机构 107相连，反应器腔体 100上设有内置或外置的换热机构 102; The slag discharge port (slag discharge port) of the reactor chamber 100 is connected to the mixer 101 through the silicon particles and the slag circulation mechanism 106, and the exhaust gas outlet of the reactor chamber 100 is connected to the exhaust gas treatment mechanism 107, and the reactor chamber 100 is connected. There is a built-in or external heat exchange mechanism 102;

尾气处理机构 107的固体排出口与混合器 101相连，尾气处理机构 107 的尾气排出口与尾气分离机构 109的尾气进口相连； The solids discharge port of the exhaust gas treatment mechanism 107 is connected to the mixer 101, and the exhaust gas discharge port of the exhaust gas treatment mechanism 107 is connected to the exhaust gas inlet of the exhaust gas separation mechanism 109;

尾气分离机构 109的尾气排出口与尾气吸附机构 110的尾气进口相连； The exhaust gas discharge port of the exhaust gas separation mechanism 109 is connected to the exhaust gas inlet of the exhaust gas adsorption mechanism 110;

尾气吸附机构 110的尾气排出口与精馏机构 11 1相连； The exhaust gas discharge port of the exhaust gas adsorption mechanism 110 is connected to the rectification mechanism 11 1;

氢气储存罐 108和四氯化硅储存罐 118分别与反应器腔体 100的原料气体入口相连，其中在四氯化硅储存罐 118与反应器腔体 100的原料气体入口之间可以连接有预热器 104。下面结合图 2所示的反应器描述该硅气转化反应的具体过程，其中，以四氯化硅、氢气和硅粉进行硅气转化反应生成三氯氢硅的过程为例进行说明。 The hydrogen storage tank 108 and the silicon tetrachloride storage tank 118 are respectively connected to the raw material gas inlet of the reactor chamber 100, wherein a pre-connection can be made between the silicon tetrachloride storage tank 118 and the raw material gas inlet of the reactor chamber 100. Heater 104. The specific process of the silicon gas shift reaction will be described below in conjunction with the reactor shown in Fig. 2, wherein the process of silicon gas conversion reaction to form trichlorosilane by silicon tetrachloride, hydrogen and silicon powder is taken as an example.

硅粒自硅斗 105注入混合器 101中与催化剂颗粒进行混合，混合均匀后从反应器腔体 100上部的固体加料口加入到反应器腔体中，以在反应器腔体内部形成堆积床反应段；其中硅粒的颗粒度可以在 1 cm以下，优选在 3mm以下，更优在 lmm以下。 The silicon particles are injected into the mixer 101 from the silicon hopper 105 to be mixed with the catalyst particles, and uniformly mixed and then introduced into the reactor chamber from the solid feed port at the upper portion of the reactor chamber 100 to form a packed bed reaction inside the reactor chamber. The segment may have a particle size of 1 cm or less, preferably 3 mm or less, more preferably 1 mm or less.

换热机构 102为反应加热以提高和保持反应温度。换热机构设置在反应器腔体内部或外部，换热机构可以包括加热机构和释热机构。其中，加热机构优选为与硅粒和催化剂颗粒形成的床层电连接的电源，即对床层加上电压，由于硅的半导体性能，床层发热致使温度升高。使用该方法为直接加热，热效率高，热利用率高，采用硅粒作为发热体还可避免污染，保证产品纯度。释热机构即为换热器，可以将反应中产生的过多热量由换热之后带到反应器之外。 The heat exchange mechanism 102 is heated by the reaction to increase and maintain the reaction temperature. The heat exchange mechanism is disposed inside or outside the reactor chamber, and the heat exchange mechanism may include a heating mechanism and a heat release mechanism. Wherein, the heating means is preferably a power source electrically connected to the bed formed by the silicon particles and the catalyst particles, i.e., a voltage is applied to the bed, and the temperature of the bed is increased due to the semiconductor properties of the silicon. Use this method for straight Heating, high thermal efficiency, high heat utilization, using silicon particles as a heating element can also avoid pollution and ensure product purity. The heat release mechanism is a heat exchanger that can carry excess heat generated in the reaction from the heat exchanger to the outside of the reactor.

加热机构还可以采用其它多种现有的加热方式：（ 1 ) 电阻丝（硅棒、高纯 SiC、高纯 SiN或石墨等材料）直接加热；（2 )微波、等离子、激光或感应等间接加热；（3 ) 间接由隔焰热辐射管所提供的燃烧加热或回转炉窑加热；（4 ) 采用外夹套和床内换热器，外夹套换热器可以采用电感加热和载热体换器，床内换热可以采用载热体加热、电感应加热和电极棒加热等方式；（5 ) 外部加热方式，比如将反应中所需的反应物（如悬浮气体和硅颗粒本身）在外部加热后再引入反应器；（6 )偶合式反应加热，采用化学反应如氯气（Cl₂ )或氯化氢（HC1 )加入到***。经过预热器 104 预加热后的原料气体（四氯化硅和氢气）从原料气入口通入反应器腔体 100。位于反应器腔体 100内部下端的硅粒由于受到反应气体的不断侵蚀，颗粒不断变少，体积变小，因而该硅粒同催化剂颗粒一起被压送到反应器腔体底部区域后经下料管排出反应器腔体，排出的颗粒经硅粒和渣料循环机构 106被送往混合器 101与原料硅粒和催化剂颗粒混合，以充分利用催化剂和未反应完全的硅粒。 The heating mechanism can also adopt other various existing heating methods: (1) direct heating of resistance wires (silicon rods, high purity SiC, high purity SiN or graphite); (2) indirect microwave, plasma, laser or induction (3) Indirect heating or rotary kiln heating provided by the flame heat radiant tube; (4) Using an outer jacket and an in-bed heat exchanger, the outer jacket heat exchanger can be insulated by induction heating and heat transfer The body exchanger, the heat exchange in the bed can be heated by heating medium, electric induction heating and electrode rod heating; (5) external heating method, such as the reactants required in the reaction (such as suspended gas and silicon particles themselves) The reactor is introduced into the system after external heating; (6) coupled reaction heating, using a chemical reaction such as chlorine (Cl ₂ ) or hydrogen chloride (HC1). The raw material gases (silicon tetrachloride and hydrogen) preheated by the preheater 104 are passed from the feed gas inlet to the reactor chamber 100. The silicon particles located at the lower end of the reactor chamber 100 are continuously eroded by the reaction gas, the particles are continuously reduced, and the volume is reduced. Therefore, the silicon particles are pressed together with the catalyst particles to the bottom portion of the reactor chamber and then discharged. The tube exits the reactor chamber, and the discharged particles are sent to the mixer 101 via the silicon particles and the slag circulation mechanism 106 to be mixed with the raw material silicon particles and the catalyst particles to make full use of the catalyst and the unreacted silicon particles.

反应尾气中含有反应产物、未完全反应的气体、固体粉尘和反应副产物气体，并且反应尾气具有大量余热；例如：该反应的反应尾气含有三氯氢硅、未反应完全的四氯化硅和氢气、以及反应副产物二氯二氢硅，并且反应尾气中携带有粉尘（包括硅粒和催化剂颗粒）。 The reaction tail gas contains a reaction product, an incomplete reaction gas, a solid dust and a reaction by-product gas, and the reaction tail gas has a large amount of waste heat; for example: the reaction tail gas of the reaction contains trichlorosilane, unreacted silicon tetrachloride, and Hydrogen, and the reaction by-product, dichlorodihydrosilane, and the reaction tail gas carries dust (including silicon particles and catalyst particles).

为了避免反应尾气中携带的粉尘在后续的处理过程中堵塞管道，并且为了对反应尾气进行提纯，可以将反应尾气通过尾气处理机构进行除尘。尾气处理机构 107可以设置在反应器腔体 100的外部（如图 2所示），也可以设置在反应器腔体内部（图中未示出），例如反应器腔体内部的顶部。 In order to prevent the dust carried in the reaction tail gas from clogging the pipeline during the subsequent treatment, and in order to purify the reaction tail gas, the reaction tail gas can be removed by the exhaust gas treatment mechanism. The exhaust gas treatment mechanism 107 may be disposed outside of the reactor chamber 100 (as shown in Figure 2) or may be disposed inside the reactor chamber (not shown), such as the top of the interior of the reactor chamber.

尾气处理机构 107可以包括一密集堆积的或处于动态的硅粒和 /或催化剂颗粒形成的床层，当反应尾气通过时，该床层能够将反应尾气中携带的粉尘过滤掉。尾气处理机构可以是一同时具有反应、换热和过滤功能的设备。具体的，反应功能体现在：当反应尾气通过尾气处理机构时，反应功能体现在：密集堆积的或动态的床层可以将反应尾气中携带的粉尘过滤掉；换热功能体现在：反应尾气在通过床层时，其中携带的余热可以给床层中的硅粒和 /催化剂颗粒进行加热，加热后的硅粒和 /催化剂颗粒可以作为反应原料加入到反应器腔体中。其中，密集堆积的或处于动态的床层中的颗粒分布视最终需求而定，可以在 0.1-5mm之间，床层深度可以为 0.1 cm- 1000cm„ The exhaust gas treatment mechanism 107 can include a densely packed or dynamic silicon particle and/or reminder The bed formed by the agent particles, the bed can filter out the dust carried in the reaction tail gas when the reaction tail gas passes. The exhaust gas treatment mechanism can be a device that has both reaction, heat exchange and filtration functions. Specifically, the reaction function is embodied in: When the reaction tail gas passes through the exhaust gas treatment mechanism, the reaction function is embodied in: The densely packed or dynamic bed can filter the dust carried in the reaction tail gas; the heat exchange function is embodied in: When passing through the bed, the residual heat carried therein can heat the silicon particles and/or catalyst particles in the bed, and the heated silicon particles and/or catalyst particles can be added to the reactor chamber as a reaction raw material. Among them, the distribution of particles in densely packed or in a dynamic bed depends on the final demand, which can be between 0.1 and 5 mm, and the depth of the bed can be 0.1 cm to 1000 cm.

其中，位于反应器顶部的一段由硅粒和催化剂颗粒组成的堆积床层，该段堆积床层相当于在反应器腔体顶部安置一个过滤器，既保证反应器腔体内的粉尘不外泄，同时又避免反应尾气对后续的反应***产生污染和堵塞。 Wherein, a section of the reactor is composed of a packed bed of silicon particles and catalyst particles, and the stacked bed layer is equivalent to a filter placed on the top of the reactor chamber to ensure that the dust in the reactor chamber is not leaked. At the same time, it avoids the reaction tail gas from polluting and clogging the subsequent reaction system.

进一步的，为了更充分的利用反应尾气的余热，还可以在尾气处理机构中设置换热装置，例如设置在尾气处理机构 107中的换热管。在该换热管中通入对待进入反应器腔体的氢气，在反应尾气通过尾气处理机构时，可以利用反应尾气中的余热对换热管中的氢气进行加热；被加热后的氢气可以直接与被预热器 104加热后的四氯化氢混合通入反应器腔体中，也可以被预热器 104进一步加热后与四氯化氢一起通入反应器腔体中。 Further, in order to more fully utilize the residual heat of the reaction off-gas, it is also possible to provide a heat exchange device, such as a heat exchange tube disposed in the exhaust gas treatment mechanism 107, in the exhaust gas treatment mechanism. The hydrogen gas to be introduced into the reactor cavity is introduced into the heat exchange tube. When the reaction tail gas passes through the exhaust gas treatment mechanism, the hydrogen in the heat exchange tube can be heated by the residual heat in the reaction tail gas; the heated hydrogen gas can be directly The hydrogen tetrachloride heated by the preheater 104 is mixed into the reactor chamber, and may be further heated by the preheater 104 and passed into the reactor chamber together with hydrogen tetrachloride.

经过尾气处理机构 107除尘并冷却的反应尾气进入尾气分离机构 109, 尾气分离机构 109根据气体成分对反应尾气进行分离；分离出的氢气作为原料气体返回反应器腔体，在返回反应器腔体之前可以先经过尾气处理机构和 /或预热器 104进行余热；分离出的四氯化硅作为原料气体返回反应器腔体，在返回反应器腔体之前可以先经过预热器 104进行余热；分离出的反应产物再通过尾气吸附机构 1 10, 以使与三氯氢硅的沸点相近的其他成份被吸附；最终将尾气吸附机构 110中排除的三氯氢硅通过精馏机构 11 1进行精馏，得到纯净的三氯氢硅。 The reaction off-gas dedusted and cooled by the exhaust gas treatment mechanism 107 enters the exhaust gas separation mechanism 109, and the exhaust gas separation mechanism 109 separates the reaction off-gas according to the gas composition; the separated hydrogen gas is returned as a raw material gas to the reactor chamber before returning to the reactor chamber. The residual heat may be first passed through the exhaust gas treatment mechanism and/or the preheater 104; the separated silicon tetrachloride is returned to the reactor cavity as a raw material gas, and the residual heat may be passed through the preheater 104 before returning to the reactor cavity; The reaction product is passed through the exhaust gas adsorption mechanism 10 to make it similar to the boiling point of trichlorosilane. The other components are adsorbed; finally, the trichlorosilane excluded from the exhaust gas adsorption mechanism 110 is subjected to rectification by the rectification mechanism 11 1 to obtain pure trichlorosilane.

反应器腔体 100内部和尾气处理机构 107内部可以是方形、圆柱形或矩形等多种形状的空间，且空间可以分层，隔段可以拆分；反应器腔体 100 尾气处理机构 107可以设置为直立、斜靠或平躺放置，在反应时可以进行顺流或逆流操作。当反应器腔体为直立或斜靠放置时，反应器腔体的高度可以为 1-100米，优选的为 1-50米，例如：当反应器腔体的高度为 1米时，反应器可以为 1级，也可以为多级，其中每一级的高度至少为 10-20cm, 当反应器中包括多段反应段时，反应器即为多级反应器；当反应器腔体的高度为 50米时，反应器可以为 1级或多级，各级高度可以不同，当反应器为多级时，每一级的高度至少为 10 - 20cm; 当反应器的高度为已确定值，例如： 50米，还可以根据反应所需的级数，设置每一级的高度；如果反应器为 1级，一级的高度为 50米；如果反应器为 5级，则每一级的高度为 10米左右；同样的，当反应器腔体的高度为 70米或者 100米时，反应器也可以为 1级或多级，可根据反应所需的级数设置每一级的高度，也可以将小尺寸反应器（如反应器腔体高度为 1米或 50米）同比例放大，还可以是多个小尺寸反应器的叠加。反应器腔体的尺寸由反应的实际情况来定，要使反应气体通过反应床层时转换效率最高同时最节能。在此，本发明并不限制反应器腔体的高度，比如反应器腔体的高度还可以为 1-1000 米。当反应器腔体为平躺时，则上述反应器腔体的长度可以为 1-100米，优选的为 1-50米，具体对反应器腔体长度的描述与上述反应器腔体高度类似，但可以是二维分布然后三维叠加，即将多个平躺的反应器腔体进行纵向叠加。当反应为多级时，每一级中的反应尾气都可以利用其余热给下一级中的硅粒进行加热，使得换热效率增加，并增加了有效反应时间。 The interior of the reactor chamber 100 and the exhaust gas treatment mechanism 107 may be square, cylindrical or rectangular, and the space may be stratified, and the partitions may be split; the reactor chamber 100 exhaust gas treatment mechanism 107 may be disposed. For standing upright, leaning or lying down, it is possible to perform a downstream or countercurrent operation during the reaction. When the reactor chamber is placed upright or leaning, the height of the reactor chamber may be 1-100 meters, preferably 1-50 meters, for example: when the height of the reactor chamber is 1 meter, the reactor It can be 1 or more stages, each of which has a height of at least 10-20 cm. When the reactor includes multiple stages of reaction, the reactor is a multistage reactor; when the height of the reactor chamber is At 50 m, the reactor can be 1 or more stages, and the heights of the stages can be different. When the reactor is multistage, the height of each stage is at least 10 - 20 cm; when the height of the reactor is a determined value, for example : 50 meters, the height of each stage can also be set according to the number of stages required for the reaction; if the reactor is level 1, the height of the first stage is 50 meters; if the reactor is level 5, the height of each level is Similarly, when the height of the reactor chamber is 70 meters or 100 meters, the reactor can also be 1 or more stages, and the height of each stage can be set according to the number of stages required for the reaction. Small size reactor (eg reactor chamber height 1) Or 50 m) with the scaled, and may be superimposed on a plurality of small size of the reactor. The size of the reactor chamber is determined by the actual conditions of the reaction, and the conversion efficiency is highest and the energy is most efficient when the reaction gas passes through the reaction bed. Here, the present invention does not limit the height of the reactor chamber, such as the height of the reactor chamber may be 1-1000 meters. When the reactor chamber is lying flat, the length of the reactor chamber may be 1-100 meters, preferably 1-50 meters, and the description of the length of the reactor chamber is similar to the height of the reactor chamber. , but it can be two-dimensionally distributed and then three-dimensionally superimposed, that is, a plurality of lying reactor chambers are longitudinally superposed. When the reaction is in multiple stages, the reaction tail gas in each stage can use the remaining heat to heat the silicon particles in the next stage, which increases the heat exchange efficiency and increases the effective reaction time.

本发明各实施例中的反应器均是以直立为例进行说明，当反应器为平躺时，固体加料口、尾气出口可以位于反应器腔体的一端，原料气体入口和排渣口可以位于反应器腔体的另一端。 The reactors in the various embodiments of the present invention are all illustrated by erecting. When the reactor is lying flat, the solid feed port and the exhaust gas outlet may be located at one end of the reactor chamber, and the raw material gas inlet And the slag discharge port can be located at the other end of the reactor chamber.

为了保证热量不散失或少散失，反应器腔体 100和尾气处理机构 107 的壳体可以由三层组成，内层为耐火内胆，中间层为由耐火纤维和矿渣棉等保温材料构成的保温层，最外层为钢壳起支持作用。 In order to ensure that the heat is not lost or lost, the housing of the reactor chamber 100 and the exhaust gas treatment mechanism 107 may be composed of three layers, the inner layer is a refractory inner liner, and the intermediate layer is an insulation composed of refractory fibers and slag wool. Layer, the outermost layer is supported by a steel shell.

为了在反应时，使硅粒不容易粘结，本发明的反应器还包括用于使硅粒和催化剂床层处于运动状态的动态发生机构，动态发生机构设置在反应器腔体 100的内部或外部。优选的，动态发生机构为气体喷嘴；该气体喷嘴设置在反应器腔体 100内，分别与原料气体入口相连，用于将原料气体喷射入反应器腔体 100内搅动硅粒床层，使床层处于运动状态，避免了硅粒之间的粘结，形成通道而降低反应速度。于动态：（1 ) 引入外力进行如喷动、转动、搅动、拌动、振动或在重力下流动通过内壁上安装的交错梳篦结构等；（2 )使反应器处于其他引力场（如离心力场等）下；（3 )使用机械振动、声波或超声波振动、 *** 式振动等方式。 In order to make the silicon particles less likely to bond during the reaction, the reactor of the present invention further includes a dynamic generating mechanism for moving the silicon particles and the catalyst bed in a state in which the dynamic generating mechanism is disposed inside the reactor chamber 100 or external. Preferably, the dynamic generating mechanism is a gas nozzle; the gas nozzle is disposed in the reactor cavity 100, and is respectively connected to the raw material gas inlet for injecting the raw material gas into the reactor cavity 100 to agitate the silicon granular bed to make the bed The layer is in motion, avoiding bonding between the silicon particles, forming channels and reducing the reaction rate. In the dynamics: (1) Introducing external forces such as spitting, rotating, agitating, mixing, vibrating or flowing under gravity through the interlaced bar structure installed on the inner wall; (2) placing the reactor in other gravitational fields (such as centrifugal force field) (3) using mechanical vibration, acoustic or ultrasonic vibration, plug-in vibration, etc.

本发明实施例提供的反应器还可以包括监测和中心控制***，对反应设备每一环节的具体工艺参数进行记录，当具体工艺参数超过正常范围后会发出警告并提供自动调节，其中反应器需要测定的参数有：床底温度（包括气体和固体温度）、出口气体（反应尾气）组成、压力、固体粒度、床层密度、传热和传质、固体颗粒的运动方向等。 The reactor provided by the embodiment of the invention may further comprise a monitoring and central control system, and record specific process parameters of each link of the reaction device, and issue a warning and provide automatic adjustment when the specific process parameter exceeds the normal range, wherein the reactor needs The parameters measured are: bed bottom temperature (including gas and solid temperature), outlet gas (reaction tail gas) composition, pressure, solid particle size, bed density, heat and mass transfer, direction of movement of solid particles, and the like.

需要说明的是：第一，在反应器腔体中，反应气体流向可以与硅粒子流向垂直，也可以与粒子流向呈任何角度；第二，依靠反应器腔体的直径和物料循环速度来控制物料在每一级反应腔体中的停留时间。 It should be noted that: First, in the reactor cavity, the flow direction of the reaction gas may be perpendicular to the flow direction of the silicon particles, or may be at any angle with the flow direction of the particles; second, depending on the diameter of the reactor chamber and the material circulation speed. The residence time of the material in each stage of the reaction chamber.

为了便于理解，本发明实施例中对反应器腔体、尾气处理机构、加热机构等进行了分别描述。而在实际的生成过程中，上述各个设备可以是一体设置在一个反应器腔体内，也可以是分开设置。例如：当一套预热器对应若干反应器腔体，可以实现在其中一个反应器腔体进行维修时，其他的反应器腔体可以继续运转，减少了停产时间。 For ease of understanding, the reactor chamber, the exhaust gas treatment mechanism, the heating mechanism, and the like are separately described in the embodiments of the present invention. In the actual generation process, each of the above devices may be integrally disposed in a reactor chamber, or may be separately disposed. For example: When a set of preheater pairs Several reactor chambers are required to allow the other reactor chambers to continue to operate while one of the reactor chambers is being serviced, reducing downtime.

本发明提供的硅气转化的反应器，使原料气体通过位于反应器腔体内的由硅粒和催化剂颗粒形成的移动床，增加了反应物的接触时间，并通过尾气处理机构除去反应尾气中的粉尘，使除去的粉尘返回反应器腔体中重新进行反应，还利用反应尾气的余热对硅粒和原料气体进行加热，从而实现了大规模、低成本的硅气转化生产过程。 The silicon gas conversion reactor provided by the invention increases the contact time of the reactants through the moving bed formed by the silicon particles and the catalyst particles in the reactor cavity, and removes the reaction tail gas through the exhaust gas treatment mechanism. Dust, the removed dust is returned to the reactor chamber for re-reaction, and the silicon particles and the raw material gas are heated by the residual heat of the reaction tail gas, thereby realizing a large-scale, low-cost silicon gas conversion production process.

图 3为本发明硅气转化的反应器实施例中一反应器腔体的示意图，图 4为本发明硅气转化的反应器实施例中另一反应器腔体的示意图。 3 is a schematic view of a reactor chamber in a reactor for the conversion of silicon gas according to the present invention, and FIG. 4 is a schematic view of another reactor chamber in the embodiment of the reactor for silicon gas conversion of the present invention.

如图 3所示，含催化剂的硅粒经加料*** 201进入位于反应器腔体顶部的第一反应段 203。由于硅气转化一般都在高压、高温下进行，并且还常有氢气和腐蚀性物质参与，而硅粒是以固体粉尘或粒状的形式加入反应器腔体中，所以硅粒的加料***可以为多重串联漏斗，也可以由增压的锁斗组成。 As shown in Figure 3, the catalyst-containing silicon particles pass through a feed system 201 into a first reaction zone 203 located at the top of the reactor chamber. Since silicon gas conversion is generally carried out under high pressure and high temperature, and hydrogen and corrosive substances are often involved, and silicon particles are added to the reactor cavity in the form of solid dust or granules, the silicon grain feeding system can be Multiple tandem funnels can also be made up of a pressurized lock bucket.

第一反应段 203为一堆积床，由有孔的支撑板托起，反应器腔体中位于第一反应段 203下方的反应区生成的含硅产品气体包含 SiHCl₃、 The first reaction section 203 is a packed bed, which is supported by a supported support plate. The silicon-containing product gas generated in the reaction zone below the first reaction section 203 in the reactor cavity contains SiHCl ₃ ,

Si¾Cl₂、 ¾和未反应的 SiCl₄, 该含硅产品气体通过第一反应段 203时其中携带的粉尘被过滤掉。含硅产品气体经过第一反应段 203之后从反应器腔体中排出，排出的气体可以进入分离器 208中进行进一步除尘，然后经换热装置 212对待参与反应的原料气体进行换热以冷却该气体。 Si3⁄4Cl ₂ , 3⁄4 and unreacted SiCl ₄ , the dust contained in the silicon-containing product gas passing through the first reaction zone 203 is filtered off. The silicon-containing product gas is discharged from the reactor chamber after passing through the first reaction section 203, and the discharged gas may enter the separator 208 for further dust removal, and then exchange heat with the raw material gas participating in the reaction via the heat exchange device 212 to cool the gas. gas.

进一步地，反应尾气还可通过文丘里将带出反应器的粉尘除去。为了最大限度地保证气固反应速率，反应器腔体中段可以为流化床反应区，例如第二反应段 205可以为流化床。在第二反应段 205内，由反应器腔体底部向上运动的过热氢气和 SiCl₄将硅粒悬浮形成两级（或多级）流化床。反应所消耗的硅粒除顶部下落补充之外，还可以从反应器腔体的中部补充，例如：可以在反应器腔体的中部设置喷射口 204, 将硅粒与液态反应物（四氯氢硅）形成的浆料通过该喷射口喷入反应器腔体中，浆料喷入反应器之后迅速气化爆裂成硅粉，混合于流化床层之中，由此可以平衡温度，减少过热。 Further, the reaction off-gas can also be removed by the venturi to carry the dust out of the reactor. In order to maximize the gas-solid reaction rate, the middle section of the reactor chamber may be a fluidized bed reaction zone, for example, the second reaction zone 205 may be a fluidized bed. In the second reaction zone 205, the superheated hydrogen and SiCl ₄ moving upward from the bottom of the reactor chamber suspend the silicon particles to form a two-stage (or multi-stage) fluidized bed. The silicon particles consumed by the reaction can be replenished from the middle of the reactor chamber in addition to the top drop, for example: an injection port 204 can be provided in the middle of the reactor chamber to separate the silicon particles from the liquid. The slurry formed by the reactant (tetrachlorosilane) is sprayed into the reactor cavity through the injection port, and the slurry is quickly vaporized into silicon powder after being sprayed into the reactor, and mixed in the fluidized bed, This balances the temperature and reduces overheating.

本发明实施例将 HC1与 SiCl₄在不同的部位加入到反应器腔体中，具体为：将 HC1从位于反应器腔体顶部的入口 202加入到反应器腔体中， HC1与第一反应段 203中的硅粒进行反应生成三氯氢硅；将被加热后的过热 SiCl₄和 ¾从位于反应器腔体中部或下部的入口 206和入口 206a加入到反应器腔体中，与第二反应段 205和第三反应段 207中的硅粒进行反应；所有反应段中生成的气体产品最终合为一股进入到下游处理分离， HC1和 SiCl₄是单独运输的，在反应过程中也不会相互影响。 In the embodiment of the present invention, HC1 and SiCl ₄ are added to the reactor cavity at different locations, specifically: adding HC1 from the inlet 202 at the top of the reactor chamber to the reactor chamber, HC1 and the first reaction section The silicon particles in 203 are reacted to form trichlorosilane; the heated superheated SiCl ₄ and _{3⁄4 are} fed into the reactor chamber from the inlet 206 and the inlet 206a located in the middle or lower portion of the reactor chamber, and the second reaction The silicon particles in the section 205 and the third reaction section 207 are reacted; the gas products formed in all the reaction sections are finally combined into one downstream processing separation, and HC1 and SiCl ₄ are transported separately, and will not be transported during the reaction. interdependent.

第一反应段 203中的硅粒与 HC1反应，硅粒的粒度逐渐变小，从而落入第二反应段 205 (流化床反应区 ) , 经过第二反应段 205的硅粒落入第三反应段 207; The silicon particles in the first reaction zone 203 react with HCl, and the particle size of the silicon particles gradually becomes smaller, thereby falling into the second reaction zone 205 (fluidized bed reaction zone), and the silicon particles passing through the second reaction zone 205 fall into the third Reaction section 207;

在反应器腔体的第三反应段 207中，由第二反应段 205下落的硅粒和渣料（包括硅中的杂质和催化剂）形成一个固定下行床，预热过的过热气体经过锥形分布板与第三反应段 207中的硅粒进行反应，下沉的硅粒和渣料经过管道 209下沉到除渣漏斗 211 ; 除渣漏斗 211中的硅渣料（包括硅粒和渣料）可以定期排出，也可以返回硅加料*** 201中，以更有效的利用硅原料和催化剂。其中，排渣的方法可以包括固体排渣和液体排渣；固体排渣即为通过重力作用使硅渣料下沉到除渣漏斗中；液态排渣为：可以在管道 209中注入液态 SiCl₄, 以将硅渣料顺利的带出到除渣漏斗中。 In the third reaction zone 207 of the reactor chamber, the silicon particles and slag (including impurities and catalyst in the silicon) falling from the second reaction zone 205 form a fixed down bed, and the preheated superheated gas passes through the cone. The distribution plate reacts with the silicon particles in the third reaction section 207, and the sinking silicon particles and slag are sunk through the pipe 209 to the slag removal funnel 211; the silicon slag material (including the silicon particles and the slag material) in the slag removal funnel 211 It can be discharged periodically or returned to the silicon charging system 201 to more efficiently utilize the silicon feedstock and catalyst. The method for discharging slag may include solid slagging and liquid slagging; the solid slag is to sink the silicon slag into the slag hopper by gravity; the liquid slag is: liquid SiCl ₄ may be injected into the pipe 209 , to smoothly carry the silicon slag into the slag funnel.

参见图 4, 为另一种反应器腔体的示意图。其中，该反应器腔体自上而下是一个多段带有分布机构的下行移动床。在反应过程中，硅粒和催化剂颗粒通过下行移动床向下移动，原料气体从底部通入反应器腔体，与向下移动的硅粒进行反应，避免形成沟流，从而降低反应速度，其它相关的过程参见图 3所示实施例中的描述。图 5为本发明硅气转化的反应器实施例中一尾气处理机构的示意图。如图 5所示，该尾气处理机构具体可以为一粒子流尾气处理器。 See Figure 4 for a schematic view of another reactor chamber. Wherein, the reactor chamber is a multi-stage descending moving bed with a distribution mechanism from top to bottom. During the reaction, the silicon particles and the catalyst particles move downward through the moving bed, and the raw material gas is introduced into the reactor chamber from the bottom to react with the downwardly moving silicon particles to avoid channeling, thereby reducing the reaction rate. The related process is described in the description of the embodiment shown in FIG. Figure 5 is a schematic illustration of an exhaust gas treatment mechanism in a reactor for the conversion of silicon gas according to the present invention. As shown in FIG. 5, the exhaust gas treatment mechanism may specifically be a particle flow exhaust gas processor.

在该处理器中，从颗粒入口 301中加入硅颗粒，使得自上而下流动着硅颗粒，形成了一个密集的粒子层 304; In the processor, silicon particles are added from the particle inlet 301 such that silicon particles flow from top to bottom to form a dense particle layer 304;

反应尾气从进口 302通入，并由百叶式分布器 303进入粒子层 304, 尾气中的粉尘可以被粒子层 304吸收； The reaction off-gas is passed from the inlet 302 and enters the particle layer 304 by the louver distributor 303, and the dust in the exhaust gas can be absorbed by the particle layer 304;

粒子层 304中的硅颗粒从颗粒出口 305排出并通过顶部的颗粒循环入口 307返回到处理器中循环利用； The silicon particles in the particle layer 304 are discharged from the particle outlet 305 and returned to the processor through the top particle recycle inlet 307 for recycling;

尾气中的热量通过指式换热器 306带出，可以为待参与反应的原料气体加热，实现能量的综合利用；并且粒子流本身也可把大量热量带出，即该处理器中从颗粒出口 305排出的硅颗粒被反应尾气加热，被加热的硅颗粒也可以不通过颗粒循环入口 307返回到处理器，而是输送到反应器腔体中参与反应； The heat in the exhaust gas is taken out by the finger heat exchanger 306, and the raw material gas to be reacted can be heated to realize the comprehensive utilization of energy; and the particle flow itself can also bring out a large amount of heat, that is, the outlet from the particle in the processor The silicon particles discharged from 305 are heated by the reaction tail gas, and the heated silicon particles may also be returned to the processor without passing through the particle circulation inlet 307, but are transported to the reactor chamber to participate in the reaction;

经冷却、除尘后的反应尾气经出口 308排出进入下一工段的分离提纯。在上述尾气处理过程中，尾气中在前段反应器中未完全反应的气体，可以在该处理器中与硅颗粒进行进一步的反应，提高了整体转换效率。并且，可以从颗粒入口 301补充硅颗粒，以弥补硅颗粒的反应损耗和磨损。 The cooled and dedusted reaction tail gas is discharged to the next stage for separation and purification through the outlet 308. During the above-described exhaust gas treatment, the gas in the exhaust gas that is not completely reacted in the previous reactor can be further reacted with the silicon particles in the processor, thereby improving the overall conversion efficiency. Also, silicon particles may be replenished from the particle inlet 301 to compensate for the reaction loss and wear of the silicon particles.

本发明实施例，使用处于运动状态的硅粒床层进行反应，避免了颗粒之间的粘结，减小了反应器体积，并且通过密集堆积的硅粒床层捕获反应尾气中的粉尘，还利用反应尾气的余热为反应原料进行加热，从而可以实现超大型、高效、节能、连续、低成本硅气转化。利用本发明提供的反应器进行硅气转化的方法实施例 In the embodiment of the invention, the reaction is carried out using a silicon bed in a moving state, the bonding between the particles is avoided, the reactor volume is reduced, and the dust in the reaction tail gas is captured by the densely packed bed of silicon particles. The waste heat of the reaction tail gas is used to heat the reaction raw material, thereby achieving ultra-large, high-efficiency, energy-saving, continuous, low-cost silicon gas conversion. Method for performing silicon gas conversion using the reactor provided by the present invention

参见图 2, 利用本发明提供的反应器进行硅气转化的方法可以包括：步骤 1、从反应器腔体 100的固体加料口中加入硅粒和催化剂颗粒的混合物，并在反应器腔体 100内形成移动床层；内，使原料气体与反应器腔体内已加热的、由硅粒和 /或催化剂颗粒的混合物形成的堆积床层进行反应； Referring to FIG. 2, a method for performing silicon gas conversion using the reactor provided by the present invention may include: Step 1. Adding silicon particles and catalyst particles from a solid feed port of the reactor chamber 100. Mixing and forming a moving bed within the reactor chamber 100; internally reacting the feed gas with a heated packed bed formed by a mixture of silicon particles and/or catalyst particles in the reactor chamber;

步骤 3、使反应产生的反应尾气通过尾气处理机构 107以除去反应尾气中的粉尘； Step 3. The reaction tail gas generated by the reaction is passed through an exhaust gas treatment mechanism 107 to remove dust in the reaction tail gas;

步骤 4、除去粉尘后的反应尾气先后经尾气分离机构 109进行分离、经尾气吸附机构 110进行吸附以及经精馏机构 1 11进行蒸馏之后得到含硅气体。 Step 4. The reaction tail gas after removing the dust is separated by the tail gas separation mechanism 109, adsorbed by the tail gas adsorption mechanism 110, and distilled by the rectification mechanism 1 11 to obtain a silicon-containing gas.

其中，尾气处理机构可以为处于动态的或密集堆积的硅粒和 /或催化剂颗粒形成的床层，步骤 3具体可以为：反应尾气通过处于动态的或密集堆积的硅粒和 /或催化剂颗粒形成的床层，以除去反应尾气中携带的粉尘。进一步的，在尾气处理机构中被反应尾气加热的硅粒和 /或催化剂颗粒可以被传输到反应器腔体的固体加料口中，以被加入到反应器腔体中参与反应。 Wherein, the exhaust gas treatment mechanism may be a bed formed of dynamic or densely packed silicon particles and/or catalyst particles, and step 3 may specifically be: the reaction tail gas is formed by dynamic or densely packed silicon particles and/or catalyst particles. The bed is removed to remove the dust carried in the reaction tail gas. Further, the silicon particles and/or catalyst particles heated by the reaction off-gas in the exhaust gas treatment mechanism can be transported to the solid feed port of the reactor chamber to be added to the reactor chamber for reaction.

并且，在反应尾气通过尾气处理机构时，还可以通过尾气处理机构中的换热装置，对待进入反应器腔体的原料气体进行加热。后，使原料气体与反应器腔体内的、处于流化状态或喷动状态或移动状态的硅粒和 /或催化剂颗粒的混合物进行反应；即原料气体进入反应器腔体之后，先经过流化床或喷动床，然后再经过位于反应器腔体顶部的堆积床。 Further, when the reaction off-gas passes through the exhaust gas treatment mechanism, the raw material gas to be introduced into the reactor chamber can be heated by the heat exchange device in the exhaust gas treatment mechanism. Thereafter, the raw material gas is reacted with a mixture of silicon particles and/or catalyst particles in a fluidized state or a sprayed state or a moving state in the reactor chamber; that is, after the raw material gas enters the reactor chamber, it is first fluidized. The bed or spouted bed is passed through a packed bed at the top of the reactor chamber.

为了向反应器腔体中加入辅助气体进行反应，可以在反应器腔体上部的辅助气体入口通入辅助气体，以使辅助气体与位于反应器腔体上部的反应物进行反应。 In order to carry out the reaction by adding an auxiliary gas to the reactor chamber, an auxiliary gas may be introduced into the auxiliary gas inlet at the upper portion of the reactor chamber to react the auxiliary gas with the reactant located at the upper portion of the reactor chamber.

具体的方法流程可以参见本发明上述各实施例中的描述。 For a detailed method flow, reference may be made to the description in the above embodiments of the present invention.

在本发明实施例颗粒硅的过程中，通过以下方法对物料进行传输或装卸：（ 1 ) 重力流动法，即靠固体粒子自身的重力流入床层和自床层流出的方法，其中为了使固体粒子顺利地流动，可以在管道的适当点通入少量的气体，使固体粒子松动以便于流动；（2 )机械输送法，通常采用的机械有：螺杆输送机、皮带给料机、圆盘给料机、星形给料机和斗式提升机等；（3 ) 气动力输送法。 In the process of the granular silicon of the embodiment of the invention, the material is transported or handled by the following methods: (1) Gravity flow method, that is, flowing into the bed and flowing out of the bed by the gravity of the solid particles themselves The method, in order to make the solid particles flow smoothly, a small amount of gas can be introduced at a suitable point of the pipeline to loosen the solid particles for flow; (2) Mechanical transport method, commonly used machinery: screw conveyor, belt Feeders, disc feeders, star feeders, bucket elevators, etc.; (3) Aerodynamic conveying method.

本发明提供的硅气转化的方法，使原料气体通过位于反应器腔体内的由硅粒和 /或催化剂颗粒形成的移动床，增加了反应物的接触时间，避免了颗粒之间的粘结，减小了反应器体积，并通过动态的或密集堆积的硅粒床层捕获反应尾气中的粉尘，还利用反应尾气的余热为反应原料进行加热，从而可以实现超大型、高效、节能、连续、低成本的硅气转化成产过程。 The method for converting silicon gas provided by the present invention allows the raw material gas to pass through a moving bed formed of silicon particles and/or catalyst particles located in the reactor chamber, thereby increasing the contact time of the reactants and avoiding the adhesion between the particles. The reactor volume is reduced, and the dust in the reaction tail gas is captured by the dynamic or densely packed bed of silicon particles, and the waste heat of the reaction tail gas is used to heat the reaction raw material, thereby achieving ultra-large, high-efficiency, energy-saving, continuous, Low-cost silicon gas is converted into a production process.

最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。 It should be noted that the above embodiments are only for explaining the technical solutions of the present invention, and are not intended to be limiting; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that: The technical solutions described in the foregoing embodiments are modified, or some of the technical features are equivalently replaced. The modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

权利要求 Rights request

1、一种硅气转化的反应器，包括反应器腔体，其特征在于：所述反应器腔体设置有固体加料口、尾气出口、原料气体入口和排渣口； A reactor for converting silicon gas, comprising a reactor chamber, characterized in that: the reactor chamber is provided with a solid feed port, a tail gas outlet, a raw material gas inlet and a slag discharge port;

2、根据权利要求 1所述的硅气转化的反应器，其特征在于，所述反应器腔体还设有外置的尾气处理机构； 2. The reactor for converting silicon gas according to claim 1, wherein the reactor chamber is further provided with an external exhaust gas treatment mechanism;

所述尾气处理机构包括处于动态的或密集堆积的硅粒和 /或催化剂颗粒形成的床层，用于除去反应尾气中携带的粉尘。 The exhaust gas treatment mechanism includes a bed formed of dynamic or densely packed silicon particles and/or catalyst particles for removing dust carried in the reaction off-gas.

3、根据权利要求 2所述的硅气转化的反应器，其特征在于，所述尾气处理机构分别与所述反应器腔体的尾气出口和固体加料口相连，用以除去所述尾气出口排出的反应尾气中携带的粉尘，并将所述硅粒和 /或催化剂颗粒形成的床层中被所述反应尾气加热的硅粒和 /或催化剂颗粒传输到所述固体加料口。 3. The silicon gas conversion reactor according to claim 2, wherein the exhaust gas treatment mechanism is respectively connected to an exhaust gas outlet of the reactor chamber and a solid feed port for removing the exhaust gas outlet. The dust carried in the reaction off-gas and the silicon particles and/or catalyst particles heated by the reaction off-gas in the bed formed by the silicon particles and/or catalyst particles are transported to the solid feed port.

4、根据权利要求 3所述的硅气转化的反应器，其特征在于，所述尾气处理机构还包括换热装置，用于通过所述反应尾气对待通过所述原料气体入口进入所述反应器腔体的原料气体进行加热。 4. The silicon gas conversion reactor according to claim 3, wherein the exhaust gas treatment mechanism further comprises a heat exchange device for entering the reactor through the feed gas inlet through the reaction tail gas The material gas of the chamber is heated.

5、根据权利要求 1-4任一所述的硅气转化的反应器，其特征在于，所述反应器腔体内部还包括位于所述堆积床反应段下方的至少一段流化床反应段或喷动床反应段或移动床反应段；所述流化床反应段包括处于流化状态的硅粒和 /或催化剂颗粒的混合物，所述喷动床反应段包括处于喷动状态的硅粒和 /或催化剂颗粒的混合物，所述移动床反应段包括处于移动状态的硅粒和 /或催化剂颗粒的混合物。 5. The silicon gas conversion reactor according to any one of claims 1 to 4, wherein the reactor chamber further comprises at least one fluidized bed reaction section located below the packed bed reaction section or a spouted bed reaction section or a moving bed reaction section; the fluidized bed reaction section comprising a mixture of silicon particles and/or catalyst particles in a fluidized state, the spouted bed reaction section comprising silicon particles in a spouted state / or a mixture of catalyst particles, the moving bed reaction section comprising a mixture of silicon particles and/or catalyst particles in a moving state.

6、根据权利要求 1-4任一所述的硅气转化的反应器，其特征在于，所述反应器腔体还设置有远离所述原料气体入口的辅助气体入口，用应。 6. A silicon gas conversion reactor according to any one of claims 1 to 4, wherein the reactor chamber is further provided with an auxiliary gas inlet remote from the feed gas inlet.

7、一种根据权利要求 1-6任一所述反应器进行硅气转化的方法，其特征在于，包括：原料气体与所述反应器腔体内已加热的、由硅粒和 /或催化剂颗粒的混合物形成的堆积床层进行反应；除去粉尘后的所述反应尾气经分离、吸附和蒸馏得到含硅气体。 7. A method of silica gas conversion in a reactor according to any of claims 1-6, comprising: a feed gas and heated, silicon particles and/or catalyst particles in said reactor chamber The deposited bed formed by the mixture is reacted; the reaction tail gas after the dust is removed is separated, adsorbed and distilled to obtain a silicon-containing gas.

8、根据权利要求 7所述的方法，其特征在于，所述使反应尾气通过尾气处理机构以除去所述反应尾气中的粉尘包括： 8. The method according to claim 7, wherein the passing the reaction off-gas through the exhaust gas treatment mechanism to remove dust in the reaction tail gas comprises:

使所述反应尾气通过由处于动态的或密集堆积的硅粒和 /或催化剂颗粒形成的床层构成的尾气处理机构，以除去所述反应尾气中携带的粉尘。 The reaction off-gas is passed through an exhaust gas treatment mechanism consisting of a bed formed of dynamic or densely packed silicon particles and/or catalyst particles to remove dust carried in the reaction off-gas.

9、根据权利要求 7所述的方法，其特征在于，所述使反应尾气通过尾气处理机构以除去所述反应尾气中的粉尘包括： 9. The method according to claim 7, wherein the passing the reaction off-gas through the exhaust gas treatment mechanism to remove the dust in the reaction tail gas comprises:

使所述反应尾气通过由处于动态的或密集堆积的硅粒和 /或催化剂颗粒形成的床层构成的尾气处理机构，以除去所述反应尾气中携带的粉尘，并将所述硅粒和 /或催化剂颗粒形成的床层中被所述反应尾气加热的硅粒和 /或催化剂颗粒传输到所述反应器腔体的固体加料口。 Excluding the reaction off-gas through an exhaust gas treatment mechanism consisting of a bed formed of dynamic or densely packed silicon particles and/or catalyst particles to remove dust carried in the reaction tail gas, and to remove the silicon particles and/or The silicon particles and/or catalyst particles heated by the reaction off-gas in the bed formed by the catalyst particles are transferred to the solid feed port of the reactor chamber.

10、根据权利要求 8所述的方法，其特征在于，还包括： 10. The method according to claim 8, further comprising:

在所述反应尾气通过所述尾气处理机构时，通过所述尾气处理机构的换热装置，对待进入所述反应器腔体的原料气体进行加热。 When the reaction off-gas passes through the exhaust gas treatment mechanism, the feed gas entering the reactor chamber is heated by the heat exchange device of the exhaust gas treatment mechanism.

11、根据权利要求 9所述的方法，其特征在于，还包括： The method according to claim 9, further comprising:

在所述反应尾气通过所述尾气处理机构时，通过所述尾气处理机构的换热装置，对待进入所述反应器腔体的原料气体进行加热。 Passing through the exhaust gas treatment mechanism when the reaction tail gas passes through the exhaust gas treatment mechanism The heat exchange device heats the material gas to be introduced into the reactor chamber.

12、根据权利要求 7-11任一所述的方法，其特征在于，在将所述预热后的原料气体通入所述反应器腔体之后，在使所述原料气体与所述反应器腔体内的所述堆积床层进行反应之前还包括： The method according to any one of claims 7 to 11, wherein after the preheated raw material gas is introduced into the reactor chamber, the raw material gas and the reactor are made The stacked bed in the chamber also includes:

使所述原料气体与所述反应器腔体内的、处于流化状态或喷动状态或移动状态的硅粒和 /或催化剂颗粒的混合物进行反应。 The feedstock gas is reacted with a mixture of silicon particles and/or catalyst particles in the reactor chamber in a fluidized or spewed or shifted state.

13、根据权利要求 7-11任一所述的方法，其特征在于，还包括：从所述反应器腔体上远离所述原料气体入口的辅助气体入口通入辅助气体，以使所述辅助气体与所述反应器腔体内的反应物进行反应。 13. The method of any of claims 7-11, further comprising: introducing an auxiliary gas from an auxiliary gas inlet of the reactor chamber remote from the feed gas inlet to cause the auxiliary The gas reacts with the reactants in the reactor chamber.