KR20100091573A - A manufacturing method an manufacturing apparatus of trichlorosilane(sihcl3) using the catalyst and the reaction heat - Google Patents

Abstract

PURPOSE: The heat generating with the inside heat generation reaction is provided and it reacts. The line or heater can be eliminated. The installation fee, and the production cost and maintenance cost are reduced. CONSTITUTION: A trichlorosilane manufacturing device with the hydrogen supply source(11). With the silicon tetrachloride tank(14) for the hydrogen being provided from the hydrogen supply source and the hydrogen and silicon tetrachloride being bubbled and injecting to reactor. With the chlorine supply source(12) for the hydrochloric acid gas being mixed to the piping one side in which the fluid bubbled in the silicon tetrachloride tank passes through and supplying.

Description

A manufacturing method an manufacturing apparatus of trichlorosilane (SiHCl3) using the catalyst and the reaction heat}

In order to efficiently manufacture trichlorosilane (SiHCl ₃ , TCS), which is the main raw material of semiconductor special gas and polysilicon for solar cell, the size of metal grade silicon particles is 50 ~ 400mesh and purity is more than 90%. The purity of hydrogen is more than 70%, the silicon tetrachloride (SiCl ₄ , STC) is more than 75%, the chlorine is more than 90% industrial use, and the tank containing silicon tetrachloride is heated above the vaporization temperature. Hydrogen is injected into the silicon tetrachloride tank and vaporized bubbling silicon tetrachloride and hydrogen are supplied to the reactor together, and chlorine is mixed with the silicon tetrachloride and hydrogen at the front end of the reactor or supplied to the reactor through a pipe independently into the reactor. In the reactor, a metal catalyst (transition metal group Pd, Pb, Cu, Pt, Ti, Sr-based) and metal silicon are charged, and the gas passing through the reactor is transferred to a distillation column equipped with a reboiler and a condenser, The silicon tetrachloride recovered by separating the trichlorosilane and silicon tetrachloride using the boiling point difference is recycled to the silicon tetrachloride tank, and the trichlorosilane having a purity of 95% or more to the storage tank. The present invention relates to a trichlorosilane production apparatus and method using a catalyst and reaction heat designed to be transported.

Trichlorosilane is a colorless liquid with an HCl odor. It has a boiling point of 32 ° C and a melting point of -127 ° C. As a main raw material, the amount of usage is increasing.

Conventional trichlorosilane manufacturing method is a method using a catalyst consisting of nickel, copper, iron, etc. in order to lower the reaction temperature is disclosed in the European Patent Publication, (0,658,359, A2), the generally known Cu catalyst In the case of using, the technical content to obtain the conversion rate of trichlorosilane of about 20% in the vicinity of 300 ℃ has been proposed, but the conversion of silicon tetrachloride is relatively low and waste of silicon tetrachloride, which is a waste, has to be treated as a catalyst and a problem. Another problem is that Cu used is volatilized with CuCl ₂ to contaminate the product.

Another related art is disclosed in Korean Patent Laid-Open Publication No. 10-2007-0008649, which discloses a method for preparing a reaction temperature in the range of 300 to 1000 ° C. using a metal catalyst, and the reaction temperature is 700 when no catalyst is used. The method of manufacturing in the range of ℃ ~ 1500 ℃ is disclosed in the Republic of Korea Patent Publication No. 10-2007-0094854, all of them are the method of receiving heat for heating the reactor is a technical configuration using a heater, the volume of the reactor, production The cost and maintenance costs are enormous constraints. For example, when the reactor volume is increased to increase the production capacity, the thermal efficiency due to heat conduction is lowered. In order to solve this problem, increasing the capacity of the heater causes an installation space, an installation cost, a production cost and As the maintenance cost increases greatly, the number of production equipment of trichlorosilane is generally considered in two points. One way to increase the choice, this is also required is an enormous installation cost and space efficient installation, there are problems such as labor costs increased.

The problem to be solved by the present invention is an apparatus for continuously producing trichlorosilane by adding chlorine that generates heat when reacting with hydrogen under a metal catalyst (Pd or Pb) using metal silicon (MG-Si) and silicon tetrachloride as raw materials As it is possible to reduce the heater capacity of the reactor or to remove the heater device by receiving and reacting the heat generated by the internal exothermic reaction to reduce the installation cost, production cost and maintenance cost.

Another problem to be solved by the present invention is to apply the technical configuration to the chlorine in the exothermic reaction to the process and the device to maintain the TCS conversion rate while maintaining the maximum output at the same cost is possible device configuration and installation cost, It is to maximize production efficiency by reducing production and maintenance costs and simplifying the heater system of the reactor.

Another problem to be solved by the present invention is to recover and recycle the metal silicon by using a cyclone during the production apparatus and process of trichlorosilane, in the distillation column to separate the silicon tetrachloride and trichlorosilane using the boiling point, the silicon tetrachloride recovered in the separation process It is designed and manufactured to recycle, which greatly reduces production cost, material cost and waste disposal cost.

In order to efficiently manufacture trichlorosilane (SiCl ₃ , TCS), which is a main raw material of semiconductor special gas and polysilicon for solar cell, the size of metal grade silicon particles is 50 ~ 400mesh and purity is more than 90%. And The purity of hydrogen is more than 70%, the purity of silicon tetrachloride (SiCl ₄ , STC) is more than 75%, the purity of chlorine is more than 90% for industrial use, and the tank containing silicon tetrachloride is above the vaporization temperature of silicon tetrachloride. And tetrahydrogen are injected into the silicon tetrachloride tank and bubbling to supply silicon tetrachloride and hydrogen to the reactor at the same time.The supply of chlorine gas to obtain the heat of reaction is a structure in which chlorine gas is independently supplied from the lower side of the reactor. Is installed in the center of the reactor to maximize the exothermic reaction and the chlorine gas injection pipe is connected to one side of the pipe with silicon tetrachloride and hydrogen to move to the bottom of the reactor is made by employing one of the selected and selected, the silicon tetrachloride In the reactor in which hydrogen and chlorine are injected, a metal catalyst (transition metal group Pd, Pb, Cu, Pt, Ti, Sr-based) and metal silicon are charged. The gas passed through the reactor is sent to a distillation column equipped with a reboiler and a condenser, and the distillation column separates the trichlorosilane and silicon tetrachloride using the boiling point difference, and the recovered and recovered silicon tetrachloride is recycled to the silicon tetrachloride tank, Purity trichlorosilane is to implement a trichlorosilane production apparatus and method using a catalyst and reaction heat designed to be transferred to the storage tank.

Another problem solving means of the present invention is to reduce the material cost by employing a cyclone at the top of the reactor to reduce the material cost to recover the fine powder metal silicon circulated to the reactor to recycle, and in the distillation column by using the difference in boiling point and trichlorosilane and In order to separate silicon tetrachloride, a heater is used at the bottom and a cooling heat exchanger is used at the top, so silicon tetrachloride having a high boiling point is recovered to the reboiler at the bottom of the distillation column, and the recovered silicon tetrachloride is fed back to the silicon tetrachloride tank for recycling. Therefore, to reduce the waste disposal cost and material cost, to provide a method and apparatus for producing trichlorosilane having a purity of 95% or more.

Another problem solving means of the present invention comprises a distillation column consisting of a reboiler, a distillation column and a condenser, in the reboiler is heated to 50 ℃ to 58 ℃ by a heater, in the distillation column gas passes through to increase the purity of trichlorosilane To increase the time required, and condensing the gas passing through the condenser to feed back the liquid generated during condensation and transfer the gas to the trichlorosilane storage tank to produce trichlorosilane with improved purity of trichlorosilane to 98% or more. And to provide an apparatus.

The present invention is a device for continuously producing trichlorosilane by adding chlorine that generates heat when reacting with hydrogen under a metal catalyst (Pd or Pb) using metal silicon (MG-Si) and silicon tetrachloride as raw materials. Reaction by receiving the heat generated by the reaction can reduce the heater capacity of the reactor or remove the heater, thereby reducing the installation cost, production cost and maintenance costs.

Another effect of the present invention is to apply the technical configuration of the chlorine in the exothermic reaction to the process and apparatus, it is possible to configure the device that can increase the output at the same cost while maintaining the maximum TCS conversion rate, installation cost, production cost and It is to reduce the maintenance cost and to maximize the work efficiency by simplifying the heater device of the reactor.

Another effect of the present invention is to recover and recycle the metal silicon by using a cyclone during the production apparatus and process of trichlorosilane, in the distillation column to separate the silicon tetrachloride and trichlorosilane using the boiling point, to recycle the silicon tetrachloride recovered in the separation process By designing and manufacturing, production cost, material cost and waste disposal cost are greatly reduced.

Hereinafter, the present invention will be described in detail. The apparatus and method for producing trichlorosilane according to the present invention is characterized by using silicon tetrachloride, metal silicon, hydrogen and chlorine as raw materials, and using a metal catalyst as a reaction catalyst, wherein the metal component is Pd, Pb, It is made of Cu, Pt, Ti, Sr-based, the tin of the transition metal group catalyst is prepared by selecting one of alumina, zeolite, silicon oxide, activated carbon and diatomaceous earth.

The present invention is configured to continuously feed the raw material in the continuous filling reactor, the particulate metal silicon is separated and recovered through a cyclone at the top of the reactor and fed back into the reactor.

The gas passing through the cyclone is continuously transferred to the distillation column connected in series through a pipe. In the distillation column, silane trichloride (boiling point: 32 ° C) and silicon tetrachloride (boiling point: 57,6 ° C) are separated by boiling point difference. Silicon tetrachloride having a high boiling point is recovered in a tank under the distillation column, recycled to a silicon tetrachloride tank, and recycled as a raw material.

The trichlorosilane passed through the top of the distillation column is condensed with a purity of 95% or more and stored in a storage tank.

Silicon tetrachloride used as a raw material of the present invention is more than 75% purity, metal silicon (MG-Si) has a purity of 90% or more, the particle size is used 50 ~ 400mesh. The purity of hydrogen is 70% or more, and the chlorine purity is 90% or more for industrial use.

The apparatus for producing trichlorosilane using the catalyst according to the present invention is configured to continuously feed raw materials into a continuous filling reactor, and a cyclone for separating and recovering fine powder metal silicon is installed at the top of the reactor.

It is preferable that the reactor has a cylindrical structure that can withstand pressure (about 10 atm) well, a catalyst made of a metal of transition metal group is charged at the bottom of the reactor, and metal silicon is introduced into the cylindrical reactor with a screw. It is injected over the catalyst layer to form a metal silicon layer.

Silicon tetrachloride and hydrogen are injected into the silicon tetrachloride tank maintained above the vaporization temperature of silicon tetrachloride and bubbled by injecting hydrogen from the hydrogen source to supply silicon tetrachloride and hydrogen together, and the chlorine supplied from the chlorine source is independently It is supplied and combined with each other in one pipe at the front end of the reactor is mixed with each other, the mixed pipe is heated to a constant temperature in the temperature between 300 ℃ ~ 500 ℃ through an electric heater installed outside the pipe. In this case, since the diameter of the heated pipe is small, the installation of the heater is simple and the heater can be configured with a small capacity, thereby reducing the installation space, installation cost, production cost, and maintenance cost.

Hereinafter, the configuration and operation of the embodiments of the present invention with reference to the accompanying drawings, the configuration and operation of the present invention shown and described in the drawings will be described by at least one embodiment, whereby the present invention described above The technical spirit and its core composition, the mixing ratio and action of the composition is not limited.

Look at the drawings to facilitate understanding of the present invention. 1 is a device diagram for the production of trichlorosilane designed according to the present invention, Figure 2 is an enlarged view of the distillation column of the trichlorosilane production apparatus designed and manufactured according to the present invention. A specific embodiment according to the present invention will be described.

EXAMPLES

A specific embodiment according to the present invention will be described with reference to the drawings. 1 is a device diagram for the production of trichlorosilane using a reaction heat and a catalyst designed and manufactured according to the present invention. The present invention relates to an apparatus and method for producing trichlorosilane with high conversion rate at low temperature and low pressure without using a heater or having a heater that heats the reactor less than the conventional manufacturing method because the reaction is carried out using a catalyst and reaction heat in the reactor. In the process of manufacturing trichlorosilane, the metal silicon generated in the process is recycled to the reactor, and the silicon tetrachloride is recycled to the silicon tetrachloride tank, thereby reducing the waste disposal cost, and reducing the material cost and production cost. To provide an apparatus and method for manufacturing.

In the present invention, the technical configuration of chlorine injection to obtain the heat of reaction through exothermic reaction is the core. Injecting chlorine to obtain the heat of reaction according to the present invention can be designed and manufactured in three structures, one of which can be selected. The first structure is to install a pipe on the lower side of the reactor maintained at 300 ℃ ~ 500 ℃, and independently supply chlorine gas from the chlorine source through the pipe. The second structure is designed to maximize the exothermic reaction by installing a chlorine inlet in the center of the reactor and supplying chlorine gas from the chlorine source through the pipe.The reaction temperature starts at 300 ℃ ~ 500 ℃, Shut off the power to the heating device. The third structure is to connect the chlorine gas injection pipe to one side of the pipe where silicon tetrachloride and hydrogen move together so that these three gases are mixed together through a preheater and injected into the bottom of the reactor. It is configured to maintain around ~ 500 ℃.

1 is a structure for supplying chlorine in the third method, which is one embodiment of the present invention, injects hydrogen into a silicon tetrachloride tank, and injects chlorine into one side of a pipe through which a bubbling fluid passes, and a heater (hereinafter, The preheated silicon tetrachloride, hydrogen and chlorine are simultaneously introduced into the reactor while passing through the 'preheater'.

The silicon tetrachloride, chlorine, and hydrogen heated by the preheater as they pass through the pipe are mixed with each other and fed to the reactor to pass through the catalyst bed, resulting in the reactions shown in Tables 1 to 3 depending on the temperature range. Is a reaction according to Scheme d.

Table 1. Thermodynamic data of the reaction taking place inside the reactor (350 ° C)

Table 2. Thermodynamic data of the reaction inside the reactor (400 ° C.)

Table 3. Thermodynamic data of the reaction inside the reactor (500 ° C)

Then, the reaction proceeds by the reaction scheme c, which is an integrated reaction of reaction scheme a and reaction scheme b, passing through the metal silicon (MG-Si) layer.

The integrated reaction made by the reaction scheme c requires an endothermic reaction to supply heat, and the necessary heat is configured to proceed by receiving the heat generated in the reaction according to the reaction scheme d. The thermal relationship control generated by Scheme d is determined by the molar ratio of hydrogen injected from the hydrogen source and chlorine injected from the chlorine source in FIG. When chlorine is added in excess of hydrogen, the reaction by the reaction formula e occurs, causing excessive hot spots, which makes the control difficult and reduces the conversion rate. Therefore, it is necessary to control the molar ratio of hydrogen and chlorine to be injected. Therefore, excess hydrogen is added to maintain the reaction according to Scheme c as the main reaction, and the heat generated by Scheme d is added as a heat source. It is desirable to.

More preferably, the molar ratio of hydrogen and chlorine may be injected between 50: 1 and 1: 1. Then the temperature inside the reactor is maintained at 320 ℃ ~ 350 ℃. Eventually, by controlling the input of hydrogen and chlorine, it is possible to reduce the power consumption of the heater installed outside the reactor as much as possible, and before the injection into the reactor, the preheating device is installed to preheat the reactor. Since the gas is configured to be injected, there is no need to use or install a heater installed in the reactor as a spare.

This can reduce the installation space, installation cost, production cost and maintenance cost of the equipment necessary to increase the production of trichlorosilane, and also the reaction is carried out while hydrogen, silicon tetrachloride and chlorine pass through the catalyst layer and the metal silicon layer inside the reactor. It is possible to reduce the drift caused by the metal silicon powder is scattered and to achieve thermal stabilization. The trichlorosilane generated in the upper part of the reactor is primarily collected by the cyclone to recover the fine metal impurities and metal silicon (MG-Si) and then transferred to the distillation column. The separated and recovered silicon tetrachloride is configured to be recycled to the reactor. At this time, the distillation column is configured to maintain a lower temperature of 50 ~ 58 ℃, the upper temperature of 30 ~ 35 ℃ by using the difference in boiling point is configured to be separated into silicon tetrachloride and trichlorosilane. The trichlorosilane separated from the distillation column is condensed with a purity of 95% or more and stored in the storage tank as a solution, and the silicon tetrachloride recovered in the distillation column tank is recycled to the silicon tetrachloride tank and reloaded as a raw material.

The structure of the manufacturing apparatus which concerns on this invention is looked at in detail based on FIG. In order to inject silicon tetrachloride and hydrogen into the reactor, silicon tetrachloride and hydrogen are supplied simultaneously by bubbling hydrogen from the hydrogen source 11 into the silicon tetrachloride tank 14 maintained above the vaporization temperature of silicon tetrachloride. The chlorine supplied from the supply source 12 is independently supplied, and is configured to combine and mix the pipes in which silicon tetrachloride and hydrogen are mixed at the front end of the reactor and the pipe for supplying chlorine into one pipe.

The preheater 15 is installed outside the pipe in which silicon tetrachloride, hydrogen and chlorine are mixed and heated to 300 ° C to 500 ° C. The preheating device 15 for preheating the pipe before being injected into the reactor 32 is a small diameter pipe, so that the preheating device 15 can be easily installed and warmed, and thus the preheating device 15 can be configured with a small capacity. There is an advantage that can reduce the installation space, installation cost, production cost and maintenance cost.

The reactor 32 is preferably designed and manufactured in a metallic cylindrical structure that can withstand the high gas pressure (about 10 atm) generated by the reaction, and the transition metal group metal (Pd, Pb, Cu, Pt) at the bottom of the reactor. , Ti, Sr-based) is charged to form a catalyst layer 16, and a metal silicon layer 17 is formed by injecting metal silicon with a screw 20 on the catalyst layer.

The reactor is configured to continuously feed the raw materials for the production of trichlorosilane into a continuous filling reactor, and a cyclone 21 for separating and recovering fine powdered metal silicon is installed at the top of the reactor, and in the cyclone 21 The fine powder silicon separated and dropped to the bottom is configured to be re-introduced into the metal silicon layer 17 of the reactor 32.

The gas passing through the cyclone 21 is transferred to the distillation tower 23 through pipes connected in series and in series, and in the distillation tower 23, trichlorosilane (boiling point: 32 ° C) and silicon tetrachloride (boiling point: 57,6 ° C) The silicon tetrachloride separated by the difference in boiling point, and the boiling point having a high boiling point by the difference in boiling point is recovered to the tank under the distillation column 23, and the recovered silicon tetrachloride is supplied to the silicon tetrachloride storage tank 30 through the pipe to the supply pump (29). ) To transfer.

A distillation column heating device 22 is installed inside the distillation column tank disposed below the distillation column 23, and the distillation column heating device 22 maintains the internal temperature of the lower portion at 50 ° C. to 58 ° C., and the upper part of the distillation column 23 is cooled. It is configured to provide a heat exchanger (24) for maintaining between 30 ℃ to 35 ℃. The cooling heat exchanger 24 may be any conventional cooler capable of cooling the temperature.

In the lower part of the distillation column tank, silicon tetrachloride having a high boiling point is collected and separated from the trichlorosilane, and the silicon tetrachloride collected in the distillation column tank is configured to move through the baffle (28, Baffle) to the silicon tetrachloride storage tank (30). The baffle 28 serves to reduce the load on the distillation column heating device 22 by reducing the heating target of the distillation column heating device 22.

Silicon tetrachloride stored in the silicon tetrachloride storage tank 30 is transferred to the silicon tetrachloride tank 14 using the supply pump 29 to be recycled as a raw material, thereby reducing material costs and waste disposal costs.

FIG. 2 is an enlarged view of the distillation column 23. The distillation column of FIG. 2 is a reboiler equipped with a distillation column heating device 22 and is positioned at the center of the distillation column to enlarge the contact area of gas to increase the purity of trichlorosilane. It consists of a distillation column and a condenser.

The reboiler is heated to 50 ° C to 58 ° C with a distillation column heater (22), in the distillation column filled with polling increases the passage time of the gas to increase the purity of trichlorosilane, condensing the gas passing through the condenser It is configured to feed back the liquid and transfer the gas to the trichlorosilane storage tank 26 so as to increase the purity of the trichlorosilane. The purity of the trichlorosilane passed through the distillation column is 95% or more.

The gas passing through the condenser is configured to pass through the heat exchanger 25 for cooling condensation in a liquid state before being transferred to the trichlorosilane storage tank 26, and to be transferred to a liquid state and stored in the trichlorosilane storage tank 26. One side of the cooling condensation heat exchanger 25 is provided with a vent 33 for discharging hydrogen and hydrochloric acid.

In the apparatus for producing trichlorosilane according to the present invention, selectively install one or more control valves for controlling the flow of gas in a plurality of pipes, and install in a place where a temperature sensor, a pressure sensor and a level gauge are needed, the control A control unit can be installed to control valves, temperature sensors, pressure sensors and level gauges automatically or manually.

The internal temperature of the reactor 32 is reacted by maintaining between 100 ℃ to 500 ℃, more preferably to make the reaction between 300 ℃ to 350 ℃. The internal pressure of the reactor 32 is between 1 atm and 10 atm.

The internal pressure of the distillation column is made between 1 atm and 5 atm, and the internal temperature of the distillation column is between 10 ° C and 100 ° C.

The reactor is a fixed bed reactor prepared by separating the catalyst layer and the metal silicon layer as shown in FIG. 1, a mixed reactor prepared by mixing the catalyst and the metal silicon, and the catalyst and the metal silicon to move in the reactor. It is possible to design and manufacture one of the fluidized bed reactors designed to increase the conversion rate by increasing the time.

More specifically, Pd catalysts include palladium salt of a concentration that is mounted to the reactor (PdNO _3, PdCl ₂₎ alumina in solution, the zeolite, after selecting a tint of a silicon oxide, activated carbon and diatomaceous earth and dried impregnated Na ₂ It was neutralized with a solution such as CO ₃ , K ₂ CO ₃ and dried, calcined at 400 ° C. and then reduced with hydrogen at 300 ° C. for 5 hours. Pb catalyst is composed of Pb, Ti, Sr, etc., and PbNO ₃ , TiCl 4, SrNO ₃ and the like in a proportion of the solution to select one of alumina, zeolite, silicon oxide, activated carbon and diatomaceous earth was impregnated and then neutralized with a neutralizing agent, was used as a dried at about 100 ℃ and then reduced at 300 ℃ to 5 hours hydrogen firing at 500 ℃ catalysts, Cu catalysts are alumina CuCl ₂ solution in a concentration, the zeolite, One of silicon oxide, activated carbon and diatomaceous earth is selected, impregnated for a certain period of time, dried, neutralized with a neutralizing agent, dried, calcined and reduced with hydrogen to be used as a catalyst.

Example 1

In the apparatus for producing trichlorosilane using a catalyst according to the present invention, a cylindrical reactor has a diameter of 10 cm and a cyclone having a diameter of 30 cm is installed on the top of 2 m in height, and a distillation column having a height of 10 m and a diameter of 2 m at the next stage of the cyclone. This is installed, the condenser is attached to the top of the distillation column is installed to maintain a temperature between 30 ℃ ~ 35 ℃, the lower column was configured to maintain 50 ℃ to 58 ℃.

At the bottom of a cylindrical reactor having a diameter of 10 cm, 0.5L of transition metal group Pd catalyst prepared by the above-described manufacturing method was charged, and 3L of metal silicon was loaded with a screw from the top.

A silicon tetrachloride tank in a 2 L vessel was maintained at a silicon tetrachloride vaporization temperature line (about 50 ° C.) and bubbled with hydrogen at 70 sccm through MFC. At this time, by heating using an electric heating device installed on the outer wall of the reactor was maintained at 350 ℃. At this time, the power consumption was about 5kw, and the conversion rate of trichlorosilane was 32%. Gas chromatography (GC) analysis of the top material through a distillation column showed TCS of 98%, STC of 1.2%, H ₂ of 0.6% and HCl of 0.2%.

Example 2

Under the same conditions as in Example 1, the chlorine is added independently from the chlorine source as shown in FIG. At this time, when chlorine was introduced at a molar ratio of hydrogen and chlorine of about 10: 1, the power consumption of the electric heater device installed outside the reactor was about 8% of Example 1, and the TCS conversion rate was 32%. Gas chromatography analysis at the top of the distillation column showed that the TCS purity was 99.2%.

Example 3

When the molar ratio of hydrogen and chlorine was adjusted to 5: 1 in Example 2, the power consumption of the electric heater device installed outside the reactor was about 2% of Example 1, and the TCS conversion rate was 20%. Gas chromatography analysis at the top of the distillation column from the distillation column showed that the TCS purity was 99.5%.

Example 4

In Example 2, the molar ratio of hydrogen and chlorine was adjusted to 1: 1, and the TCS conversion was 35% when the reactor temperature was increased from 350 ° C. to 500 ° C. to 550 ° C., and analyzed by gas chromatography at the top of the distillation column. One result showed that the purity of TCS was 98.5%.

Example 5

In Example 2, the electric heater device installed outside the reactor was removed, and a preheating device was installed in a pipe located before the raw material was supplied to the reactor, and the raw material was input to the reactor by preheating to 350 ° C. The temperature inside the reactor was maintained at 300 ℃ ~ 350 ℃, the TCS conversion was 31%, the results of gas chromatography analysis at the top of the distillation column showed a purity of 99% TCS.

Example 6

When the molar ratio of hydrogen and chlorine was adjusted to 1: 1 in Example 5, the temperature of the reactor was warmed to 400 ° C to 450 ° C, and the TCS conversion was 35%. Analysis of gas chromatography at the top showed T. purity of 98.8%.

As can be seen from Examples 1 to 6 described above, the capacity of a heater installed outside the reactor in the case of using the preheater and the catalyst, and the reaction heat generated by the chlorine input when chlorine is added. The installation space, installation cost, production cost and maintenance cost can be greatly reduced by reducing the cost or removing the heater device.

The above-described embodiment is one embodiment according to the present invention described on the basis of the preheater and the reactor heating apparatus shown in FIG. 1, and another structure of the chlorine gas injection for obtaining the reaction heat is the first structure described above. The pipe is installed at one side of the reactor lower side maintained at 300 ℃ ~ 500 ℃, to supply chlorine gas independently from the chlorine supply source through the pipe. The second structure is designed to maximize the exothermic reaction by installing the chlorine inlet in the center of the reactor and supplying the chlorine gas from the chlorine source through the pipe.The reaction temperature starts from 300 ℃ ~ 500 ℃ (It means that the reaction is made by the heat of its own reaction) If the power to the reactor heating device is cut off.

The first, second and third structures, which are different structures for injecting chlorine, greatly reduce the capacity of the heating device of the reactor or greatly reduce the operating time of the heating device, thereby greatly increasing the installation cost and the production cost of trichlorosilane. Can be reduced.

In the present invention, a preheating device is installed at the front end of a reactor, and a catalyst made of transition metal group metal (Pd, Pb, Cu, Pt, Ti, Sr-based) is charged to form a catalyst layer, and chlorine may be added to the reactor. In this case, since the capacity of the heater device installed outside the reactor can be reduced or the heater device can be removed, installation space, installation cost, production cost, and maintenance cost can be greatly reduced, and fine powder metal can be installed by installing a cyclone on the reactor. Since the silicon is separated and recovered and recycled, and the silicon tetrachloride separated and recovered in the distillation column is configured to be recycled, the production cost and material cost can be reduced, so the industrial applicability is very high.

1 is a device diagram for the production of trichlorosilane using a catalyst and reaction heat designed according to the present invention

2 is an enlarged view showing a distillation column in a trichlorosilane production apparatus designed according to the present invention.

<Description of the symbols for the main parts of the drawings>

11; Hydrogen source 12; Chlorine Source

13; Silicon tetrachloride tank heating apparatus 14; Silicon Tetrachloride Tank

15; Preheater (piping) 16; Catalyst bed

17; Metalsilicon layer 18; Reactor heating device

19; Metal silicon tank 20; screw

21; Cyclone 22; Distillation column heating device

23; Distillation column 24; Cooling Heat Exchanger

25; Heat exchanger 26 for cold condensation; Trichlorosilane Storage Tank

27; Silicon tetrachloride collected in a distillation column tank; Baffle

29; Feed pump (to silicon tetrachloride storage tank) 30; Silicon Tetrachloride Storage Tank

31; Feed pump (silicon tetrachloride tank) 32; Reactor

33; Vent

Claims (12)

In the manufacturing apparatus for manufacturing trichlorosilane, A hydrogen source for supplying hydrogen to the silicon tetrachloride tank; A silicon tetrachloride tank for receiving hydrogen from the hydrogen source through a pipe and bubbling hydrogen and silicon tetrachloride into the reactor; A chlorine supply source for mixing and supplying chlorine gas to one side of a pipe through which the bubbled fluid passes in the silicon tetrachloride tank; A preheater installed at the front of the reactor and installed outside the pipe where hydrogen, silicon tetrachloride and chlorine are mixed to preheat the mixed fluid and inject it into the reactor; A reactor in which a transition metal group catalyst and a metal silicon are charged to generate trichlorosilane by reacting while hydrogen and chlorine gas are mixed and injected into the silicon tetrachloride in the silicon tetrachloride tank; And In order to separate the silicon tetrachloride and trichloride produced in the reactor by the difference in boiling point, the trichlorosilane production apparatus using a metal catalyst and a reaction heat consisting of a distillation column having a heating device at the bottom and a cooling heat exchanger at the top. In the manufacturing apparatus for manufacturing trichlorosilane, A hydrogen source for supplying hydrogen to the silicon tetrachloride tank; A silicon tetrachloride tank for receiving hydrogen from the hydrogen source through a pipe and bubbling hydrogen and silicon tetrachloride into the reactor; A chlorine supply source for mixing and supplying chlorine gas to one side of a pipe through which the bubbled fluid passes in the silicon tetrachloride tank; A reactor in which a transition metal group catalyst and a metal silicon are charged to generate trichlorosilane by reacting while hydrogen and silicon tetrachloride are mixed and injected into the silicon tetrachloride in the silicon tetrachloride tank; A reactor electric heating device installed outside the reactor to heat the reactor; And In order to separate the silicon tetrachloride and trichloride produced in the reactor by the difference in boiling point, the trichlorosilane production apparatus using a metal catalyst and a reaction heat consisting of a distillation column having a heating device at the bottom and a cooling heat exchanger at the top. In the manufacturing apparatus for manufacturing trichlorosilane, A hydrogen source for supplying hydrogen to the silicon tetrachloride tank; A silicon tetrachloride tank for receiving hydrogen from the hydrogen source through a pipe and bubbling hydrogen and silicon tetrachloride into the reactor; A chlorine supply source for installing a chlorine gas inlet at one side of the reactor or at the center of the reactor and supplying chlorine gas to the reactor through a pipe; In the silicon tetrachloride tank, an exothermic reaction is performed by hydrogen injected through a pipe, silicon tetrachloride, and chlorine gas injected from a chlorine source, and a transition metal group catalyst and metal silicon are charged to generate trichlorosilane using the exothermic heat. Reactor; A reactor electric heating device installed outside the reactor to heat the reactor; And An apparatus for producing trichlorosilane using a metal catalyst and reaction heat consisting of a distillation column having a heating device and a cooling heat exchanger in a lower portion in order to separate silicon tetrachloride and trichlorosilane produced in the reactor by using a difference in boiling point. The method according to any one of claims 1 to 3, The transition metal group catalyst is Pd, Pb, Cu, Ni, Ti, Sr and Pt trichlorosilane production apparatus using a metal catalyst and the reaction heat, characterized in that the production by selecting one or two or more. The method according to claim 4, The dye of the transition metal group catalyst is selected from alumina, zeolite, silicon oxide, activated carbon and diatomaceous earth to prepare a trichloride silane using a metal catalyst and the reaction heat, characterized in that the charge into the reactor. The method according to any one of claims 1 to 3, And a molar ratio of hydrogen and chlorine introduced from the hydrogen source and the chlorine source is mixed between 50: 1 and 1: 1 to inject the trichlorosilane using the metal catalyst and the heat of reaction. The method according to any one of claims 1 to 3, The reactor is composed of a fixed bed reactor prepared by separating the catalyst layer and the metal silicon layer, a mixed reactor made by mixing and charging the catalyst and the metal silicon, and a catalyst and the metal silicon to be moved in the reactor to increase the reaction time to increase the conversion rate. Trichlorosilane production apparatus using a metal catalyst and the heat of reaction produced by selecting one of the fluidized bed reactor manufactured to be. The method according to any one of claims 1 to 3, The reaction temperature of the reactor is between 100 ° C and 500 ° C, the internal pressure of the reactor is between 1 atm and 10 atm, the internal pressure of the distillation column is between 1 and 5 atm, the internal temperature of the distillation column Trichlorosilane production apparatus using a metal catalyst, characterized in that made between 10 ℃ to 100 ℃. The method according to any one of claims 1 to 3, The distillation column is a reboiler having a heating device installed at the bottom; Trichloride using a metal catalyst, consisting of a distillation column to expand the contact area of the gas to increase the purity of trichlorosilane and a condenser to feed back the changed liquid and transfer the gas to the storage tank of trichlorosilane. Silane manufacturing equipment. In the production method for producing trichlorosilane, Supplying hydrogen through a pipe from a hydrogen supply source to a silicon tetrachloride tank; Receiving hydrogen through a pipe from the hydrogen supply source and bubbling hydrogen and silicon tetrachloride in a silicon tetrachloride tank and injecting the hydrogen into the reactor through the pipe; Supplying chlorine gas from a chlorine supply source to one side of a pipe through which the bubbled fluid passes in the silicon tetrachloride tank; Preheating the mixed gas using a preheater installed in a pipe in which hydrogen, silicon tetrachloride, and chlorine are mixed in front of the reactor; Injecting the preheated hydrogen, silicon tetrachloride and chlorine mixed fluid into a transition metal group catalyst and a metal silicon-loaded reactor to generate trichlorosilane; And In the distillation column equipped with a heating device and a cooling heat exchanger at the bottom, the silicon tetrachloride and the trichlorosilane contained in the gas generated by the reaction in the reactor are separated by using the difference in boiling point using the heating device and the cooling heat exchanger installed in the distillation column. Method for producing trichlorosilane using a metal catalyst and heat of reaction consisting of a process for obtaining trichlorosilane. In the production method for producing trichlorosilane, Supplying hydrogen through a pipe from a hydrogen supply source to a silicon tetrachloride tank; Receiving hydrogen through a pipe from the hydrogen supply source and bubbling hydrogen and silicon tetrachloride in a silicon tetrachloride tank and injecting the hydrogen into the reactor through the pipe; Supplying chlorine gas from the chlorine source into the reactor through a pipe installed at one side of the reactor or a chlorine inlet installed at the center of the reactor; In the silicon tetrachloride tank, hydrogen and silicon tetrachloride are injected through a pipe, chlorine gas is supplied from a chlorine source to a reactor through a pipe, heat generated by supplied chlorine and hydrogen, and heat supplied from a heating device installed outside the reactor. Generating trichlorosilane by reacting in a reactor loaded with a transition metal group catalyst and a metal silicon by using; And A method of producing trichlorosilane using a metal catalyst and heat of reaction comprising a step of separating silicon tetrachloride and trichlorosilane using a difference in boiling point in a distillation column having a heating device and a cooling heat exchanger in a lower portion of the gas produced by the reactor. The method according to claim 10 or 11, A cyclone for separating and recovering fine powdered metal silicon from the gas passed through the reactor, and recycling the powdered metal silicon separated and recovered from the cyclone into the reactor; And A method for producing trichlorosilane using a metal catalyst and heat of reaction further comprising the step of recycling the silicon tetrachloride collected and recovered in the distillation column tank to a silicon tetrachloride tank using the difference in boiling point in the distillation column.

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