JP2012153583A - Apparatus for producing hydrogen selenide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for producing hydrogen selenide which improves the yield of the hydrogen selenide, and can produce high-purity hydrogen selenide continuously.SOLUTION: The apparatus for producing the hydrogen selenide includes: a route 12 and a route 13 for charging hydrogen and metallic selenium, respectively, to a reactor 11 that generates the hydrogen selenide from the hydrogen and the metallic selenium; a route 14 for purging a reaction gas that is generated in the reactor and contains the hydrogen selenide; a hydrogen selenide collector 15 for collecting the hydrogen selenide in the reaction gas; heating and cooling devices 16a and 16b which can be switched between a cooling operation for cooling the reaction gas to collect the metal selenium and a heating operation for heating the hydrogen to evaporate the metallic selenium; a metal selenium charging vessel 29 that has purge routes 35a and 35b; and a gas circulation route 17 for purging the reaction gas from the hydrogen selenide collector and returning it to the hydrogen charging route.

Description

  The present invention relates to a hydrogen selenide production apparatus, and more particularly to a hydrogen selenide production apparatus that produces hydrogen selenide by reacting metal selenium with hydrogen under heating.

  Hydrogen selenide is an important material as a doping gas for silicon semiconductors, and is also an important material for compound semiconductors such as zinc selenide, particularly as a raw material for solar cells such as CIS and CZTS in recent years. In general, hydrogen selenide is produced by bringing hydrogen into contact with a selenium compound such as metal selenium or selenium oxide in a reactor heated to 500 to 700 ° C., and directly hydrogenating selenium to form gaseous selenide. A method of generating hydrogen is employed (see, for example, Patent Document 1).

JP 2007-246342 A

  However, in the conventional method, since most of the hydrogen charged into the reaction furnace is discharged from the reaction furnace without being reacted, there is a problem that the amount of hydrogen consumed is larger than the amount of hydrogen selenide produced. In addition, since the conventional hydrogen selenide production apparatus is a batch system, when a new selenium compound is introduced into the reaction furnace after completion of one reaction process, the temperature of the reaction furnace is lowered and the reaction furnace After removing the highly toxic hydrogen selenide and metal selenium vapor from inside, open the reactor and introduce new selenium compound, and then remove the atmospheric components that entered during the introduction of this selenium compound from the reactor It was necessary to heat the temperature of the reactor to a predetermined temperature.

  For this reason, a lot of energy is consumed for heating and cooling the reactor, and since hydrogen selenide and metal selenium are excluded from the reactor during cooling, there is also a problem that the yield of hydrogen selenide is low. . Furthermore, unreacted metal selenium present as impurities in the gas of the production system and metal selenium produced by re-decomposition of hydrogen selenide easily agglomerate and solidify. It has been difficult to produce hydrogen selenide continuously for a long time due to problems such as precipitation in the pipe and blocking the piping system.

  Accordingly, an object of the present invention is to provide a hydrogen selenide production apparatus capable of increasing the yield of hydrogen selenide and continuously producing high-purity hydrogen selenide.

  In order to achieve the above object, the hydrogen selenide production apparatus of the present invention comprises a reaction furnace for producing gaseous hydrogen selenide by bringing metal selenium and hydrogen as raw materials into contact with each other at a preset heating temperature, and the reaction A hydrogen charging path for charging the hydrogen into the furnace, a metal selenium charging path for charging the metal selenium into the reaction furnace, and a reaction for extracting a reaction gas containing gaseous hydrogen selenide generated in the reaction furnace from the reaction furnace A gas extraction path, and a hydrogen selenide collector that collects the hydrogen selenide in the reaction gas extracted in the reaction gas extraction path at a preset cooling temperature, and from the reaction furnace, the The reaction gas withdrawn to the hydrogen selenide collector is cooled to condense and collect unreacted metal selenium contained in the reaction gas and metal selenium that has been decomposed by the generated hydrogen selenide. And a heating operation in which hydrogen introduced into the reaction furnace is heated from the hydrogen charging path and the metal selenium collected in the cooling operation is vaporized to be entrained in hydrogen and charged into the reaction furnace. The metal selenium charging path includes a metal selenium charging container, charging path opening / closing means provided between the metal selenium charging container and the reactor, and the metal selenium charging path. A purge path for replacing the gas in the container, and the hydrogen selenide collector collects the reaction gas after collecting the hydrogen selenide by the hydrogen selenide collector. A gas circulation path is provided which is extracted from the vessel and returned to the hydrogen input path.

  Furthermore, in the hydrogen selenide production apparatus of the present invention, a plurality of the hydrogen selenide collectors are provided, and an operation for repairing the hydrogen selenide in the reaction gas and an operation for collecting the repaired hydrogen selenide are alternately performed. The metal selenium charging path includes a relay container between the metal selenium charging container and the reaction furnace, and a charging path opening / closing means is provided between the metal selenium charging container, the relay container, and the reaction furnace. Metal selenium refining that is provided with each of them, purifies the metal selenium by removing the impurities contained in the metal selenium by circulating a purifying gas while heating to the relay container at a preset purification temperature Means is provided.

  According to the hydrogen selenide production apparatus of the present invention, since the raw metal selenium can be fed into the reaction furnace from the metal selenium charging path without opening the reaction furnace, the energy for heating and cooling the reaction furnace can be reduced. Can do. In addition, unreacted metal selenium in the reaction gas withdrawn from the reactor and metal selenium produced by re-decomposition of hydrogen selenide are collected by a heating / cooling device during the cooling operation and entrained with hydrogen during the heating operation. Therefore, the metal selenium can be effectively used as a raw material, and the metal selenium does not precipitate in the reaction gas extraction path to block the path. Furthermore, the hydrogen in the reaction gas can be effectively used as a raw material by returning the reaction gas after the hydrogen selenide is collected by the hydrogen selenide collector to the hydrogen input path. Accordingly, hydrogen selenide can be continuously produced, and metal selenium and hydrogen can be effectively used, so that the yield of hydrogen selenide can be improved.

It is a systematic diagram which shows one example of a hydrogen selenide manufacturing apparatus of this invention. It is explanatory drawing which shows an example of a driving | running state. It is explanatory drawing which shows the other example of a driving | running state.

  The hydrogen selenide production apparatus shown in this embodiment includes a reaction furnace 11 for generating hydrogen selenide from raw metal selenium and hydrogen, a hydrogen input path 12 for supplying hydrogen to the reaction furnace 11, and a metal for the reaction furnace 11. Metal selenium input path 13 for supplying selenium, reaction gas extraction path 14 for extracting reaction gas containing hydrogen selenide produced by reaction in the reaction furnace 11, and reaction gas extraction path 14 were extracted. A hydrogen selenide collector 15 for collecting hydrogen selenide in the reaction gas, a pair of heating and cooling devices 16a, 16b provided in the middle of the hydrogen input path 12 and the reaction gas extraction path 14, and hydrogen selenide A hydrogen gas circulation path 17 is provided which collects hydrogen selenide by the collector 15 and extracts the reaction gas after the hydrogen selenide collector 15 and returns it to the hydrogen input path 12.

  The reaction furnace 11 includes a metal selenium holding part 18 for holding metal selenium charged from the metal selenium charging path 13, a reaction furnace heating means 19 for heating the inside of the reaction furnace 11 to a preset temperature, a reaction furnace 11 and an in-furnace pressure detector 20 for monitoring the pressure in the reactor 11. The temperature in the reaction furnace 11 is set to 400 to 700 ° C. at which metal selenium and hydrogen can react in the reaction furnace 11, for example, 500 ° C. in consideration of reaction rate and heating energy. This reactor 11 is charged with an excess of hydrogen than is necessary for the reaction, and gaseous hydrogen selenide produced by the reaction of metal selenium with hydrogen is entrained by unreacted hydrogen and the reaction gas. As shown in FIG.

  The hydrogen input path 12 is a path for supplying hydrogen from a hydrogen supply source (not shown) to the reaction furnace 11 with the flow rate adjusted by the flow rate regulator 21 and provided at the inflow portion to the heating and cooling units 16a and 16b. The hydrogen channel switching valves 22a and 22b are configured to introduce hydrogen into one of the heating and cooling devices 16a and 16b. In addition, the reaction gas extraction path 14 is configured to extract the reaction gas from one of the heating and cooling devices 16a and 16b by the reaction gas flow path switching valves 23a and 23b provided at the outflow portions from the heating and cooling devices 16a and 16b. Is formed.

  The heating / cooling devices 16a and 16b set in advance a heating operation for heating the hydrogen supplied from the hydrogen input passage 12 to a preset heating temperature and a reaction gas extracted from the reaction furnace 11 to the reaction gas extraction passage 14. The cooling operation for cooling to the cooled temperature is alternately performed, and one heating / cooling channel 24a, 24b in which hydrogen or a reactive gas flows and hydrogen flowing in the heating / cooling channel 24a, 24b are heated. Heating means 25a, 25b for cooling and cooling means (not shown) for cooling the reaction gas. Switching between the heating operation and the cooling operation in the heating / cooling devices 16a and 16b is performed by opening and closing the hydrogen flow path switching valves 22a and 22b and the reaction gas flow path switching valves 23a and 23b in a preset order, and heating means 25a, 25b and the cooling means are operated in a preset order.

  The cooling operation in the heating / cooling devices 16a and 16b is performed by condensing unreacted metal selenium contained in the high-temperature reaction gas extracted from the reaction furnace 11 and metal selenium that has been decomposed by the generated hydrogen selenide. It is an operation for collecting in the cooling channels 24a and 24b, and the cooling temperature of the heating and cooling channels 24a and 24b is a temperature at which metal selenium can be collected, usually in a temperature range of 0 to 100 ° C., for example, The temperature is set to 100 ° C. in consideration of cooling energy. Thereby, metal selenium can be separated and removed in advance from the reaction gas flowing into the hydrogen selenide collector 15 via the reaction gas extraction path 14.

  On the other hand, the heating operation in the heating / cooling devices 16a and 16b preheats the hydrogen charged into the reactor 11, and condenses it in the heating and cooling flow paths 24a and 24b by condensing in the cooling operation performed before the heating operation. The collected liquid metal selenium is heated and vaporized, and the vaporized metal selenium is entrained with hydrogen and re-introduced into the reaction furnace 11. The heating temperature of the heating and cooling flow paths 24 a and 24 b is set to be metal selenium. At a temperature that does not adversely affect the temperature in the reaction furnace 11, usually 200 to 500 ° C., for example, reliable vaporization of metal selenium, temperature decrease in the reaction furnace 11, and heating energy Considering this, the temperature is set to 300 ° C.

  The hydrogen selenide collector 15 has a cooling means 26 such as a cooling jacket, and is introduced into the hydrogen selenide collector 15 from the reaction gas extraction path 14 and is accompanied by hydrogen selenide. By cooling the reaction gas comprising, hydrogen selenide in the reaction gas is liquefied or solidified and separated and collected from the reaction gas. The hydrogen selenide trapping temperature of the hydrogen selenide collector 15 is set to a low temperature of −50 ° C. or lower, preferably −100 ° C. or lower with liquid nitrogen or the like. Hydrogen that is not liquefied or solidified at the cooling temperature of the hydrogen selenide collector 15 is extracted from the hydrogen selenide collector 15 to the hydrogen gas circulation path 17 and is passed through the blower 27 and the flow rate controller 28. It merges with the hydrogen flowing through the hydrogen input path 12.

  In the metal selenium charging path 13, a metal selenium charging container 29 and a relay container 30 are provided in series. A charging path opening / closing means 31 is provided between the metal selenium charging container 29 and the relay container 30, between the metal selenium charging container 29 and the relay container 30, and between the relay container 30 and the reactor 11. , 32, and 33, the metal selenium input container 29 is provided with purge paths 35a and 35b having purge valves 34a and 34b, and the relay container 30 is provided with a purge path 37a having purge valves 36a and 36b. , 37b and a heating means 30a.

  Further, as shown by an imaginary line in FIG. 1, a second hydrogen selenide collector 15a is provided, a second reaction gas extraction path 14a, a second hydrogen gas circulation path 17a, and each reaction gas extraction By providing switching valves 38a, 38b, 39a, 39b for switching the outlet paths 14, 14a and the respective hydrogen gas circulation paths 17, 17a, the two hydrogen selenide collectors 15, 15a are operated to collect hydrogen selenide. And the collected hydrogen selenide collecting operation can be used alternately.

  Next, the procedure for continuously producing hydrogen selenide will be described with reference to FIGS. 2 and 3, only the main components in the hydrogen selenide production apparatus shown in FIG.

  First, as shown by the solid line in FIG. 2, when one heating / cooling device 16a performs a heating operation and the other heating / cooling device 16b performs a cooling operation, the hydrogen supplied from the hydrogen charging path 12 is in an open state. The metal selenium condensed and collected in the previous cooling operation is vaporized while being preheated by the heating / cooling device 16a heated to a predetermined temperature through the one hydrogen flow path switching valve 22a. It flows into the reaction furnace 11 heated to a predetermined temperature with selenium. Part of the hydrogen flowing into the reaction furnace 11 reacts with the metal selenium held in the metal selenium holding unit 18 and the metal selenium entrained from the heating / cooling device 16a to generate hydrogen selenide.

  The generated hydrogen selenide flows into the other heating / cooling device 16b which is entrained by the unreacted hydrogen and cooled to a predetermined temperature, and the unreacted metal selenium and the metal selenium obtained by re-decomposing the hydrogen selenide are condensed. To separate from the reaction gas. The reaction gas separated from the metal selenium is extracted from the heating / cooling device 16b through the reaction gas flow path switching valve 23b to the reaction gas extraction path 14 and cooled to a predetermined temperature. It flows into the collector 15.

  The hydrogen selenide contained in the reaction gas flowing into the low-temperature hydrogen selenide collector 15 is collected by being liquefied or solidified and separated from the reaction gas. The reaction gas (hydrogen) from which hydrogen selenide has been separated is extracted into the hydrogen gas circulation path 17, boosted to a pressure that can flow into the hydrogen input path 12 by the blower 27, and then the flow rate is adjusted by the flow rate regulator 28. The hydrogen is introduced into the hydrogen input path 12, joined with hydrogen supplied from the hydrogen supply source via the flow rate regulator 21, passes through the heating / cooling device 16 a, and is circulated and supplied into the reaction furnace 11.

  In addition, a predetermined amount of the raw metal selenium is charged into the metal selenium input container 29 with only the input path opening / closing means 31 on the input side of the metal selenium input container 29 being opened. After the metal selenium is charged into the metal selenium charging container 29, the charging path opening / closing means 31 is closed and the purge valves 34a and 34b are opened, and a purge gas such as nitrogen gas as an inert gas is charged into the metal selenium from the purge path 35a. By introducing into the container 29 and discharging the gas in the metal selenium input container 29 to the purge path 35b, the air component that has entered the metal selenium input container 29 when the metal selenium is supplied is purged.

  After replacing the air component in the metal selenium input container 29 with an inert gas, only the input path opening / closing means 32 between the metal selenium input container 29 and the relay container 30 is opened, and the metal selenium is relayed from the metal selenium input container 29. Move to container 30. The purge valves 36a and 36b are opened in a state where the input path opening / closing means 32 and 33 on both sides of the relay container 30 are shut off, and a purge gas is introduced into the relay container 30 from the purge path 37a. The gas component that has entered the relay container 30 when the metal selenium is moved from the metal selenium charging container 29 to the relay container 30 is purged. After the gas replacement in the relay container 30 is completed, the metal selenium in the relay container 30 can be charged into the reaction furnace 11 by opening only the charging path opening / closing means 33. After the metal selenium is charged into the reaction furnace 11, the inside of the relay container 30 is purged with an inert gas such as nitrogen gas in the same manner as described above, so that the toxic gas generated in the reaction furnace 11 is transferred from the relay container 30 to the metal. It can be prevented from diffusing outside through the selenium charging container 29.

  Thus, by introducing the metal selenium as a raw material into the reaction furnace 11 using the metal selenium input container 29 and the relay container 30 arranged in series, impurities that adversely affect the reaction in the reaction furnace 11 and It is possible to reliably prevent the atmospheric components from entering the reaction furnace 11 and to reliably prevent the toxic gas generated in the reaction furnace 11 from diffusing to the outside. Further, the heating means 30a is provided in the relay container 30 so that the metal selenium can be heated, so that the metal selenium can be heated to perform the purification process of the metal selenium, and the metal selenium does not react with hydrogen. The metal selenium can be effectively purified by heating to an appropriate temperature of, for example, 300 ° C. and using hydrogen as the purge gas. At the same time, since metallic selenium can be preheated and charged into the reaction furnace 11, a temperature drop in the reaction furnace 11 can also be suppressed.

  Even if only the metal selenium input container 29 is provided without providing the relay container 30, the atmospheric components can be converted into the reactor 11 by sufficiently purging the metal selenium input container 29 before opening the input path opening / closing means. It is possible to prevent the toxic gas from entering the gas and diffusing the toxic gas to the outside.

  The heating operation of the heating / cooling device 16a and the cooling operation of the heating / cooling device 16b are switched in accordance with conditions such as a preset time or a preset hydrogen selenide collection amount, and are shown by a solid line in FIG. As described above, one heating / cooling device 16a performs a cooling operation for cooling the reaction gas, and the other heating / cooling device 16b performs a heating operation for preheating hydrogen. Accordingly, in one heating / cooling device 16a, an operation of condensing and collecting metal selenium in the reaction gas is performed by cooling the reaction gas extracted from the reaction furnace 11, and in the other heating / cooling device 16b, The raw material hydrogen to be charged into the reaction furnace 11 is preheated, the metal selenium condensed in the previous cooling operation is vaporized, and the vaporized metal selenium is entrained with hydrogen and introduced into the reaction furnace 11. At this time, by providing three or more heating / cooling devices and switching between heating and cooling in a predetermined order, heating and cooling during operation switching can be performed smoothly and reliably.

  When a predetermined amount of hydrogen selenide is collected in the hydrogen selenide collector 15, the hydrogen selenide collector 15 is heated to a temperature higher than the vaporization temperature of hydrogen selenide to capture the hydrogen selenide. The hydrogen selenide collected in the collector 15 is collected as product gas. Also at this time, by providing a plurality of hydrogen selenide collectors, the hydrogen selenide collector and the hydrogen selenide collecting operation are alternately performed in the hydrogen selenide collector, thereby continuously performing selenide. It becomes possible to collect hydrogen fluoride.

  By producing hydrogen selenide with the hydrogen selenide production apparatus configured as described above, the metal selenium in the reaction gas can be reused as a raw material, and the hydrogen extracted from the hydrogen selenide collector 15 can also be reused as a raw material. Therefore, the utilization efficiency of metal selenium and hydrogen as raw materials can be greatly improved, and the yield of hydrogen selenide can be greatly improved.

  Using the hydrogen selenide production apparatus having the configuration shown in FIG. 1, 5 kg of metal selenium is charged into the reactor, and the hydrogen from the hydrogen gas source and the circulating hydrogen are combined while heating the reactor to 500 ° C. The reactor was charged at the specified flow rate. The temperature of the heating / cooling device on the hydrogen input side for performing the heating operation was set to 300 ° C., and the temperature of the heating / cooling device on the reaction gas side for performing the cooling operation was set to 100 ° C. The temperature of the hydrogen selenide collector was set to -196 ° C. When the amount of hydrogen selenide collected in the hydrogen selenide collector becomes 1 kg, the heating operation and the cooling operation of the heating / cooling device are switched, and the switching of the heating / cooling operation is switched to 1 kg of the hydrogen selenide collection amount. Repeatedly, hydrogen was circulated until no hydrogen selenide was generated from the reactor. As a result, the collected amount of hydrogen selenide was 5.1 kg, the input amount of metal selenium was 5.0 kg, the yield was 99.5%, the input amount of hydrogen was 1415 NL (NL is the volume [liter] in the standard state, The same applies hereinafter), and the yield was 99.6%.

  The same operation as in Example 1 was performed except that the amount of metal selenium charged into the reactor was 25 kg, and the heating / cooling operation switching in the heating / cooling device was repeated every 5 kg of hydrogen selenide. As a result, the collected amount of hydrogen selenide was 25.4 kg, the input amount of metal selenium was 25.0 kg, the yield was 99.1%, the input amount of hydrogen was 7050 NL, and the yield was 99.6%. .

  As shown by an imaginary line in FIG. 1, a hydrogen selenide production apparatus in which two hydrogen selenide collectors were installed so as to be switchable was used. First, 25 kg of metal selenium was charged into the reactor, and hydrogen was charged at a specified flow rate while the reactor was heated to 500 ° C. The temperature of the heating / cooling device on the hydrogen input side for performing the heating operation was set to 300 ° C., and the temperature of the heating / cooling device on the reaction gas side for performing the cooling operation was set to 100 ° C. The temperature of the hydrogen selenide collector was set to -196 ° C. The heating / cooling operation in the heating / cooling device was switched every 5 kg of hydrogen selenide collecting in the hydrogen selenide collector.

  Further, when the amount of hydrogen selenide collected reaches 15 kg, 25 kg of metal selenium is charged into the metal selenium charging container, gas replacement with nitrogen gas is performed, and then 25 kg of metal selenium is moved to the relay container 30, The interior of the reactor 30 was purged and replaced with hydrogen gas, and then metal selenium was charged into the reactor 11. When 30 kg of hydrogen selenide was collected in one hydrogen selenide collector, the hydrogen selenide collector for collecting hydrogen selenide was switched to the other hydrogen selenide collector. Thereafter, while switching the heating / cooling operation of the heating / cooling device, hydrogen was circulated until no hydrogen selenide was generated from the reaction furnace. As a result, the collected amount of hydrogen selenide was 50.8 kg, the input amount of metal selenium was 50.0 kg, the yield was 99.1%, the input amount of hydrogen was 14100 NL, and the yield was 99.6%. .

Comparative Example 1
In the hydrogen selenide production apparatus having the configuration shown in FIG. 1, 10 kg of metal selenium is charged into the reactor in a state in which the heating / cooling operation of the heating / cooling device is not switched and hydrogen circulation through the hydrogen gas circulation path is stopped. While the reactor was heated to 500 ° C., hydrogen from a hydrogen gas source was charged at a specified flow rate. The temperature of the heating / cooling device was set to 100 ° C. corresponding to the cooling operation, and unreacted metal selenium and re-decomposed metal selenium were condensed and collected. The temperature of the hydrogen selenide collector was set to -196 ° C, and the gas (hydrogen) after hydrogen selenide separation was discharged from the system without being circulated by the hydrogen selenide collector. As a result, the collected amount of hydrogen selenide was 9.6 kg, the input amount of metal selenium was 10.0 kg, the yield was 93.6%, the input amount of hydrogen was 6660 NL, and the yield was 39.9%. .

Comparative Example 2
The same operation as in Comparative Example 1 was performed except that the amount of metal selenium charged into the reactor was 25 kg. When about 20 kg of hydrogen selenide was collected in the hydrogen selenide collector, a phenomenon in which the pressure in the reactor gradually increased began to appear. When about 21 kg of hydrogen selenide was collected, Was stopped to stop the reaction. As a result, the collected amount of hydrogen selenide was 20.8 kg, the input amount of metal selenium was 25.0 kg, the yield was 81.1%, the input amount of hydrogen was 16,100 NL, and the yield was 35.7%. .

  DESCRIPTION OF SYMBOLS 11 ... Reaction furnace, 12 ... Hydrogen input path, 13 ... Metal selenium input path, 14, 14a ... Reaction gas extraction path, 15, 15a ... Hydrogen selenide collector, 16a, 16b ... Heating / cooling device, 17, 17a DESCRIPTION OF SYMBOLS ... Hydrogen gas circulation path, 18 ... Metal selenium holding part, 19 ... Reactor heating means, 20 ... In-furnace pressure detector, 21 ... Flow controller, 22a, 22b ... Hydrogen flow path switching valve, 23a, 23b ... Reaction gas Flow path switching valve, 24a, 24b ... Heating / cooling flow path, 25a, 25b ... Heating means, 26 ... Cooling means, 27 ... Blower, 28 ... Flow rate regulator, 29 ... Metal selenium charging container, 30 ... Relay container, 30a ... Heating means, 31, 32, 33 ... charging path opening / closing means, 34a, 34b ... purge valve, 35a, 35b ... purge path, 36a, 36b ... purge valve, 37a, 37b ... purge path, 38a, 38b, 3 a, 39b ... switching valve

Claims (4)

  A reaction furnace for contacting gaseous metal selenium and hydrogen at a preset heating temperature to produce gaseous hydrogen selenide, a hydrogen input path for supplying the hydrogen to the reaction furnace, and the reaction furnace Metal selenium input path for supplying metal selenium, reaction gas extraction path for extracting reaction gas containing gaseous hydrogen selenide generated in the reaction furnace from the reaction furnace, and reaction gas extracted to the reaction gas extraction path A hydrogen selenide collector that collects the hydrogen selenide therein at a preset cooling temperature, and cools the reaction gas withdrawn from the reactor into the hydrogen selenide collector. Cooling operation for condensing and collecting unreacted metal selenium contained in the reaction gas and metal selenium produced by re-decomposition of hydrogen selenide and introducing the hydrogen into the reactor through the hydrogen input path A plurality of heating and cooling units that are alternately switched to a heating operation that is entrained in hydrogen and charged into the reactor by vaporizing the metal selenium collected by the cooling operation by heating the element, and charging the metal selenium The path comprises a metal selenium input container, an input path opening / closing means provided between the metal selenium input container and the reactor, and a purge path for replacing the gas in the metal selenium input container, The hydrogen selenide collector is provided with a gas circulation path for extracting the reaction gas after collecting the hydrogen selenide by the hydrogen selenide collector from the hydrogen selenide collector and returning it to the hydrogen input path. An apparatus for producing hydrogen selenide, wherein   2. The selenium according to claim 1, wherein a plurality of the hydrogen selenide collectors are provided, and an operation of repairing hydrogen selenide in the reaction gas and an operation of collecting the repaired hydrogen selenide are alternately performed. Hydrogen fluoride production equipment.   The metal selenium charging path includes a relay container between the metal selenium charging container and the reaction furnace, and includes a charging path opening / closing means between the metal selenium charging container, the relay container, and the reaction furnace. The hydrogen selenide production apparatus according to claim 1 or 2, wherein   The relay container is provided with metal selenium refining means for purifying metal selenium by removing the impurities contained in the metal selenium by circulating a purifying gas while heating to a preset refining temperature. The hydrogen selenide production apparatus according to claim 3.

Images