Method of processing discharge gas discharged from production process of gallium nitride compound semiconductor

Abstract

The present invention provides a method of processing discharge gas containing ammonia, hydrogen, nitrogen, and an organic metal compound discharged from the production process of a gallium nitride compound semiconductor. The discharge gas is brought into contact with a cleaning agent prepared by impregnating an alkali metal compound with a metal oxide to remove the organic metal compound from the discharge gas. The discharge gas from which an organic metal compound is removed is brought into contact with an ammonia decomposition catalyst on heating to decompose the ammonia into nitrogen and hydrogen. The discharge gas in which ammonia is decomposed is brought into contact with palladium alloy membrane on heating to recover hydrogen that has penetrated through the palladium alloy membrane. After an organic metal compound is removed to liquefy the ammonia contained in the discharge gas as described above, a pressurization process and a cooling process is conducted by a heat pump to pressurize and cool the discharge gas from which an organic metal compound is removed to liquefy the ammonia contained in the discharge gas and separate the liquefied ammonia from hydrogen and nitrogen so as to recover the liquefied ammonia. The recovered hydrogen and ammonia are supplied to and reused in the production process of a gallium nitride compound semiconductor.

1 . A method of recovering hydrogen comprising:
 a removal step of bringing discharge gas containing ammonia, hydrogen, nitrogen, and an organic metal compound discharged from the production process of a gallium nitride compound semiconductor into contact with a cleaning agent prepared by impregnating an alkali metal compound with a metal oxide to remove the organic metal compound from the discharge gas;   an ammonia decomposition step of bringing the discharge gas from which an organic metal compound is removed after the removal step into contact with an ammonia decomposition catalyst on heating to decompose the ammonia into nitrogen and hydrogen; and   a hydrogen recovery step of bringing the discharge gas in which ammonia is decomposed after the ammonia decomposition step into contact with palladium alloy membrane on heating to recover hydrogen that has penetrated through the palladium alloy membrane.   
     
     
         2 . The method of recovering hydrogen according to  claim 1 , wherein the cleaning agent is prepared by impregnating potassium hydroxide, sodium hydroxide, potassium oxide, or potassium carbonate with a metal oxide containing copper oxide and manganese oxide as the main components. 
     
     
         3 . The method of recovering hydrogen according to  claim 1 , wherein the ammonia decomposition catalyst is formed by supporting ruthenium on an alumina. 
     
     
         4 . The method of recovering hydrogen according to  claim 1 , further comprising a pressurization step of pressurizing the discharge gas with a compressor after the ammonia decomposition step and before the hydrogen recovery step. 
     
     
         5 . The method of recovering hydrogen according to  claim 1 , wherein the content of ammonia contained in discharged gas discharged from the production process is 10 to 40 vol %. 
     
     
         6 . A method of reusing hydrogen comprising a resupply step of supplying hydrogen recovered by the method of recovering hydrogen according to  claim 1  to the production process. 
     
     
         7 . A method of recovering ammonia comprising:
 a removal step of bringing discharge gas containing ammonia, hydrogen, nitrogen, and an organic metal compound discharged from the production process of a gallium nitride compound semiconductor into contact with a cleaning agent prepared by impregnating an alkali metal compound with a metal oxide to remove the organic metal compound from the discharge gas; and   an ammonia recovery step of conducting a pressurization process and a cooling process by a heat pump to pressurize and cool the discharge gas from which an organic metal compound is removed after the removal step to liquefy the ammonia contained in the discharge gas and separate the liquefied ammonia from hydrogen and nitrogen so as to recover the liquefied ammonia.   
     
     
         8 . The method of recovering ammonia according to  claim 7 , wherein the cleaning agent is prepared by impregnating potassium hydroxide, sodium hydroxide, potassium oxide, or potassium carbonate with a metal oxide containing copper oxide and manganese oxide as the main components. 
     
     
         9 . The method of recovering ammonia according to  claim 7 , wherein the content of ammonia contained in discharged gas discharged from the production process is 10 to 40 vol %. 
     
     
         10 . The method of recovering ammonia according to  claim 7 , wherein the pressure of discharge gas during the pressurization process is 0.5 to 2 MPaG. 
     
     
         11 . The method of recovering ammonia according to  claim 7 , wherein the temperature of discharge gas during the cooling process is −30 to −60° C. 
     
     
         12 . The method of recovering ammonia according to  claim 7 , further comprising a bubbling process of bubbling discharge gas pressurized by the pressurization process in liquid ammonia. 
     
     
         13 . The method of recovering ammonia according to  claim 12 , further comprising a stirring and removal step of stirring the liquid ammonia and removing hydrogen and nitrogen contained in the liquid ammonia. 
     
     
         14 . The method of recovering ammonia according to  claim 13 , wherein the stirring and removal step further removes methane or ethane resulted from the decomposition of the organic metal compound derived from one or more kinds of organic metal sources selected from trimethylgallium, triethylgallium, trimethylindium, triethylindium, trimethylaluminum, and triethylaluminum from the liquid ammonia. 
     
     
         15 . The method of recovering ammonia according to  claim 7 , wherein
 the production process includes decomposing the organic metal compound derived from one or more kinds of organic metal sources selected from trimethylgallium, triethylgallium, trimethylindium, triethylindium, trimethylaluminum, and triethylaluminum during vapor phase growth, and   the ammonia recovery step includes separating methane or ethane resulted from the decomposition of the organic metal compound during the production process from the ammonia when the ammonia is liquefied.   
     
     
         16 . The method of recovering ammonia according to  claim 7 , wherein refrigerant used in the cooling process conducted by the heat pump is ammonia. 
     
     
         17 . The method of recovering ammonia according to  claim 7 , wherein carrier gases used in the production process are hydrogen and nitrogen. 
     
     
         18 . The method of recovering ammonia according to  claim 7 , wherein the production process includes bubbling hydrogen or nitrogen in liquid source of one or more kinds selected from trimethylgallium, triethylgallium, trimethylindium, triethylindium, trimethylaluminum, and triethylaluminum to obtain a source gas containing the organic metal compound derived from an organic metal source used in the production process. 
     
     
         19 . The method of recovering ammonia according to  claim 13 , wherein the stirring and removal step decreases the content of hydrogen and nitrogen contained in liquid ammonia as impurities to 1000 ppm or less. 
     
     
         20 . A method of reusing ammonia, comprising:
 a mixed gas generation step of evaporating liquefied ammonia recovered by the method of recovering ammonia according to  claim 7  and mixing the evaporated ammonia with additional ammonia different from the evaporated ammonia to obtain mixed gas; and   a resupply step of purifying the mixed gas after the mixed gas generation step and supplying the purified mixed gas to the production process.   
     
     
         21 . The method of reusing ammonia according to  claim 20 , wherein the amount supplied of the additional ammonia is substantially equal to the amount of ammonia lost by the method of recovering ammonia according to  claim 7  after discharged gas is discharged from the production process. 
     
     
         22 . The method of reusing ammonia according to  claim 20 , wherein the additional ammonia is ammonia for industrial purposes, containing hydrogen and nitrogen as impurities.