Methods for producing silane
View Patent ↗Methods and systems for producing silane that use electrolysis to regenerate reactive components therein are disclosed. The methods and systems may be substantially closed-loop with respect to halogen, an alkali or alkaline earth metal and/or hydrogen.
1. A process for producing silane from a source of alkali or alkaline earth metal halide salt, the process comprising:
electrolyzing an alkali or alkaline earth metal halide salt to produce metallic alkali or alkaline earth metal and halogen gas;
contacting the metallic alkali or alkaline earth-metal with hydrogen to produce an alkali or alkaline earth metal hydride;
producing a halogenated silicon feed gas comprising at least one halosilane selected from the group consisting of silicon tetrahalide, trihalosilane, dihalosilane and monohalosilane by contacting the halogen gas with at least one of:
(1) silicon to produce silicon tetrahalide; and
(2) hydrogen to produce a hydrogen halide, wherein the hydrogen halide is further contacted with silicon to produce a mixture comprising silicon tetrahalide and trihalosilane; and
contacting the halogenated silicon feed gas with the alkali or alkaline earth metal hydride to produce silane and an alkali or alkaline earth-metal halide salt, the halogenated silicon feed gas being introduced into a disproportionation system prior to contacting the halogenated feed gas with the alkali or alkaline earth metal hydride.
2. The process as set forth in claim 1 wherein the metallic alkali or alkaline earth-metal is contacted with hydrogen in a solvent selected from the group consisting of toluene, dimethyl ether, diglyme, NaAlCl 4 and mixtures thereof.
3. The process as set forth in claim 2 wherein the metallic alkali or alkaline earth-metal is added to a reaction vessel containing the solvent to form a reaction mixture and wherein hydrogen gas is bubbled through the reaction mixture.
4. The process as set forth in claim 1 wherein the alkali or alkaline earth-metal hydride is contacted with the halogenated silicon feed gas in a solvent selected from the group consisting of toluene, dimethyl ether, diglyme, NaAlCl 4 and mixtures thereof.
5. The process as set forth in claim 4 wherein the solvent contains a catalyst.
6. The process as set forth in claim 5 wherein the catalyst is selected from the group consisting of tri-ethyl aluminum, various lewis acids, trace alkali metals and mixtures thereof.
7. The process as set forth in claim 1 wherein spent solvent comprising the halide salt and the solvent is produced upon contacting the alkali or alkaline earth-metal hydride with the halogenated silicon feed gas, the method comprising regenerating the solvent by separating the halide salt and the solvent.
8. The process as set forth in claim 7 wherein the halide salt and solvent are separated by evaporating the solvent from the salt and condensing the solvent after evaporation.
9. The process as set forth in claim 1 wherein the halogenated silicon feed gas comprises one or more metal halide impurities, the method comprising cooling the halogenated silicon feed gas to precipitate the metal halide impurities.
10. The process as set forth in claim 1 wherein halide salt is electrolyzed by:
introducing the salt to a vessel containing a cathode, an anode disposed within the cathode, and a separator disposed between the cathode and anode;
applying current to the cathode and anode to produce halogen gas and metallic alkali or alkaline earth metal; and
discharging halogen gas and metallic alkali or alkaline earth metal from the vessel.
11. The process as set forth in claim 10 wherein at least one compound selected from the group consisting of calcium chloride, aluminum chloride and sodium carbonate is added to the vessel to lower the melting point of the halide salt.
12. The process as set forth in claim 1 wherein granular silicon and at least one of halogen gas and hydrogen halide are introduced into a fluidized bed reactor wherein the halogen gas or hydrogen halide fluidize the granular silicon in the reactor.
13. The process as set forth in claim 1 wherein the alkali or alkaline earth-metal salt produced by contacting the halogenated silicon feed gas with the alkali or alkaline earth metal hydride is electrolyzed to produce metallic alkali or alkaline earth metal and halogen gas.
14. The process as set forth in claim 1 wherein the alkali or alkaline earth metal is selected from the group consisting of lithium, sodium, potassium, magnesium, barium, calcium and mixtures thereof.
15. The process as set forth in claim 1 wherein the alkali or alkaline earth metal is sodium.
16. The process as set forth in claim 1 wherein the alkali or alkaline earth metal halide salt comprises a halogen selected from the group consisting of fluorine, chlorine, bromine, iodine and mixtures thereof.
17. The process as set forth in claim 1 wherein the alkali or alkaline earth metal halide salt comprises chlorine.
18. process for producing silane in a substantially closed-loop system with respect to alkali or alkaline earth metals, the process comprising:
contacting a halogenated silicon feed gas with an alkali or alkaline earth metal hydride to produce silane and an alkali or alkaline earth-metal halide salt, the halogenated silicon feed gas being introduced into a disproportionation system prior to contacting the halogenated feed gas with the alkali or alkaline earth metal hydride;
electrolyzing the halide salt to produce metallic alkali or alkaline earth metal and halogen gas;
contacting the metallic alkali or alkaline earth-metal with hydrogen to produce an alkali or alkaline earth metal hydride; and
contacting the alkali or alkaline earth-metal hydride produced by contacting the metallic alkali or alkaline earth metal and hydrogen with the halogenated silicon feed gas to produce silane and an alkali or alkaline earth-metal halide salt.
19. The process as set forth in claim 18 wherein the metallic alkali or alkaline earth-metal is contacted with hydrogen in a solvent selected from the group consisting of toluene, dimethyl ether, diglyme, NaAlCl 4 and mixtures thereof.
20. The process as set forth in claim 19 wherein the metallic alkali or alkaline earth-metal is added to a reaction vessel containing the solvent to form a reaction mixture and wherein hydrogen gas is bubbled through the reaction mixture.
21. The process as set forth in claim 18 wherein the alkali or alkaline earth-metal hydride is contacted with the halogenated silicon feed gas in a solvent selected from the group consisting of toluene, dimethyl ether, diglyme, NaAlCl 4 and mixtures thereof.
22. The process as set forth in claim 21 wherein the solvent contains a catalyst.
23. The process as set forth in claim 22 wherein the catalyst is selected from the group consisting of tri-ethyl aluminum, various lewis acids, trace alkali metals and mixtures thereof.
24. The process as set forth in claim 19 wherein spent solvent comprising the halide salt and the solvent is produced upon contacting the alkali or alkaline earth-metal hydride with the halogenated silicon feed gas, the method comprising regenerating the solvent by separating the halide salt and the solvent.
25. The process as set forth in claim 24 wherein the halide salt and solvent are separated by evaporating the solvent from the salt and condensing the solvent after evaporation.
26. The process as set forth in claim 18 wherein the halogenated silicon feed gas comprises one or more metal halide impurities, the method comprising cooling the halogenated silicon feed gas to precipitate the metal halide impurities.
27. The process as set forth in claim 18 wherein halide salt is electrolyzed by:
introducing the salt to a vessel containing a cathode, an anode disposed within the cathode, and a separator disposed between the cathode and anode;
applying current to the cathode and anode to produce halogen gas and metallic alkali or alkaline earth metal; and
discharging halogen gas and metallic alkali or alkaline earth metal from the vessel.
28. The process as set forth in claim 27 wherein at least one compound selected from the group consisting of calcium chloride, aluminum chloride and sodium carbonate is added to the vessel to lower the melting point of the halide salt.
29. The process as set forth in claim 18 wherein granular silicon and at least one of halogen gas and hydrogen halide are introduced into a fluidized bed reactor wherein the halogen gas or hydrogen halide fluidize the granular silicon in the reactor.
30. The process as set forth in claim 18 wherein the alkali or alkaline earth metal is selected from the group consisting of lithium, sodium, potassium, magnesium, barium, calcium and mixtures thereof.
31. The process as set forth in claim 18 wherein the alkali or alkaline earth metal is sodium.
32. The process as set forth in claim 18 wherein the alkali or alkaline earth metal halide salt comprises a halogen selected from the group consisting of fluorine, chlorine, bromine, iodine and mixtures thereof.
33. The process as set forth in claim 18 wherein the alkali or alkaline earth metal halide salt comprises chlorine.
34. A process for producing silane in a substantially closed-loop system with respect to halogens, the process comprising:
contacting a halogenated silicon feed gas comprising at least one halosilane selected from the group consisting of silicon tetrahalide, trihalosilane, dihalosilane and monohalosilane with an alkali or alkaline earth metal hydride to produce silane and an alkali or alkaline earth-metal halide salt;
electrolyzing the halide salt to produce metallic alkali or alkaline earth metal and halogen gas;
producing a halogenated silicon feed gas comprising at least one halosilane selected from the group consisting of silicon tetrahalide, trihalosilane, dihalosilane and monohalosilane by contacting the halogen gas with at least one of:
(1) silicon to produce silicon tetrahalide; and
(2) hydrogen to produce hydrogen halide, wherein the hydrogen halide is further contacted with silicon to produce a mixture comprising silicon tetrahalide and trihalosilane; and
contacting the halogenated silicon feed gas with an alkali or alkaline earth metal hydride to produce silane and an alkali or alkaline earth-metal halide salt, the halogenated silicon feed gas being introduced into a disproportionation system prior to contacting the halogenated feed gas with the alkali or alkaline earth metal hydride.
35. The process as set forth in claim 34 wherein the halogenated silicon feed gas comprises one or more metal halide impurities, the method comprising cooling the halogenated silicon feed gas to precipitate the metal halide impurities.
36. The process as set forth in claim 34 wherein halide salt is electrolyzed by:
introducing the salt to a vessel containing a cathode, an anode disposed within the cathode, and a separator disposed between the cathode and anode;
applying current to the cathode and anode to produce halogen gas and metallic alkali or alkaline earth metal; and
discharging halogen gas and metallic alkali or alkaline earth metal from the vessel.
37. The process as set forth in claim 36 wherein at least one compound selected from the group consisting of calcium chloride, aluminum chloride and sodium carbonate is added to the vessel to lower the melting point of the halide salt.
38. The process as set forth in claim 34 wherein granular silicon and at least one of halogen gas and hydrogen halide are introduced into a fluidized bed reactor wherein the halogen gas or hydrogen halide fluidize the granular silicon in the reactor.
39. The process as set forth in claim 34 wherein the alkali or alkaline earth-metal salt produced by contacting the halogenated silicon feed gas with the alkali or alkaline earth metal hydride is electrolyzed to produce metallic alkali or alkaline earth metal and halogen gas.
40. The process as set forth in claim 34 wherein the alkali or alkaline earth metal is selected from the group consisting of lithium, sodium, potassium, magnesium, barium, calcium and mixtures thereof.
41. The process as set forth in claim 34 wherein the alkali or alkaline earth metal is sodium.
42. The process as set forth in claim 34 wherein the alkali or alkaline earth metal halide salt comprises a halogen selected from the group consisting of fluorine, chlorine, bromine, iodine and mixtures thereof.
43. The process as set forth in claim 34 wherein the alkali or alkaline earth metal halide salt comprises chlorine.