Direct synthesis of calcium borohydride
View Patent ↗A method is disclosed for directly preparing an alkaline earth metal borohydride, i.e. Ca(BH 4 ) 2 , from the alkaline earth metal hydride and the alkaline earth metal boride. The borohydride thus prepared is doped with a small portion of a metal chloride catalyst compound, such as RuCl 3 , TiCl 3 , or a mixture of TiCl 3 and palladium metal. The process provides for mechanically mixing the dry reagents under an inert atmosphere followed by charging the mixed materials with high pressure hydrogen at about 70 MPa while heating the mixture to about 400° C. The method is relatively simple and inexpensive and provides reversible hydride compounds which are free of the usual contamination introduced by prior art wet chemical methods.
1. A method of producing a complex borohydride compound capable of reversible hydrogenation, comprising:
mechanically mixing an alkaline earth metal hydride with an alkaline earth metal boride powder and a powder of metal chloride catalyst compound in order to provide a compound mixture, wherein the metal chloride catalyst comprises about 4 to about 8 weight percent of the combined weight of the alkaline earth metal hydride and the alkaline earth metal boride; and
hydrogenating the compounded mixture at an elevated temperature and pressure to provide an alkaline earth metal borohydride compound.
2. The method according to claim 1 , further comprising the step of compacting the compounded powder mixture prior to the step of hydrogenating the compounded powder mixture.
3. The method according to claim 2 , wherein the molar ratio of the alkaline earth metal hydride and an alkaline earth metal boride is at least 2:1.
4. The method according to claim 3 , wherein the alkaline earth metal hydride is selected from the group of hydrides consisting essentially of CaH 2 .
5. The method according to claim 3 , wherein the alkaline earth metal boride is selected from the group of borides consisting essentially of CaB 6 .
6. The method according to claim 3 , wherein said metal chloride catalyst compound is selected from the group of compounds consisting essentially of TiCl 3 , a mixture of palladium and TiCl 3 , and RuCl 3 .
7. The method according to claim 1 , wherein said step of mechanically mixing comprises a process selected from the group consisting of ball milling, plate or impact grinding, and blending, stirring, or agitating with or without a mechanical aid.
8. The method according to claim 7 , wherein said step of mechanically mixing comprises ball milling the alkaline earth metal hydride, the alkaline earth metal boride, and the metal chloride catalyst for about 30 minutes.
9. The method according to claim 8 , wherein said step of mechanically mixing is carried out in an atmosphere consisting essentially of high purity argon gas.
10. The method according to claim 8 , wherein said step of mechanically mixing is carried out at about room temperature.
11. The method according to claim 1 , wherein said step of hydrogenation is performed at a temperature of above about 400° C., and wherein said hydrogen pressure is maintained at about a pressure of 70 MPa.
12. The method according to claim 1 , wherein the hydrogen pressure is maintained for at least about 2 hours.