Rochow-Müller direct synthesis using nanosized copper catalyst precursors
View Patent ↗A Direct Synthesis of making organohalosilanes with greater selectivity to the dialkyldihalosilane is disclosed herein. By using nanosized copper catalyst precursors, and preferably nanosized promoters as well, D/T values of greater than 10, and preferably greater than 15, are obtainable with silicon conversions in excess of 80 wt. %. Shorter induction times are realized using the nanosized copper catalysts in the Direct Synthesis. The nanosized copper catalyst precursors most preferably have an average particle size of less than 100 nanometers.
1. A method for Direct Synthesis of organohalosilanes comprising the steps of: providing a slurry of silicon, an organohalide of formula RX wherein R is a saturated or unsaturated aliphatic or aromatic hydrocarbon radical having from 1 to 10 carbon atoms, and X is a halogen, a copper catalyst precursor and one or more promoters in a thermally stable organic liquid solvent, and reacting said silicon, said organohalide and said copper catalyst precursor in said slurry for a time and at a temperature to effectuate high selectivity to diorganodihalosilanes.
2. The method of claim 1 wherein the thermally stable organic liquid solvent has a boiling point above 250° C.
3. The method of claim 1 wherein said thermally stable organic liquid solvent is selected from the group consisting of linear and branched paraffins, cycloparaffins, naphthalenes, alkylated benzenes, dialkylated benzenes, aromatic ethers and polyaromatic hydrocarbons.
4. The method of claim 2 wherein the thermally stable organic liquid solvent is provided in a sufficient amount such that a gravimetric ratio of solids to solvent is about 1:1 to about 1:4.
5. The method of claim 1 wherein the promoters are selected from the group consisting of zinc, cadmium, antimony, phosphorus, arsenic, lanthanides, alkali metal halides and tin.
6. The method of claim 4 wherein the step of providing one or more promoters comprises providing about 0.005 to about 0.50 wt % zinc, about 0.0005 to about 0.01 wt % tin, about 0.001 to about 0.20 wt % phosphorus, and about 0.0005 to about 0.05 wt % antimony based on an amount of said silicon.
7. The method of claim 1 wherein the step of reacting the silicon, organohalide and copper catalyst precursor is performed in a slurry reactor in which said silicon, said organohalide, said copper metal catalyst, and said one or more promoters are slurried in said reactor with the thermally stable organic liquid solvent.
8. The method of claim 1 wherein the silicon has a particle size distribution wherein at least 90 w % of said silicon is between about 1 to about 300 microns.
9. The method of claim 1 wherein the silicon has a particle size distribution wherein at least 90 wt % of said silicon is between about 1 to about 100 microns.
10. The method of claim 1 wherein the silicon has a particle size distribution wherein at least 90 wt % of said silicon is less than 1000 nanometers.
11. The method of claim 1 wherein R is methyl, ethyl, vinyl, allyl, or phenyl.
12. The method of claim 1 wherein organohalide of formula RX is selected from the group consisting of methyl chloride, methyl bromide, ethyl chloride, vinyl chloride, and chlorobenzene.
13. The method of claim 1 wherein the organohalide of formula RX is methyl chloride or chlorobenzene.
14. The method of claim 1 wherein the copper catalyst precursor has a surface area greater than about 5 m 2 /g and an average particle size from about 0.1 to about 500 nanometers.
15. The method of claim 1 wherein the copper catalyst precursor has a surface area greater than about 10 m 2 /g and an average particle size from about 0.1 to about 100 nanometers.
16. The method of claim 1 wherein the copper catalyst precursor has a lead concentration of less than about 0.005 wt % based on an amount of said copper catalyst precursor and less than 0.001 wt % based on an amount of said silicon.
17. The method of claim 1 wherein the step of providing a copper catalyst precursor comprises generating the copper catalyst precursor in situ during said direct synthesis.
18. The method of claim 1 wherein the copper catalyst precursor in an amount from about 0.08 to about 1 parts by weight copper catalyst precursor per 100 parts by weight silicon.
19. A method of synthesizing organohalosilanes having high selectivity to dialkyldihalosilanes comprising the steps of: providing a slurry reactor having an agitation means therein and a thermally stable organic liquid reaction solvent; providing silicon having a particle size of no greater than 500 microns with a concentration of lead of less than 0.0001 wt % based on a weight of said silicon; providing a copper catalyst precursor having an average particle size from about 0.1 to about 600 nanometers; activating said silicon with said copper catalyst precursor to form copper activated silicon; providing one or more promoters selected from the group consisting of zinc, cadmium, antimony, phosphorus, arsenic, lanthanides, alkali metal halides and tin, having an average particle size of less than 1000 nanometers; and providing an organohalide to react with the copper activated silicon in a liquid slurry including the thermally stable organic liquid solvent and thereby selectively forming a dialkyldihalosilane.
20. The method of claim 19 wherein the copper catalyst precursor is selected from the group consisting of copper, copper (I) oxide, copper (II) oxide, copper (I) chloride, copper (II) chloride, copper (I) carboxylates, copper (II) carboxylates and mixtures thereof.
21. The method of claim 19 wherein the step of activating said silicon metal with said copper catalyst precursor to form copper activated silicon is performed in situ.
22. The method of claim 19 wherein the step of activating said silicon with said copper catalyst precursor to form copper activated silicon comprises activating said silicon with said copper catalyst precursor and promoters in a dry state in a separate rotary, vibrating, fluidized bed reactor or fix bed reactor.
23. The method of claim 19 wherein said step of activating said silicon with said copper catalyst precursor occurs in the presence of a gaseous hydrogen halide or an alkylhalosilane.
24. The method of claim 19 further including the step of providing foam control agents.
25. The method of claim 19 wherein said method is conducted in a continuous or batch fashion.
26. The method of claim 19 wherein the step of providing said copper catalyst precursor comprises generating the copper catalyst precursors in situ in the reaction solvent.
27. The method of claim 19 further including providing additional silicon, copper catalyst precursors, and promoters.
28. The method of claim 19 further including the recovering, remediating and recycling the thermally stable reaction solvent.
29. A method of controlling a Direct Synthesis for making an organohalosilane comprising the steps of: providing a silicon; providing one or more copper catalyst precursors having an average particle size of less than 600 nanometers; providing one or more promoters selected from the group consisting of zinc, cadmium, antimony, phosphorus, arsenic, lanthanides, alkali metal halides, tin, and mixtures thereof, having an average particle size of less than 500 nanometers; heating said silicon, said one or more copper catalyst precursors, and said one or more promoters in a thermally stable organic liquid solvent; and forming copper activated silicon for reaction with an organohalide in a slurry including the thermally stable organic liquid solvent.
30. The method of claim 29 wherein said heating step occurs at a temperature greater than 180° C. in the presence of hydrogen chloride such that a short induction time is required prior to reaction with an organohalide.
31. The method of claim 29 wherein the one or more copper catalyst precursors are selected from the group consisting of copper, copper (I) oxide, copper (II) oxide, copper (I) chloride, copper (II) chloride, copper (I) carboxylates, copper (II) carboxylates and mixtures thereof.
32. The method of claim 29 wherein the step of heating said silicon, said one or more copper catalyst precursors, and said one or more promoters occurs as a slurry at a temperature of about 150 to about 350° C. for about 0.01 to about 24 hours.
33. A composition useful for the Direct Synthesis of organohalosilanes comprising: silicon having a particle size of less than about 500 microns; one or more copper catalyst precursors having an average particle size from about 0.1 to about 600 nanometers, a surface area as low as 0.1 m 2 /g, in an amount from about 0.01 to about 5 parts by weight per 100 parts of said silicon; one or more promoters selected from the group consisting of about 0.05 to about 0.50 wt % zinc, about 0.0005 to about 0.015 wt % tin, about 0.001 to about 0.20 wt % phosphorus and about 0.0005 to about 0.05 wt % antimony based on the amount of said silicon, the promoter having an average particle size of less than 1000 nanometers; and a thermally stable organic liquid reaction solvent present in an amount that provides a gravimetric ratio of solids to solvent of about 1:2 to about 1:4.
34. The composition of claim 33 wherein said copper catalyst precursors are selected from the group consisting of copper metal, copper (I) oxide, copper (II) oxide, copper (I) chloride, copper (II) chloride, copper (I) carboxylates, copper (II) carboxylates, other copper salts, and mixtures thereof.
35. The composition of claim 33 wherein said copper catalyst precursor is present in an amount of about 0.05 to about 2 parts by weight per 100 parts of said silicon.
36. The composition of claim 33 wherein said copper catalyst precursor is present in an amount of about 0.08 to about 1 parts by weight per 100 parts of said silicon.
37. The composition of claim 33 the promoters include zinc and tin in amount having a Zn/Sn gravimetric ratio of from about 12 to 60.
38. The method of claim 1 wherein the copper compound is selected from the group consisting of copper, copper (I) oxide, copper (II) oxide, copper (I) chloride, copper (II) chloride, copper (I) carboxylate, copper (II) carboxylate and mixtures thereof.
39. The method of claim 1 wherein the promoters are in liquid form.
40. The method of claim 1 wherein the copper catalyst precursor has an average particle size of less than 600 nanometers, the promoter has an average particle size of less than 1000 nanometers and the silicon has a particle size no larger than 500 microns.
41. The method of claim 1 wherein the copper catalyst precursor has an average particle size of from about 0.1 to about 500 nanometers, the promoter has an average particle size of less than 500 microns and the silicon has a particle size distribution wherein at least 90 wt % of the silicon has a particle size of between about 1 to about 100 microns.
42. The method of claim 1 wherein the copper catalyst precursor has an average particle size of from about 0.1 to about 100 nanometers, and the silicon has a particle size distribution wherein at least 90 wt % of the silicon has a particle size of less than 1000 nanometers.
43. The method of claim 29 wherein the promoters include zinc and tin wherein a Zn/Sn gravimetric ratio is from about 12 to about 60, a Zn/Cu gravimetric ratio is from about 0.04 to about 0.2, and the Zn/Sn gravimetric ratio is maintained during the Direct Synthesis wherein D/T selectivity for a dialkyldihalosilane is greater than 10.
44. The method of claim 33 wherein about 0.008 to about 4.5 parts of elemental copper of the copper catalyst precursor is present based upon 100 parts by weight of silicon.