Method of making organohalosilanes
View Patent ↗The invention pertains to a process for the preparation of organohalosilanes. The process comprises contacting a first finely-divided silicon comprising from 0.08 to 0.25% (w/w) of aluminum with an organohalide in a reactor at a temperature of from 250 to 350° C. in the presence of a Direct Process catalyst comprising copper, and a promotor; and introducing a second finely-divided silicon into the reactor comprising from 0.001 to <0.10% (w/w) of aluminum into the reactor as needed in an amount sufficient to maintain an aluminum concentration of from 0.08 to 0.2% (w/w), based on a weight of unreacted silicon and aluminum.
1. A method of preparing organohalosilanes, the method comprising:
(i) contacting a first finely-divided silicon comprising from 0.08 to 0.25% (w/w) of aluminum with an organohalide in a reactor at a temperature of from 250 to 350° C. in the presence of a Direct Process catalyst comprising copper, and a promotor; and
(ii) introducing a second finely-divided silicon comprising from 0.001 to<0.10% (w/w) of aluminum into the reactor as needed in an amount sufficient to maintain an aluminum concentration from 0.08 to 0.2% (w/w), based on a total weight of unreacted silicon and aluminum.
2. The method of claim 1 wherein the method produces organohalosilanes characterized by the formula R a H b SiX 4-a-b (II), wherein R is hydrocarbyl, X is halo, a has a value of 1, 2, or 3; b has the value of 0, 1, or 2; and a+b has a value of 1, 2, or 3.
3. The method of claim 2 , wherein the organohalide is characterized by the formula RX (I), wherein R is hydrocarbyl and X is halo.
4. The method of claim 3 wherein the R is alkyl.
5. The method of claim 1 , wherein the catalyst comprising copper is selected from granular copper powder, stamped copper, Cu—Zn alloy, Cu—Si alloy, Cu—Sb alloy, cuprous oxide, cupric oxide, cupric chloride, cuprous chloride, copper nitride, copper hydroxide, and copper formate.
6. The method of claim 5 wherein the catalyst is from 0.01 to 10 parts by weight copper per 100 parts by weight of the first finely-divided silicon.
7. The method of claim 1 wherein the first and second finely-divided silicon have a maximum particle size diameter up to 200 μm and a particle size mass distribution characterized by a 10 th percentile of 1 to 6 μm, a 50 th percentile from 5 to 25 μm, and a 90 th percentile of 25 to 60 μm.
8. The method of claim 1 , wherein the promotor is selected from phosphorous, phosphorous compounds, zinc, zinc compounds, tin, tin compounds, antimony, antimony compounds, arsenic, arsenic compounds, cesium, cesium compounds, aluminum and aluminum compounds.
9. The method of claim 1 , wherein the reactor is a fluidized bed reactor.
10. The method of claim 9 , wherein the second finely-divided silicon is introduced into the fluidized bed reactor continuously.
11. The method of claim 9 , wherein the bed of the fluidized bed reactor is fluidized with the organohalide or a mixture of the organohalide and an inert gas.
12. The method of claim 1 , wherein the contacting of the first finely-divided silicon comprising from 0.08 to 0.25% (w/w) of aluminum with the organohalide in the reactor is at a temperature of from 280 to 340°C.
13. The method of claim 2 , wherein the second finely-divided silicon is introduced until the organohalosilanes are produced with a selectivity above 0.20 or a silicon conversion below 65%.
14. The method of claim 1 , further comprising: (iii) introducing additional first finely-divided silicon before, during or after step (ii).
15. The method of claim 1 , wherein the second finely-divided silicon is introduced until selectivity is above 0.35, where selectivity means weight ratio of organotrihalosilane to diorganodihalosilane produced.
16. The method of claim 1 , wherein the second finely-divided silicon is introduced until selectivity is above 0.10 and the silicon conversion is below 80%, where selectivity means weight ratio of organotrihalosilane to diorganodihalosilane produced, and where silicon conversion is total weight of silicon reacted divided by cumulative weight of silicon fed to the reactor multiplied by 100.