Nanosized copper catalyst precursors for the direct synthesis of trialkoxysilanes
View Patent ↗The present invention provides a process for using nanosized copper, nanosized copper oxides, nanosized copper chlorides, other nanosized copper salts, and mixtures thereof, as sources of catalytic copper in the Direct Synthesis of trialkoxysilanes of the formula HSi(OR) 3 wherein R is an alkyl group containing from 1 to 6 carbon atoms inclusive. The nanosized copper, nanosized copper oxides, nanosized copper chlorides, other nanosized copper salts, and their mixtures of this invention have average particle sizes that are in the range from about 0.1 to about 60 nanometers, preferably from about 0.1 to about 30 nanometers, and most preferably from about 0.1 to about 15 nanometers. Nanosized sources of catalytic copper afford high dispersion of catalytic sites on silicon and contribute to high reaction rates, high selectivity and high silicon conversion. The nanosized copper catalyst precursors of the invention permit the use of substantially reduced levels of copper compared to conventional practice.
1. A process for using a nanosized copper catalyst precursor selected from the group consisting of nanosized copper, nanosized copper oxides, nanosized copper chlorides, other nanosized copper salts, and mixtures thereof as sources of catalytic copper in the direct synthesis of trialkoxysilane of formula HSi(OR) 3 wherein R is an alkyl group containing from 1 to 6 carbon atoms inclusive, said process comprising:
(a) forming a reaction mixture comprising a thermally stable solvent, silicon metal, a catalytically effective amount of said nanosized copper catalyst precursor having an average particle size in a range from about 0.1 to about 60 nanometers, wherein said thermally stable solvent is selected from the group consisting of linear paraffins, branched paraffins, cycloparaffins, alkylated benzenes, aromatic ethers and polyaromatic compounds, and said thermally stable solvent has a boiling point above 250° C.;
(b) agitating and heating this mixture to form copper-activated silicon in situ and injecting into said reaction mixture methanol and/or ethanol vapor to react with said copper-activated silicon to produce said trialkoxysilane; and
(c) recovering said trialkoxysilane from the reaction product.
2. The process of claim 1 wherein the copper-activated silicon is reacted initially with methanol vapor and later with ethanol vapor.
3. The process of claim 1 wherein forming said reaction mixture includes mixing with a solvent that has been used in preparation of said nanosized copper catalyst precursor.
4. The process of claim 1 wherein forming said reaction mixture includes providing a foam control agent.
5. The process of claim 1 wherein the trialkoxysilane is trimethoxysilane or triethoxysilane and the direct synthesis of trimethoxysilane or triethoxysilane occurs with about 300 to about 5000 parts per million copper based on an amount of silicon.
6. A process for the direct synthesis of triallkoxysilanes comprising the steps of:
(a) providing a slurry of silicon metal, and a copper catalyst precursor having an average particle size of about 0.1 to 60 nanometers in a thermally stable solvent, wherein said thermally stable solvent is selected from the group consisting of linear paraffins, branched paraffins, cycloparaffins, alkylated benzenes, aromatic ethers and polyaromatic compounds, and said thermally stable solvent has a boiling point above 250° C.;
(b) forming a copper-silicon intermetallic;
(c) reacting said copper-silicon intermetallic with an alcohol of formula ROH wherein R is an alkyl group having 1 to 6 carbon atoms inclusive, to form a trialkoxysilane of the formula HSi(OR) 3 wherein R is as previously defined;
(d) recovering the trialkoxysilane via an insulated exit line without refluxing the trialkoxysilane; and
(e) remediating the thermally stable solvent for subsequent Direct Synthesis of trialkoxysilanes.
7. The process of claim 6 wherein in step (a) said slurry is formed with nanosized silicon metal.
8. The process of claim 6 wherein in step (a) said silicon metal is produced by acid leaching and said copper catalyst precursor comprises nanosized copper chloride.
9. The process of claim 6 wherein in step (a), said thermally stable solvent is a member selected from the group consisting of linear and branched paraffins, cycloparaffins, alkylated benzenes, aromatic ethers, and polyaromatic hydrocarbons.
10. The process of claim 6 wherein in step (a), an initial copper concentration is about 300 to about 5000 ppm based on an amount of said silicon metal.
11. The process of claim 6 wherein in step (a), said copper catalyst precursor is selected from the group consisting of nanosized copper, nanosized copper oxides, nanosized copper chlorides, other nanosized copper salts, and mixtures thereof.
12. The process of claim 6 wherein in step (b) said copper-silicon intermetallic is formed by heating said copper catalyst precursor in said slurry for about 0.01 to about 24 hours at a temperature of about 20 to about 400° C.
13. The process of claim 6 wherein in step (b) said copper-silicon intermetallic is formed in situ.
14. The process of claim 6 wherein in step (b) said copper-silicon intermetallic is formed in a separate reaction vessel prior to reaction with said alcohol.
15. The process of claim 6 wherein in step (c) said alcohol is introduced as a gaseous stream to react with said copper-silicon intermetallic.
16. The process of claim 6 wherein in step (c) more than one alcohol is present to react with said copper-silicon intermetallic.
17. The process of claim 6 wherein step (c) comprises reacting said copper-silicon intermetallic with ethanol at a temperature of about 200 to about 210° C.
18. A composition useful for the direct synthesis of trialkoxysilanes comprising:
silicon metal having a particle size of less than about 500 μm;
one or more copper catalyst precursors having an average particle size from about 0.1 nm to about 60 nm, 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 metal such that about 0.008 to about 4.5 parts elemental copper is present based on 100 parts by weight of said silicon metal; and
a thermally stable reaction solvent present in an amount that provides a gravimetric ratio of solids to solvent of about 1:2 to about 1:4.
19. The composition of claim 18 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.
20. A process for using a nanosized copper catalyst precursor selected from the group consisting of nanosized copper, nanosized copper oxides, nanosized copper chlorides, other nanosized copper salts, and mixtures thereof as sources of catalytic copper in the direct synthesis of trialkoxysilane of formula HSi(OR) 3 wherein R is an alkyl group containing from 1 to 6 carbon atoms inclusive, said process comprising:
(a) forming a reaction mixture comprising a thermally stable solvent, silicon metal, a catalytically effective amount of said nanosized copper catalyst precursor having an average particle size in a range from about 0.1 to about 60 nanometers;
(b) agitating and heating this mixture to form copper-activated silicon in situ and injecting into said reaction mixture an alcohol to react with said copper-activated silicon to produce said trialkoxysilane wherein alcohol introduction into the reaction mixture is delayed until thermal decomposition and dehydration of the catalyst precursor are complete; and
(c) recovering said trialkoxysilane from the reaction product.
21. The process of claim 20 wherein catalyst precursor has an average particle size in a range of from 0.1 to 50 nanometers.
22. The process of claim 20 wherein catalyst precursor has an average particle size in a range of from 0.1 to 30 nanometers.
23. The process of claim 20 wherein catalyst precursor has an average particle size in a range of from 0.1 to 20 nanometers.
24. The process of claim 20 wherein catalyst precursor has an average particle size in a range of from 0.1 to 15 nanometers.
25. The process of claim 20 wherein catalyst precursor has an average particle size in a range of from 30 to 60 nanometers.
26. The process of claim 20 wherein catalyst precursor has an average particle size in a range of from 35 to 55 nanometers.
27. The process of claim 20 wherein catalyst precursor has an average particle size in a range of from 40 to 50 nanometers.
28. A process for using a nanosized copper catalyst precursor selected from the group consisting of nanosized copper, nanosized copper oxides, nanosized copper chlorides, other nanosized copper salts, and mixtures thereof, said process comprising:
(a) forming a reaction mixture comprising a thermally stable solvent, silicon metal, a catalytically effective amount of said nanosized copper catalyst precursor having an average particle size in a range from about 0.1 to about 60 nanometers;
(b) agitating and heating this mixture to form copper-activated silicon in situ and injecting into said reaction mixture an alcohol to react with said copper-activated silicon to produce said trialkoxysilane; and
(c) recovering said trialkoxysilane from the reaction product.