Noble metal promoted supported indium oxide catalyst for the hydrogenation of CO
Supported catalyst for use in a process for the synthesis of methanol, characterized in that the supported catalyst comprises indium oxide in the form of In 2 O 3 and at least one noble metal being palladium, Pd, wherein both indium oxide and at least one noble metal are deposited on a support remarkable in that the supported catalyst is a calcined supported catalyst comprising from 0.01 to 10.0 wt. % of palladium and zirconium dioxide (ZrO 2 ) in an amount of at least 50 wt. % on the total weight of said supported catalyst.
1. Supported catalyst for use in a process for the synthesis of methanol, characterized in that the supported catalyst comprises indium oxide in the form of In 2 O 3 and at least one noble metal being palladium, Pd, wherein both indium oxide and at least one noble metal are deposited on a support characterized in that the supported catalyst is a calcined supported catalyst comprising:
from 0.01 to 10.0 wt. % of palladium and
zirconium dioxide (ZrO 2 ) in an amount of at least 50 wt. %
on the total weight of said supported catalyst;
wherein the average particle size of the noble metal phase is less than 5 nm as determined by STEM-EDX or the average crystal size of In 2 O 3 is less than 20 nm, as determined by XRD.
2. The supported catalyst according to claim 1 , characterized in that the supported catalyst comprises from 0.5 wt. % to 2.0 wt. %. of palladium based on the total weight of said supported catalyst.
3. The supported catalyst according to claim 1 , characterized in that the support comprises zirconium dioxide (ZrO 2 ) in an amount of at least 80 wt. %, based on the total weight of said supported catalyst.
4. The supported catalyst according to claim 1 , characterized in that the support comprises zirconium dioxide (ZrO 2 ) in an amount of at least 90 wt. % based on the total weight of said supported catalyst.
5. The supported catalyst according to claim 1 , characterized in that the supported catalyst is a calcined supported catalyst and in that the indium oxide content in the form of In 2 O 3 ranges from 1 to 20% by weight based on the total weight of said supported catalyst.
6. The supported catalyst according to claim 1 , characterized in that the supported catalyst is a calcined supported catalyst and in that the indium oxide content in the form of In 2 O 3 ranges from 5 to 15% by weight based on the total weight of said supported catalyst.
7. The supported catalyst according to claim 1 , characterized in that the supported catalyst is a calcined supported catalyst.
8. The supported catalyst according to claim 1 , characterized in that the supported catalyst is a calcined supported catalyst and has a surface area in the range of about 30 m 2 g −1 to about 200 m 2 g −1 , as determined according to N 2 sorption analysis according to ASTM D3663-03.
9. A method to prepare a supported catalyst according claim 1 characterized in that the supported catalyst is prepared by impregnation or by deposition precipitation.
10. A method according to claim 9 , characterized in that the supported catalyst is a calcined supported catalyst, and in that the method comprises a step of calcination of the supported catalyst performed at a temperature of at least 473 K (199.85° C.).
11. The method according to claim 9 , characterized in that the supported catalyst is a calcined supported catalyst, and in that the method comprises a step of calcination of the supported catalyst performed at a temperature of at least 573 K (299.85° C.).
12. Process for methanol synthesis comprising:
providing a feed stream comprising hydrogen and carbon oxides selected from carbon dioxide or a mixture of carbon dioxide and carbon monoxide, wherein carbon dioxide represents from 1 to 50 mol % of the total molar content of the feed stream, carbon monoxide is contained from 0 to 85 mol % of the total molar content, and H 2 is comprised from 5 to 99 mol % of the total molar content of the feed stream;
providing a catalyst according to claim 1 ;
putting in contact said feed stream with said catalyst at a reaction temperature of at least 373 K (99.85° C.) and under a pressure of at least 0.5 MPa; and
recovering the methanol from the effluents by a separation process;
wherein the feed stream is put in contact with the supported catalyst at a weight hourly space velocity ranging from 1,000 to 60,000 cm3 STP g cal h −1 .
13. Process according to claim 12 , characterized in that:
the reaction temperature is at least 463 K (189.85° C.).
14. Process according to claim 12 , characterized in that the feed stream is put in contact with the supported catalyst at a weight hourly space velocity ranging from 10,000 to 60,00cm 3 STP g cal h −1 .
15. Process according to claim 12 , characterized in that the feed stream is put in contact with the supported catalyst at a weight hourly space velocity ranging from 24,000 to 48,000 cm 3 STP g cal h −1 .
16. Process according to claim 12 , characterized in that the molar ratio of hydrogen to carbon dioxide in the feed stream is at least 1:1.
17. Process according to claim 12 , characterized in that the molar ratio of hydrogen to carbon dioxide in the feed stream is at least 3:1.
18. Process according to claim 12 , characterized in that prior to reaction the supported catalyst is activated in situ by raising the temperature to at least 553 K (279.85° C.) in a flow of a gas feed stream for activation selected from inert gases, hydrogen, carbon monoxide, carbon dioxide or mixture thereof.