Conversion of solid biomass into a liquid hydrocarbon materials

Patent metadata

Field	Value
Publication number	US-10167429-B2
Application number	US-201515319194-A
Country	US
Kind code	B2
Filing date	Jun 29, 2015
Priority date	Jul 1, 2014
Publication date	Jan 1, 2019
Grant date	Jan 1, 2019

Abstract

The present invention provides a process for producing liquid hydrocarbon products from a solid biomass feedstock, said process comprising the steps of:
a) providing in a first hydropyrolysis reactor vessel a first hydropyrolysis catalyst composition; b) contacting the solid biomass feedstock with said first hydropyrolysis catalyst composition and molecular hydrogen in said first hydropyrolysis reactor vessel to produce a product stream comprising partially deoxygenated hydropyrolysis product, H 2 O, H 2 , CO 2 , CO, C 1 -C 3 gases, char and catalyst fines; c) removing said char and catalyst fines from said product stream; d) hydroconverting said partially deoxygenated hydropyrolysis product in a hydroconversion reactor vessel in the presence of one or more hydroconversion catalyst and of the H 2 O, CO 2 , CO, H 2 , and C 1 -C 3 gas generated in step a), to produce a vapor phase product comprising substantially fully deoxygenated hydrocarbon product, H 2 O, CO, CO 2 , and C 1 -C 3 gases.

First claim

That which is claimed is:

1. A process for producing liquid hydrocarbon products from a solid biomass feedstock comprising:
a) providing, in a hydropyrolysis reactor vessel, a hydropyrolysis catalyst composition that comprises one or more active metals selected from cobalt, molybdenum, nickel, tungsten, ruthenium, platinum, palladium, iridium and iron on an oxide support, wherein the one or more active metals are present in an oxidic state, and wherein the term ‘oxidic state’ means that 95% or more of the one or more active metals are present in an oxidation state greater than zero as oxides;
b) contacting the solid biomass feedstock with the hydropyrolysis catalyst composition and molecular hydrogen in the hydropyrolysis reactor vessel at a temperature in the range of from 350 to 600° C. and a pressure in the range of from 0.50 to 7.50 MPa, to produce a product stream comprising partially deoxygenated hydropyrolysis product, H 2 O, H 2 , CO 2 , CO, C 1 -C 3 gases, char and catalyst fines;
c) removing the char and catalyst fines from the product stream;
d) hydroconverting the partially deoxygenated hydropyrolysis product in a hydroconversion reactor vessel in the presence of one or more hydroconversion catalyst and of the H 2 O, CO 2 , CO, H 2 , and C 1 -C 3 gas generated in step a), to produce a vapour phase product comprising substantially fully deoxygenated hydrocarbon product, H 2 O, CO, CO 2 , hydrogen and C 1 -C 3 gases.

2. The process according to claim 1 , wherein the one or more active metals are selected from one or more of cobalt, molybdenum, nickel, tungsten, and iron.

3. The process according to claim 1 , wherein the hydroconversion catalyst is selected from sulfided catalysts comprising one or more metals from the group consisting of nickel, cobalt, molybdenum or tungsten supported on a metal oxide.

4. The process according to claim 1 , wherein the hydroconversion catalyst comprises one or more active metals selected from cobalt, molybdenum, nickel, tungsten, ruthenium, palladium, platinum, iridium and iron on an oxide support, wherein the one or more active metals is present in an oxidic state.

5. The process according to claim 1 , wherein the solid biomass feedstock contains any combination of solid feedstocks containing waste plastics, feedstocks containing lignocellulose and municipal solid waste containing lignocellulosic material, waste plastics or food waste.

6. The process according to claim 5 , wherein the solid biomass feedstock comprises material selected from one or more of woody biomass and agricultural and forestry products and residues and municipal solid wastes containing lignocellulosic material.

7. The process according to claim 1 , further comprising condensing the vapour phase product of step d) to provide a liquid phase product comprising substantially fully deoxygenated C4+ hydrocarbon liquid and aqueous material and separating the liquid phase product from a gas phase product comprising H 2 , CO, CO 2 , and C 1 -C 3 gases.

8. The process according to claim 7 , wherein the gas phase product comprising H 2 , CO, CO 2 , and C 1 -C 3 gases are subjected to a reforming and water-gas shift process in order to produce hydrogen.

9. The process according to claim 8 , wherein the gas phase product is first purified to remove any H 2 S, organic sulfur compounds and NH 3 present before being subjected to the reforming and water-gas shift process.

10. The process according to claim 8 , wherein the hydrogen produced in the reforming and water-gas shift process is used as at least a portion of the molecular hydrogen in at least one of steps a) and c).

11. A process for producing liquid hydrocarbon products from a solid biomass feedstock comprising:
a) providing a hydropyrolysis catalyst composition that comprises one or more active metals selected from cobalt, molybdenum, nickel, tungsten, ruthenium, platinum, palladium, iridium and iron on an oxide support, wherein 95% or more of the one or more active metals are present in an oxidation state greater than zero as oxides;
b) contacting the solid biomass feedstock with the hydropyrolysis catalyst composition and molecular hydrogen in a hydropyrolysis reactor vessel at a temperature in the range of from 350 to 600° C. and a pressure in the range of from 0.50 to 7.50 MPa, to produce a product stream comprising partially deoxygenated hydropyrolysis product, H 2 O, H 2 , CO 2 , CO, C 1 -C 3 gases, char and catalyst fines;
c) removing the char and catalyst fines from the product stream;
d) hydroconverting the partially deoxygenated hydropyrolysis product in a hydroconversion reactor vessel in the presence of one or more hydroconversion catalyst and the H 2 O, CO 2 , CO, H 2 , and C 1 -C 3 gas generated in step a), to produce a vapour phase product comprising substantially fully deoxygenated hydrocarbon product, H 2 O, CO, CO 2 , hydrogen and C 1 -C 3 gases.

12. The process according to claim 11 , wherein the partially deoxygenated hydropyrolysis product is material in which at least 50 wt % of the oxygen present in the solid biomass feedstock has been removed.

13. The process according to claim 11 , wherein the partially deoxygenated hydropyrolysis product is material in which at least 70 wt % of the oxygen present in the solid biomass feedstock has been removed.

14. The process according to claim 11 , wherein the substantially deoxygenated hydropyrolysis product is material in which at least 95 wt % of the oxygen present in the solid biomass feedstock has been removed.

15. The process according to claim 11 , wherein the substantially deoxygenated hydropyrolysis product contains less than 2 wt % oxygen.

16. The process according to claim 11 , wherein the substantially deoxygenated hydropyrolysis product contains less than 1 wt % oxygen.

17. The process according to claim 11 , further comprising condensing the vapour phase product of step d) to provide a liquid phase product comprising substantially fully deoxygenated C4+ hydrocarbon liquid and aqueous material and separating the liquid phase product from a gas phase product comprising H 2 , CO, CO 2 , and C 1 -C 3 gases.

18. The process according to claim 17 , wherein the gas phase product comprising H 2 , CO, CO 2 , and C 1 -C 3 gases are subjected to a reforming and water-gas shift process in order to produce hydrogen.

19. The process according to claim 18 , wherein the gas phase product is first purified to remove any H 2 S, organic sulfur compounds and NH 3 present before being subjected to the reforming and water-gas shift process.

20. The process according to claim 18 , wherein the hydrogen produced in the reforming and water-gas shift process is used as at least a portion of the molecular hydrogen in at least one of steps a) and c).

Assignees

• Shell Oil Co

Inventors

• Urade Vikrant Nanasaheb
• Chilkoor Soundararajan Laxmi Narasimhan
• Panchagnula Madhusudhan Rao
• Del Paggio Alan Anthony

Classifications

• C10K3/04

  reducing the carbon monoxide content {, e.g. water-gas shift [WGS]} · CPC title

• C10G3/47

  containing platinum group metals or compounds thereof · CPC title

• C10G1/086

  Characterised by the catalyst used · CPC title

• C10G2300/202

  Heteroatoms content, i.e. S, N, O, P · CPC title

• C10G1/10

  from rubber or rubber waste · CPC title