Method of extending biomass conversion catalyst life

Patent metadata

Field	Value
Publication number	US-9822048-B2
Application number	US-201615378099-A
Country	US
Kind code	B2
Filing date	Dec 14, 2016
Priority date	Dec 14, 2015
Publication date	Nov 21, 2017
Grant date	Nov 21, 2017

Abstract

A method of extending the catalyst life of a hydrogenolysis catalyst activity in the presence of biomass and aqueous solution is described. Lignocellulosic biomass solids and aqueous solution is provided to in a hydrothermal digestion unit in the presence of a digestive solvent, and a supported hydrogenolysis catalyst containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into a solid metal oxide support. The lignocellulosic biomass solids in the hydrothermal digestion unit is heated to a temperature in the range of 180° C. to less than 300° C. in the presence of digestive solvent, hydrogen, and in the range of 0.15 wt. % to 12.5 wt. %, based on catalyst, of H 2 S or H 2 S source at least partially soluble in aqueous solution, and the supported hydrogenolysis catalyst forming a product solution containing plurality of oxygenated hydrocarbons, the hydrothermal digestion unit maintaining protective sulfur concentration.

First claim

We claim:

1. A method of extending the catalyst life of a hydrogenolysis catalyst activity in the presence of biomass and aqueous solution comprising: (i) providing lignocellulosic biomass solids and aqueous solution in a hydrothermal digestion unit in the presence of a digestive solvent, and a supported hydrogenolysis catalyst containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into a solid metal oxide support; (ii) heating the lignocellulosic biomass solids in the hydrothermal digestion unit to a temperature in the range of 180° C. to less than 300° C. in the presence of digestive solvent, hydrogen, and in the range of 0.15 wt. % to 12.5 wt. %, based on catalyst, of H 2 S or H 2 S source at least partially soluble in aqueous solution, and the supported hydrogenolysis catalyst thereby forming a product solution containing plurality of oxygenated hydrocarbons, said hydrothermal digestion unit maintaining protective sulfur concentration.

2. The method of claim 1 wherein the residence time of the hydrothermal digestion unit (Vol/Feed) is in the range of 0.5 to 20 h.

3. The method of claim 1 wherein the H 2 S source comprises at least one of SO 2 , dimethylsulfoxide, cysteine, dimethylsulfide, dimethyldisulfide, N-butylmercaptan, tertiarybutyl polysulfide, sodium sulfide, sodium thiosulfate, and di-tert-butyl polysulfide.

4. The method of claim 1 wherein H 2 S and/or a gaseous H 2 S source is added to H 2 stream inlet.

5. The method of claim 4 wherein H 2 S and/or SO 2 is added to H 2 stream inlet.

6. The method of claim 1 wherein at least a portion of the product solution is recycled to the hydrothermal digestion unit via a liquid recycle stream.

7. The method of claim 1 wherein at least one of dimethyl sulfoxide, dimethyl sulfide, dimethyldisulfide, n-butylmercaptan, teriarybutylpolysulfide, cysteine is added to the liquid recycle stream.

8. The method of claim 1 wherein further monitoring the H 2 S level in the gas phase in the hydrothermal digestion unit and adjusting the addition of H 2 S or H 2 S source to maintain H 2 S partial pressure or protective sulfur concentration in the hydrothermal digestion unit.

9. The method of claim 1 wherein H 2 S source is DMSO.

10. The method of claim 1 wherein H 2 S source is cysteine.

11. The method of claim 1 wherein H 2 S or H 2 S source or protective sulfur is recycled to the hydrothermal digestion unit.

12. The method of claim 1 wherein H 2 S or H 2 S source is present in the range of 0.15 to 10 wt. % based on catalyst.

13. The method of claim 12 wherein H 2 S or H 2 S source is present in the range of 0.15 to 5 wt. %, based on catalyst.

14. The method of claim 2 wherein H 2 S or H 2 S source or protective sulfur is recycled to the hydrothermal digestion unit.

15. The method of claim 8 wherein H 2 S or H 2 S source or protective sulfur is recycled to the hydrothermal digestion unit.

16. The method of claim 15 wherein at least a portion of the product solution is recycled to the hydrothermal digestion unit via a liquid recycle stream.

17. The method of claim 8 wherein H 2 S and/or a gaseous H 2 S source is added to H 2 stream inlet.

18. The method of claim 17 wherein H 2 S and/or SO 2 is added to H 2 stream inlet.

Assignees

• Shell Oil Co

Inventors

• Boon Andries Quirin Maria
• Powell Joseph Broun

Classifications

• B01J37/20 Primary

  Sulfiding · CPC title

• C10G1/065

  in the presence of a solvent · CPC title

• B01J23/882

  and cobalt · CPC title

• B01J23/755

  Nickel · CPC title

• C10G3/00

  Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids (production from non-melting solid oxygen-containing carbonaceous materials C10G1/00) · CPC title