Methods and systems for supplying hydrogen to a hydrocatalytic reaction

Patent metadata

Field	Value
Publication number	US-10106746-B2
Application number	US-201715832805-A
Country	US
Kind code	B2
Filing date	Dec 6, 2017
Priority date	Dec 8, 2016
Publication date	Oct 23, 2018
Grant date	Oct 23, 2018

Abstract

Systems and methods involving hydrocatalytic reactions that use molecular hydrogen obtained from a biogas generated from at least a portion of the hydrocatalytic reaction product. Hydrocatalytic reactions can require significant quantities of molecular hydrogen, particularly if the molecular hydrogen is being introduced under dynamic flow conditions. The present disclosure provides systems and methods that can allow for reducing the carbon footprint of the fuels formed from the hydrocatalytic reaction because at least a portion of the hydrogen used in the hydrocatalytic reaction has low carbon footprint. A fuel with low carbon footprint can qualify for certain governmental status that provides certain benefits.

First claim

The invention claimed is:

1. A method comprising:
(a) providing cellulosic biomass solids, molecular hydrogen, a slurry catalyst capable of activating molecular hydrogen, and a digestion solvent to a hydrothermal digestion unit in a hydrocatalytic reaction zone, wherein the slurry catalyst comprises at least one of Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, Os, and any alloys thereof;
(b) heating the cellulosic biomass solids, molecular hydrogen, a catalyst capable of activating molecular hydrogen, and digestion solvent to a temperature in a range of 110 degrees to 300 degrees C. and under a pressure in a range of 30 to 450 bar to produce a reaction product comprising an alcoholic component that comprises at least one of a monohydric alcohol, a glycol, and a triol;
(c) providing at least a portion of the reaction product to a separation zone to recover a top fraction comprising the alcoholic component and a bottom fraction comprising compounds having a normal boiling point of greater than 350 degrees C.;
(d) providing at least a portion of the top fraction to a further processing zone to produce a higher molecular weight compound comprising >C 4 hydrocarbons, wherein said further processing zone comprises a condensation reaction;
(e) providing at least a portion of the bottom fraction to a biogas generation zone to produce a biogas comprising methane, wherein said biogas generation zone comprises anaerobic digestion of the bottom fraction;
(f) providing at least a portion of the biogas from step (e) to a hydrogen generation zone to convert at least a portion of said biogas to molecular hydrogen; and
(g) providing at least a portion of the molecular hydrogen from the hydrogen generation zone to said hydrothermal digestion unit in the hydrocatalytic reaction zone.

2. The method of claim 1 wherein the slurry catalyst comprises a poison-tolerant catalyst.

3. The method of claim 1 further comprising generating or receiving a renewable fuel credit for said higher molecular weight compound.

4. The method of claim 3 , wherein the renewable fuel credit is a RIN or a Low Carbon Fuel Standard credit.

5. The method of claim 1 wherein the digestion solvent comprises water.

6. The method of claim 1 , wherein the digestion solvent comprises an organic solvent.

7. The method of claim 1 wherein the condensation reaction takes place at a temperature in a range of 275 degrees C. and 450 degrees C.

8. The method of claim 1 wherein step (e) further comprises: providing waste organic material in addition to the bottom fraction as feed to the biogas generation zone.

9. The method of claim 1 wherein the hydrogen generation zone comprises autothermal reforming (ATR).

10. The method of claim 1 wherein the hydrogen generation zone comprises steam methane reforming (SMR).

11. The method of claim 9 wherein the hydrogen generation zone further comprises a water gas shift reaction.

12. The method of claim 10 wherein the hydrogen generation zone further comprises a water gas shift reaction.

13. A system comprising:
(a) a hydrothermal digestion unit in a hydrocatalytic reaction zone, said hydrothermal digestion unit comprising cellulosic biomass solids, molecular hydrogen, a slurry catalyst capable of activating molecular hydrogen, and a digestion solvent to, wherein the slurry catalyst comprises at least one of Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, Os, and any alloys thereof, wherein said hydrothermal digestion unit is configured to produce a reaction product comprising an alcoholic component that comprises at least one of a monohydric alcohol, a glycol, and a triol when the cellulosic biomass solids, molecular hydrogen, a catalyst capable of activating molecular hydrogen, and digestion solvent are heated to a temperature in a range of 110 degrees to 300 degrees C. and under a pressure in a range of 30 to 450 bar;
(b) a separation zone that is in fluid communication with the hydrocatalytic zone to receive at least a portion of the reaction product, wherein the separation zone is configured to recover a top fraction comprising the alcoholic component and a bottom fraction comprising compounds having a normal boiling point of greater than 350 degrees C.;
(d) a further processing zone in fluid communication with the separation zone to receive at least a portion of the top fraction, wherein the further processing zone is configured to produce a higher molecular weight compound comprising >C 4 hydrocarbons, and wherein said further processing zone comprises a condensation reaction;
(e) a biogas generation zone in fluid communication with the separation zone to receive at least a portion of the bottom fraction, wherein the biogas generation zone is configured to produce a biogas comprising methane, wherein said biogas generation zone comprises anaerobic digestion of the bottom fraction; and
(f) a hydrogen generation zone in fluid communication with the biogas generation zone to receive at least a portion of the biogas, wherein the hydrogen generation zone is configured to convert at least a portion of said biogas to molecular hydrogen; and wherein the hydrogen generation zone is in fluid communication with the hydrocatalytic reaction zone to provide at least a portion of said molecular hydrogen to said hydrothermal digestion unit.

Assignees

• Shell Oil Co

Inventors

• Boon Andries Quirin Maria
• Powell Joseph Broun

Classifications

• C01B2203/0244

  the reforming step being an autothermal reforming step, e.g. secondary reforming processes · CPC title

• C10G3/46

  in combination with chromium, molybdenum, tungsten metals or compounds thereof · CPC title

• C10G3/49

  containing crystalline aluminosilicates, e.g. molecular sieves · CPC title

• C12M43/00

  Combinations of bioreactors or fermenters with other apparatus · CPC title

• C01B2203/0233

  the reforming step being a steam reforming step · CPC title