Process scheme for catalytic production of renewable hydrogen from oxygenate feedstocks

Patent metadata

Field	Value
Publication number	US-9452931-B2
Application number	US-201314076321-A
Country	US
Kind code	B2
Filing date	Nov 11, 2013
Priority date	Nov 15, 2012
Publication date	Sep 27, 2016
Grant date	Sep 27, 2016

Abstract

A process is described for flowing an oxygenate feed over a catalyst in an adiabatic fixed bed reactor to product a reactor effluent and heat. The reaction inside the adiabatic fixed bed reactor occurs at a reaction temperature from about 200° C. to about 375° C. The reactor effluent is then condensed to separate the liquid products and the gaseous products. A separation step then separates the gaseous products into hydrogen and off-gas.

First claim

The invention claimed is:

1. A process comprising:
flowing an oxygenate feed over an adiabatic fixed bed reactor, at a reaction temperature from about 200° C. to about 375° C., to produce a reactor effluent and heat;
condensing the reactor effluent to separate the liquid products and the gaseous products; and
separating the gaseous products into hydrogen and off-gas;
wherein the adiabatic fixed bed reactor comprises a metal catalyst comprising x % Ni, y % Cu, z % Fe, xx % K, yy % MgO, zz % CeO 2 and: XXX % Al 2 O 3 wherein x ranges from 0 to 30 wt %, y ranges from 0 to 20 wt %; z ranges from 0 to 20 wt %; xx ranges from 0 to 20 wt %; yy ranges from 0 to 20 wt %; zz ranges from 0 to 20 wt %; and xxx ranges from 20 to 90 wt %.

2. The process of claim 1 , wherein hydrogen is produced from an oxygenate feed absent the use of a steam methane reformer.

3. The process of claim 1 , wherein the reaction temperature ranges from about 275° C. to about 325° C.

4. The process of claim 1 , wherein the heat is used to maintain the reaction temperature inside the adiabatic fixed bed reactor.

5. The process of claim 1 , wherein the liquid products are flowed back to be mixed into the oxygenate feed.

6. The process of claim 1 , wherein the off-gas is used to generate heat to maintain the reaction temperature inside the adiabatic fixed bed reactor.

7. The process of claim 1 , wherein the off-gas is reacted in a conventional steam methane reformer.

8. The process of claim 1 , wherein a pressure swing absorber, membrane separator, or liquid solvent system is used to separate the liquid products and the gaseous products.

9. The process of claim 1 , wherein the liquid products are flashed to produce a fuel gas steam.

10. The process of claim 9 , wherein the fuel gas stream is combusted and used in a heat exchanger.

11. The process of claim 9 , wherein the fuel gas stream is combusted and used in the adiabatic fixed bed reactor.

12. A process comprising:
mixing organic oxygenates with water to produce an oxygenate feed;
flowing the oxygenate feed over an adiabatic fixed bed reactor containing a metal catalyst, at a reaction temperature from about 275° C. to about 325° C., to produce reactor effluent and heat;
using the heat from the reaction to maintain the reaction temperature inside the adiabatic fixed bed reactor;
condensing the reactor effluent to separate the liquid products and the gaseous products;
flowing the liquid products back to be mixed into the oxygenate feed; and
separating the gaseous products into hydrogen and off-gas;
wherein the adiabatic fixed bed reactor comprises a metal catalyst comprising x % Ni, y % Cu, z % Fe, xx % K, yy % MgO, zz % CeO 2 and: XXX % Al 2 O 3 wherein x ranges from 0 to 30 wt %, y ranges from 0 to 20 wt %; z ranges from 0 to 20 wt %; xx ranges from 0 to 20 wt %; yy ranges from 0 to 20 wt %; zz ranges from 0 to 20 wt %; and xxx ranges from 20 to 90 wt %.

13. The process of claim 12 , wherein the off-gas is used to generate heat to maintain the reaction temperature inside the adiabatic fixed bed reactor.

14. The process of claim 12 , wherein the off-gas is reacted in a conventional steam methane reformer.

15. A process comprising:
mixing organic oxygenates with water to produce an oxygenate feed;
flowing the oxygenate feed over an adiabatic fixed bed reactor containing a metal catalyst, at a temperature from about 275° C. to about 325° C., to produce reactor effluent and heat;
using the heat from the reaction to maintain the reaction temperature of the adiabatic fixed bed reactor;
condensing the reactor effluent to separate the liquid products and the gaseous products;
flashing the liquid products to produce a fuel gas stream;
utilizing the fuel gas steam to assist in the maintenance of the reaction temperature inside the adiabatic fixed bed reactor;
separating the gaseous products into hydrogen and off-gas; and
reacting a portion of the off-gas in a conventional steam methane reformer to produce more hydrogen and using a portion of the off-gas to generate heat to assist in the maintenance the reaction temperature inside the adiabatic fixed bed reactor;
wherein the adiabatic fixed bed reactor comprises a metal catalyst comprising x % Ni, y % Cu, z % Fe, xx % K, yy % MgO, zz % CeO 2 and: XXX % Al 2 O 3 wherein x ranges from 0 to 30 wt %, y ranges from 0 to 20 wt %; z ranges from 0 to 20 wt %; xx ranges from 0 to 20 wt %; yy ranges from 0 to 20 wt %; zz ranges from 0 to 20 wt %; and xxx ranges from 20 to 90 wt %.

Assignees

• Phillips 66 Co

Inventors

• Paul Uchenna P
• Randolph Bruce B
• Nelson Jon M
• Fjare Kristi A
• Smith Danielle K
• Cragun Mark Rumel
• Sadok Richard D

Classifications

• C01B2203/043

  Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration · CPC title

• C01B2203/0233

  the reforming step being a steam reforming step · CPC title

• C01B2203/1217

  Alcohols · CPC title

• C01B3/323 Primary

  Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents · CPC title

• C01B2203/1082

  Composition of support materials · CPC title