Methods and systems for generating polyols

• US 7,767,867 B2
• Filed: 05/07/2007
• Issued: 08/03/2010
• Est. Priority Date: 05/08/2006
• Status: Active Grant

• Current Assignee: Virent, Inc. (Marathon Petroleum Corporation)
• Original Assignee: Virent Energy Systems, Inc. (Marathon Petroleum Corporation)
• Inventors: Cortright, Randy D.
• Primary Examiner(s): Price; Elvis O
• Application Number:
  US11/800,671
• Publication Number:
  US 20080025903A1
• Time in Patent Office: 1,184 Days
• Field of Search: 423/437.1, 252/183.13, 562/400, 568/400, 568/420, 568/700, 568/840, 568/852, 568/861
• US Class Current: 568/861
• CPC Class Codes: B01J 23/8906 Iron and noble metals
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/06 Integration with other chemical processes
• CPC Class Codes: C01B 2203/1047 Group VIII metal catalysts
• CPC Class Codes: C01B 2203/1052 Nickel or cobalt catalysts
• CPC Class Codes: C01B 2203/1058 Nickel catalysts
• CPC Class Codes: C01B 2203/1064 Platinum group metal catalysts
• CPC Class Codes: C01B 2203/107 Platinum catalysts
• CPC Class Codes: C01B 2203/1076 Copper or zinc-based catalysts
• CPC Class Codes: C01B 2203/1211 Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 2203/1217 Alcohols
• CPC Class Codes: C01B 3/323 Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
• CPC Class Codes: C07C 27/06 by hydrogenation of oxides of carbon
• CPC Class Codes: C07C 29/60 by elimination of -OH groups, e.g. by dehydration C07C29/34 takes precedence
• CPC Class Codes: C07C 31/205 1,3-Propanediol; 1,2-Propanediol
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

Disclosed are methods for generating propylene glycol, ethylene glycol and other polyols, diols, ketones, aldehydes, carboxylic acids and alcohols from biomass using hydrogen produced from the biomass. The methods involve reacting a portion of an aqueous stream of a biomass feedstock solution over a catalyst under aqueous phase reforming conditions to produce hydrogen, and then reacting the hydrogen and the aqueous feedstock solution over a catalyst to produce propylene glycol, ethylene glycal and the other polyols, diols, ketones, aldehydes, carboxylic acids and alcohols. The disclosed methods can be run at lower temperatures and pressures, and allows for the production of oxygenated hydrocarbons without the need for hydrogen from an external source.

Claims

1. A method of generating an oxygenated compound, the method comprising the steps of:

a) contacting a first catalytic material comprising one or more Group VIII metals with a first portion of an aqueous feedstock solution comprising water and at least one water-soluble oxygenated hydrocarbon having two or more carbon atoms, at;

i. a temperature of about 80°

C. to 400°

C.;

ii. a weight hourly space velocity of at least about 1.0 gram of the oxygenated hydrocarbon per gram of the first catalytic material per hour; and

iii. a pressure where at least a portion of the water and the oxygenated hydrocarbons are condensed liquids, to produce an aqueous phase reforming (APR) stream that comprises hydrogen and at least one of carbon dioxide and carbon monoxide; and

b) reacting the APR stream with a second portion of the feedstock solution over a second catalytic material, the second catalytic material different than the first catalytic material and selected from the group consisting of;

iron, ruthenium, copper, rhenium, cobalt, nickel, alloys thereof, and mixtures thereof, at;

i. a temperature of about 100°

C. to 300°

C.; and

ii. a pressure of about 200 psig to about 1200 psig, to produce a reaction product comprising one or more oxygenated compounds selected from the group consisting of a polyol, a ketone, an aldehyde, a carboxylic acid and an alcohol.

2. The method of claim 1, wherein the second portion of the feedstock solution further comprises oxygenated hydrocarbons formed by contacting the feedstock solution with the first catalytic material.

3. The method of claim 1, wherein the second portion of the feedstock solution is contacted with the APR stream and the second catalytic material at a pressure greater than about 365 psig.

4. The method of claim 1, wherein the molar ratio of the first catalytic material to the second catalytic material is about 5:

1 to 1;

5.

5. The method of claim 1, wherein the first catalytic material comprises at least one transition metal selected from the group consisting of platinum, nickel, palladium, ruthenium, rhodium, rhenium, iridium, alloys thereof, and mixtures thereof.

6. The method of claim 5, wherein the second catalytic material is selected from the group consisting of iron, nickel, rhenium, ruthenium, and cobalt.

7. The method of claim 6, wherein the molar ratio of the first catalytic material to the second catalytic material is about 5:

1 to 1;

5.

8. The method of claim 1, wherein the first catalytic material and the second catalytic material are combined in a catalytic mixture.

9. The method of claim 8, wherein the first catalytic material comprises at least one transition metal selected from the group consisting of:

platinum, nickel, palladium, ruthenium, rhodium, rhenium, iridium, alloys thereof and mixtures thereof; and

the second catalytic metal is iron or rhenium.

10. The method of claim 8, wherein the molar ratio of the first catalytic material to the second catalytic material is about 5:

1 to 1;

5.

11. The method of claim 8, wherein the first portion of the feedstock solution and the second portion of the feedstock solution are contacted with the first catalytic material and the second catalytic material in a reactor vessel at a temperature of about 200°

C. to 270°

C.

12. The method of claim 8, wherein the catalytic mixture is adhered to an activated carbon support and comprises 5 wt % of the first and second catalytic materials.

13. The method of claim 12, wherein the first catalytic material is platinum and the second catalytic material is iron.

14. The method of claim 1, wherein the first catalytic material is adhered to a support.

15. The method of claim 14, wherein the support is an activated carbon.

16. The method of claim 1, wherein the second portion of the feedstock solution is contacted with the second catalytic material at a weight hourly space velocity of about 1.0 grams to 5.0 grams of oxygenated hydrocarbon per gram of the second catalytic material per hour.

17. The method of claim 1, wherein the second portion of the feedstock solution is contacted with the second catalytic material at a temperature of about 120°

C. to 300°

C. and the first portion of the feedstock solution is contacted with the first catalytic material at a temperature of about 200°

C. to 270°

C.

18. The method of claim 1, wherein the second portion of the feedstock solution is reacted with the APR stream and an external hydrogen, wherein the molar ratio of the hydrogen in the APR stream to external hydrogen is at least 3:

1.

19. The method of claim 1, wherein the feedstock solution comprises at least 20 wt % glycerol.

20. The method of claim 19, wherein the first catalytic material and the second catalytic material are combined in a catalytic mixture, and the feedstock solution is contacted with the catalytic mixture at a pressure of about 72 psig to 1300 psig and a weight hourly space velocity of about 1.0 to 5.0 grams of glycerol per gram of the catalytic mixture per hour, and wherein the reaction product includes propylene glycol.

21. The method of claim 1, wherein the reaction product has a carbon yield of propylene glycol of 40% or greater.

22. The method of claim 1, wherein the reaction product comprises carbon dioxide, propylene glycol and one or more of the following products:

a second diol, a carboxylic acid, an aldehyde, a carboxylic acid and an alcohol.

25. The method of claim 14, wherein the support is selected from the group consisting of carbon, silica, silica-alumina, alumina, zirconia, titania, ceria, vanadia, and mixtures thereof.

26. The method of claim 25, wherein the support comprises zirconia.

27. The method of claim 8, wherein the first catalytic material is platinum and the second catalytic material is rhenium.

23. A method of generating propylene glycol comprising the step of contacting a heterogeneous catalyst comprising platinum and iron with an aqueous feedstock solution comprising water and glycerol, at:

a) a temperature of about 100°

C. to 300°

C.;

b) a weight hourly space velocity of at least about 1.0 gram of glycerol per gram of the heterogeneous catalyst per hour; and

c) a pressure where the water and the glycerol remain condensed liquids to produce a reaction product comprising propylene glycol.

24. The method of claim 23, wherein

a) the heterogeneous catalyst consists essentially of about 5 wt % iron and platinum in a molar ratio of about 1:

1 on an activated carbon support;

b) the feedstock comprises at least about 20 wt % glycerol;

c) the feedstock is contacted with the heterogeneous catalyst at a weight hourly space velocity of about 1.0 to 5.0 grams of glycerol per gram of the heterogeneous catalyst per hour and a pressure of about 250-600 psig;

or

d) the reaction product has a carbon yield of propylene glycol of 40% or greater.

28. A method of generating propylene glycol comprising the step of contacting a heterogeneous catalyst comprising platinum, ruthenium and a Group IVA metal with an aqueous feedstock solution comprising water and glycerol, at:

a) a temperature of about 100°

C. to 300°

C.;

b) a weight hourly space velocity of at least about 1.0 gram of glycerol per gram of the heterogeneous catalyst per hour; and

c) a pressure where the water and the glycerol remain condensed liquids to produce a reaction product comprising propylene glycol.