Renewable Acrylic Acid Production and Products Made Therefrom

• US 20150183708A1
• Filed: 06/07/2013
• Published: 07/02/2015
• Est. Priority Date: 06/08/2012
• Status: Active Grant

• Current Assignee: CJ Cheiljedang Corporation (CJ Group)
• Original Assignee: Metabolix Incorporated
• Inventors: Harris, Stephen, Sparks, Kevin A., Peoples, Oliver P., Shabtai, Yossef, McChalicher, Christopher W.J., van Walsem, Johan, Mirley, Christopher, Schweitzer, Dirk
• Granted Patent: US 9,850,192 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: A61L 15/60 Liquid-swellable gel-forming materials, e.g. super-absorbents
• CPC Class Codes: C07C 51/09 from carboxylic acid esters or lactones
• CPC Class Codes: C07C 51/377 by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups C07C51/36 - C07C51/373 take precedence
• CPC Class Codes: C07C 57/04 Acrylic acid; Methacrylic acid
• CPC Class Codes: C07C 67/03 by reacting an ester group with a hydroxy group
• CPC Class Codes: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 69/54 Acrylic acid esters; Methacrylic acid esters
• CPC Class Codes: C07C 69/73 of unsaturated acids
• CPC Class Codes: C08F 22/1006 of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
• CPC Class Codes: C08G 63/06 derived from hydroxycarboxylic acids
• CPC Class Codes: C12N 15/52 Genes encoding for enzymes or proenzymes
• CPC Class Codes: C12P 7/40 containing a carboxyl group including Peroxycarboxylic acids
• CPC Class Codes: C12P 7/42 Hydroxy-carboxylic acids
• CPC Class Codes: C12P 7/62 Carboxylic acid esters
• CPC Class Codes: C12P 7/625 Polyesters of hydroxy carboxylic acids
• CPC Class Codes: Y02E 50/30 Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

Processes and methods for making biobased acrylic acid products including acrylic acid, acrylic acid oligomers, acrylic acid esters, acrylic acid polymers and articles from renewable carbon resources are described herein.

Claims

1. A process for production of a biobased acrylic acid product, comprising:

a) combining a genetically engineered biomass comprising poly-3-hydroxypropionate, a heat transfer fluid having a boiling temperature to obtain a biomass mixture, and, optionally, a catalyst; and

b) heating the biomass mixture at a heating temperature to convert the poly-3-hydroxypropionate to an acrylic acid product;

wherein a yield of the acrylic acid product is at least 80% and the biobased carbon content of the acrylic acid product is at least 90%.

2. The process of claim 1,

wherein the yield of the acrylic acid product is at least 85% and the biobased carbon content of the acrylic acid product is at least 95%.

3. The process of claim 1,

the biobased carbon content of the acrylic acid product is at least 98%.

4. The process of claim 1, wherein the process further includes an initial step of culturing a recombinant host with a renewable feedstock to produce a poly-3-hydroxypropionate biomass.

5. The process of claim 4, wherein a source of the renewable feedstock is selected from glucose, fructose, sucrose, arabinose, maltose, lactose, xylose, ethanol, methanol, glycerol, fatty acids, vegetable oils, and biomass derived synthesis gas or a combination thereof.

6. The process of claim 1, wherein the biomass host is a bacteria, yeast, fungi, algae, cyanobacteria, or a mixture of any two or more thereof.

7. The process of claim 6, wherein the biomass host is bacteria.

8. The process of claim 7, wherein the bacteria is selected from Escherichia coli, Alcaligenes eutrophus (renamed as Ralstonia eutropha), Bacillus spp., Alcaligenes latus, Azotobacter, Aeromonas, Comamonas, Pseudomonas), Pseudomonas, Ralstonia, Synechococcus sp PCC7002, Synechococcus sp. PCC 7942, Synechocystis sp. PCC 6803, Thermosynechococcus elongatus BP-I, Chlorobium tepidum, Chloroflexusauranticus, Chromatium tepidum and Chromatium vinosum Rhodospirillum rubrum, Rhodobacter capsulatus, and Rhodopseudomonas palustris.

9. The process of claim 6, wherein the recombinant host is algae.

10. The process of claim 1, wherein the heating temperature is from 100°

C. to 350°

C.

11. The process of claim 1, wherein the boiling temperature of the heat transfer fluid is above the heating temperature.

13. The process of claim 11, further including the step of recovering the heat transfer fluid from the biomass mixture.

17. The process of claim 1, wherein the catalyst is sodium hydrogen sulfate or sulfuric acid or phosphoric acid.

18. The process of claim 17, wherein the weight percent of catalyst is in the range of about 4% to about 50%.

19. The process of claim 1, wherein heating reduces the water content of the biomass to about 5 wt %, or less.

20. The process of claim 1, wherein the heating temperature is from about 200°

C. to about 350°

C.

22. The process of claim 1, wherein the heating is for a time period from about 30 seconds to about 5 minutes or from about 5 minutes to about 2 hours.

24. The process of claim 1, further comprising recovering the acrylic acid product.

25. The process of claim 1, wherein the acrylic acid product comprises less than 5% by weight of side products.

33. The process of claim 1, wherein the genetically engineered biomass is from a recombinant host having a poly-3-hydroxypropionate pathway, wherein the host has stably incorporated one or more genes encoding one or more enzymes selected from vicinal diol dehydratase, aldehyde dehydrogenase, 1,3-propanediol oxidoreductase, glycerol-3-phosphate dehydrogenase and glycerol-3-phosphatase.

34. The process of claim 1, wherein the weight % of the catalyst is in the range of about 4% to about 50%, and the heating is at about 250°

C.

35. The process of claim 1, wherein the catalyst is about 4% by weight calcium hydroxide and the heating is at a temperature of 250°

C.

45. The process of claim 1, wherein the acrylic acid product is about 85% by weight or greater based on one gram of an acrylic acid in the acrylic acid product per gram of poly-3-hydroxypropionate.

12. (canceled)

14-16. -16. (canceled)

21. (canceled)

23. (canceled)

26. (canceled)

27. (canceled)

28. A process for production of a biobased butyl acrylic acid ester product, comprising

a) combining a genetically engineered biomass comprising poly-3-hydroxypropionate, n-butanol and a catalyst;

b) heating the biomass with the n-butanol and catalyst to reflux for 15-24 hours; and

c) converting the poly-3-hydroxypropionate to a butyl acrylic acid ester product;

wherein a yield of the acrylic acid ester product is at least 80% and the biobased carbon content of the acrylic acid product is at least 40%.

29. The process of claim 28, wherein the catalyst is sulfuric acid, hydrochloric acid, phosphoric acid, trifluoroacetic anhydride, p-toluene sulphonic acid, methane sulfonic acid, silica, titanium dioxide, alumina, a clay, zinc oxide, zinc chloride, iron chloride or dibutyl tin laurate.

30. The process of claim 28, wherein the n-butanol has 0% biobased content or 100% biobased content.

31. The process of claim 28, wherein the biomass is not pyrolyzed.

32. (canceled)

36-42. -42. (canceled)

43. A poly-3-hydroxypropionate biomass produced from renewable resources which is suitable as a feedstock for producing acrylic acid product, wherein the level of poly-3-hydroxypropionate in the biomass is greater than 50% by weight of the biomass.

44. (canceled)

46-63. -63. (canceled)