Renewable acrylic acid production and products made therefrom

Patent metadata

Field	Value
Publication number	US-9850192-B2
Application number	US-201314406491-A
Country	US
Kind code	B2
Filing date	Jun 7, 2013
Priority date	Jun 8, 2012
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

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.

First claim

What is claimed is:

1. A process for production of a biobased acrylic acid product, comprising:
a) combining a genetically engineered host biomass comprising poly-3-hydroxypropionate, a heat transfer fluid having a boiling temperature, and optionally a catalyst to obtain a biomass mixture; 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 , 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 98%.

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

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 genetically engineered 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 genetically engineered 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, Pseudomonads ), Pseudomonas, Ralstonia, Klebsiella ), 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 genetically engineered 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.

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

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

14. The process of claim 13 , wherein the weight percent of catalyst is in the range of about 4% to about 50%.

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

16. The process of claim 1 , wherein the heating temperature is from about 200° C. to about 350° C.

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

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

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

20. The process of claim 1 , wherein the genetically engineered host 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.

21. 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.

22. 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.

23. The process of claim 1 , wherein the yield of 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.

24. A process for production of a biobased butyl acrylic acid ester product, comprising
a) combining a genetically engineered host biomass comprising poly-3-hydroxypropionate, n-butanol and a catalyst to produce a biomass mixture;
b) heating the biomass mixture 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%.

25. The process of claim 24 , 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.

26. The process of claim 24 , wherein the n-butanol has 0% biobased content or 100% biobased content.

27. The process of claim 24 , wherein the biomass mixture is not pyrolyzed.

Assignees

• Metabolix Inc
• Cj Cheiljedang Corp

Inventors

• Harris Stephen
• Sparks Kevin A
• Peoples Oliver P
• Shabtai Yossef
• Mcchalicher Christopher W J
• Van Walsem Johan
• Mirley Christopher
• Schweitzer Dirk

Classifications

• C12N15/52

  Genes encoding for enzymes or proenzymes · CPC title

• C12P7/40

  containing a carboxyl group {including Peroxycarboxylic acids} · CPC title

• C07C51/09

  from carboxylic acid esters or lactones · CPC title

• C12P7/62

  Carboxylic acid esters · CPC title

• A61L15/60 Primary

  Liquid-swellable gel-forming materials, e.g. super-absorbents · CPC title