Process for gamma-butyrolactone production

1. A process for production of a biobased gamma-butyrolactone product, comprising

a) combining a genetically engineered biomass comprising poly-4-hydroxybutyrate and a catalyst; and

b) heating the biomass with the catalyst to convert the poly 4-hydroxybutyrate to a gamma-butyrolactone product, wherein the catalyst is sodium carbonate or calcium hydroxide.

2. The process of claim 1 , wherein the genetically engineered biomass is from a recombinant host having a poly-4-hydroxybutyrate pathway, wherein the host has an inhibiting mutation in its CoA-independent NAD-dependent succinic semialdehyde dehydrogenase gene or its CoA-independent NADP-dependent succinic semialdehyde dehydrogenase gene, or having the inhibiting mutations in both genes, and having stably incorporated one or more genes encoding one or more enzymes selected from a succinyl-CoA:coenzyme A transferase wherein the succinyl-CoA:coenzyme A transferase is able to convert succinate to succinyl-CoA, a succinate semialdehyde dehydrogenase wherein the succinate semialdehyde dehydrogenase is able to convert succinyl-CoA to succinic semialdehyde, a succinic semialdehyde reductase wherein the succinic semialdehyde reductase is able to convert succinic semialdehyde to 4-hydroxybutyrate, a CoA transferase wherein the CoA transferase is able to convert 4-hydroxybutyrate to 4-hydroxybutyryl-CoA, and a polyhydroxyalkanoate synthase wherein the polyhydroxyalkanoate synthase is able to polymerize 4-hydroxybutyryl-CoA to poly-4-hydroxybutyrate.

3. The process of claim 1 wherein the genetically engineered biomass is from a recombinant host having stably incorporated one or more genes encoding one or more enzymes selected from: a phosphoenolpyruvate carboxylase wherein the phosphoenolpyruvate carboxylase is able to convert phosphoenolpyruvate to oxaloacetate, an isocitrate lyase wherein the isocitrate lyase is able to convert isocitrate to glyoxalate, a malate synthase wherein the malate synthase is able to convert glyoxalate to malate and succinate, a succinate-CoA ligase (ADP-forming) wherein the succinate-CoA ligase (ADP-forming) is able to convert succinate to succinyl-CoA, an NADP-dependent glyceraldeyde-3-phosphate dehydrogenase wherein the NADP-dependent glyceraldeyde-3-phosphate dehydrogenase is able to convert glyceraldehyde 3-phosphate to 1,3-bisphosphoglycerate forming NADPH+H + , an NAD-dependent glyceraldeyde-3-phosphate dehydrogenase wherein the NAD-dependent glyceraldeyde-3-phosphate dehydrogenase is able to convert glyceraldehyde 3-phosphate to 1,3-bisphosphoglycerate forming NADH+H + , a butyrate kinase wherein the butyrate kinase is able to convert 4-hydroxybutyrate to 4-hydroxybutyryl-phosphate, a phosphotransbutyrylase wherein the phosphotransbutyrylase is able to convert 4-hydroxybutyryl-phosphate to 4-hydroxybutyryl-CoA; and optionally having a disruption in one or more genes selected from yneI, gabD, pykF, pykA, maeA and maeB.

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-4-hydroxybutyrate biomass.

5. The process of claim 4 , wherein a source of the renewable feedstock is selected from glucose, fructose, sucrose, arabinose, maltose, lactose, xylose, 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, Pseudomonads ), 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 heating is at a temperature of from about 100° C. to about 350° C.

11. The process of claim 1 , wherein the weight percent of catalyst is in the range of about 4% to about 50%.

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

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

14. The process of claim 13 , wherein the heating temperature is from about 225° C. to about 300° C.

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

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

17. The process of claim 1 , further comprising recovering the gamma-butyrolactone product.

18. The process of claim 1 , wherein the gamma-butyrolactone product comprises less than 5% by weight of side products.

19. The process of claim 1 , wherein the gamma-butyrolactone is further processed to form one or more of the following: 1,4-butanediol (BDO), tetrahydrofuran (THF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), 2-pyrrolidinone, N-vinylpyrrolidone (NVP) and polyvinylpyrrolidone (PVP).

20. The process of claim 1 , wherein the genetically engineered biomass is from a recombinant host having a poly-4-hydroxybutyrate pathway, wherein the host has optionally an inhibiting mutation in its CoA-independent NAD-dependent succinic semialdehyde dehydrogenase gene or its CoA-independent NADP-dependent succinic semialdehyde dehydrogenase gene, or having inhibiting mutations in both genes, and having stably incorporated genes encoding the following enzymes: a succinyl-CoA:coenzyme A transferase wherein the succinyl-CoA:coenzyme A transferase is able to convert succinate to succinyl-CoA, a succinate semialdehyde dehydrogenase wherein the succinate semialdehyde dehydrogenase is able to convert succinyl-CoA to succinic semialdehyde, a succinic semialdehyde reductase wherein the succinic semialdehyde reductase is able to convert succinic semialdehyde to 4-hydroxybutyrate, a CoA transferase wherein the CoA transferase is able to convert 4-hydroxybutyrate to 4-hydroxybutyryl-CoA, and a polyhydroxyalkanoate synthase wherein the polyhydroxyalkanoate synthase is able to polymerize 4-hydroxybutyryl-CoA to poly-4-hydroxybutyrate.

21. The process of claim 1 , wherein the genetically engineered biomass is from a recombinant host having stably incorporated genes encoding the following enzymes: a phosphoenolpyruvate carboxylase wherein the phosphoenolpyruvate carboxylase is able to convert phosphoenolpyruvate to oxaloacetate, an isocitrate lyase wherein the isocitrate lyase is able to convert isocitrate to glyoxalate, a malate synthase wherein the malate synthase is able to convert glyoxalate to malate and succinate, a succinate-CoA ligase (ADP-forming) wherein the succinate-CoA ligase (ADP-forming) is able to convert succinate to succinyl-CoA, an NADP-dependent glyceraldeyde-3-phosphate dehydrogenase wherein the NADP-dependent glyceraldeyde-3-phosphate dehydrogenase is able to convert glyceraldehyde 3-phosphate to 1,3-bisphosphoglycerate forming NADPH+H + , an NAD-dependent glyceraldeyde-3-phosphate dehydrogenase wherein the NAD-dependent glyceraldeyde-3-phosphate dehydrogenase is able to convert glyceraldehyde 3-phosphate to 1,3-bisphosphoglycerate forming NADH+H + , a butyrate kinase wherein the butyrate kinase is able to convert 4-hydroxybutyrate to 4-hydroxybutyryl-phosphate, a phosphotransbutyrylase wherein the phosphotransbutyrylase is able to convert 4-hydroxybutyryl-phosphate to 4-hydroxybutyryl-CoA; and optionally having a disruption in one or more genes selected from yneI, gabD, pykF, pykA, maeA and maeB.

22. The process of claim 1 , wherein the genetically engineered biomass is from a recombinant host having a poly-4-hydroxybutyrate pathway, wherein the host has stably incorporated one or more genes encoding one or more enzymes selected from a succinyl-CoA:coenzyme A transferase wherein the succinyl-CoA:coenzyme A transferase is able to convert succinate to succinyl-CoA, a succinate semialdehyde dehydrogenase wherein the succinate semialdehyde dehydrogenase is able to convert succinyl-CoA to succinic semialdehyde, a succinic semialdehyde reductase wherein the succinic semialdehyde reductase is able to convert succinic semialdehyde to 4-hydroxybutyrate, a CoA transferase wherein the CoA transferase is able to convert 4-hydroxybutyrate to 4-hydroxybutyryl-CoA, and a polyhydroxyalkanoate synthase wherein the polyhydroxyalkanoate synthase is able to polymerize 4-hydroxybutyryl-CoA to poly-4-hydroxybutyrate.

23. The process of claim 1 , wherein the genetically engineered biomass is from a recombinant host having stably incorporated one or more genes encoding one or more enzymes selected from: a phosphoenolpyruvate carboxylase wherein the phosphoenolpyruvate carboxylase is able to convert phosphoenolpyruvate to oxaloacetate, an isocitrate lyase wherein the isocitrate lyase is able to convert isocitrate to glyoxalate, a malate synthase wherein the malate synthase is able to convert glyoxalate to malate and succinate, a succinate-CoA ligase (ADP-forming) wherein the succinate-CoA ligase (ADP-forming) is able to convert succinate to succinyl-CoA, an NADP-dependent glyceraldeyde-3-phosphate dehydrogenase wherein the NADP-dependent glyceraldeyde-3-phosphate dehydrogenase is able to convert glyceraldehyde 3-phosphate to 1,3-bisphosphoglycerate forming NADPH+H + , an NAD-dependent glyceraldeyde-3-phosphate dehydrogenase wherein the NAD-dependent glyceraldeyde-3-phosphate dehydrogenase is able to convert glyceraldehyde 3-phosphate to 1,3-bisphosphoglycerate forming NADH+H + , a butyrate kinase wherein the butyrate kinase is able to convert 4-hydroxybutyrate to 4-hydroxybutyryl-phosphate, a phosphotransbutyrylase wherein the phosphotransbutyrylase is able to convert 4-hydroxybutyryl-phosphate to 4-hydroxybutyryl-CoA; and optionally having a disruption in one or more genes selected from yneI, gabD, pykF, pykA, maeA and maeB.

24. 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 300° C.

25. The process of claim 1 , wherein the catalyst is about 4% by weight calcium hydroxide and the heating is at a temperature of 300° C.

26. A biobased gamma-butyrolactone product produced by the process of claim 1 .

27. The product of claim 26 , wherein the gamma-butyrolactone product comprises less than 5% by weight of side products.

28. A poly-4-hydroxybutyrate biomass produced from renewable resources which is suitable as a feedstock for producing gamma-butyrolactone product, wherein the level of poly-4-hydroxybutyrate in the biomass is greater than 50% by weight of the biomass.

29. The biobased gamma-butyrolactone product of claim 26 , wherein the gamma-butyrolactone in the product has 100% biobased carbon content.

30. The process of claim 1 , wherein product is about 85% by weight or greater based on one gram of a gamma-butyrolactone in the product per gram of poly-4-hydroxybutyrate.