Process for producing a monomer component from a genetically modified polyhydroxyalkanoate biomass

1. A method of producing a lower alkyl acrylate from a poly-3-hydroxybutyrate biomass obtained from genetically modified organisms, comprising:

(A) producing biobased crotonic acid from the poly-3-hydroxybutyrate biomass by:

(1) heating the poly-3-hydroxybutyrate biomass in the presence of a pyrolysis catalyst under suitable pyrolysis conditions to produce the crotonic acid from the poly-3-hydroxybutyrate biomass, wherein the heating is performed for no more than 5 minutes at a temperature from 230° C. to about 350° C. or at a temperature greater than 500° C. for no more than 20 seconds and wherein the crotonic acid yield is at least about 70% based on one gram of crotonic acid per gram of poly-3-hydroxybutyrate; and

(2) recovering the crotonic acid, thereby producing the biobased crotonic acid

and

(B) producing the lower alkyl acrylate from the biobased crotonic acid by:

(1) reacting the biobased crotonic acid with a lower alkyl alcohol under suitable conditions to form a lower alkyl crotonate ester, and isolating the lower alkyl crotonate ester;

(2) reacting ethylene with 2-butene in the presence of a second metathesis catalyst under suitable conditions to produce propylene, and isolating propylene;

(3) reacting the lower alkyl crotonate ester via cross-metathesis with a sufficient amount of propylene in the presence of a first metathesis catalyst under suitable conditions to form the lower alkyl acrylate and the 2-butene, and isolating the lower alkyl acrylate; and

(4) recovering 2-butene, thereby producing recovered 2-butene, and feeding the recovered 2-butene as a starting material in reaction (B)(2),

wherein the lower alkyl is a C2-C4 alkyl.

2. The method of claim 1 , further comprising drying the poly-3-hydroxybutyrate biomass prior to heating to produce a dried poly-3-hydroxybutyrate biomass.

3. The method of claim 1 , wherein the poly-3-hydroxybutyrate biomass is from a recombinant host selected from a plant crop, bacteria, a yeast, a fungus, an algae, a cyanobacteria, or a mixture of any two or more thereof.

4. The method of claim 3 , wherein the host is bacteria.

5. The method of claim 4 , 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, Chromatium vinosum, Rhodospirillumrubrum, Rhodobacter capsulatus , and Rhodopseudomonas palustris.

6. The method of claim 3 , wherein the host is a plant crop.

7. The method of claim 6 , wherein the plant crop is selected from tobacco, sugarcane, corn, switchgrass, miscanthus sorghum, sweet sorghum, or a mixture of any two or more thereof.

8. The method of claim 2 , wherein the drying is at a temperature of 100° C. to 175° C.

9. The method of claim 2 , wherein the dried poly-3-hydroxybutyrate biomass has a water content of 5 wt %, or less.

10. The method of claim 1 , wherein the duration of heating is for about 1 minute to no more than 5 minutes.

11. The method of claim 1 , wherein the duration of heating is from 1 minute to 2 minutes.

12. The method of claim 1 , wherein the pyrolysis catalyst is a metal catalyst or an organic catalyst.

13. The method of claim 1 , wherein the first metathesis catalyst is not exposed to ethylene.

14. The method of claim 1 , wherein the first metathesis catalyst is a Hoveyda-Grubb's cross metathesis catalyst.

15. The method of claim 14 , wherein the first metathesis catalyst is 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium.

16. The method of claim 1 , wherein the lower alkyl is butyl.

17. The method of claim 1 , wherein the poly-3-hydroxybutyrate biomass comprises a co-polymer of 3-hydroxybutyrate.

18. The method of claim 1 , wherein the heating is pyrolysis, torrefaction or flash pyrolysis.

19. The method of claim 1 , wherein the biomass is from a recombinant algae selected from Chlorella minutissima, Chlorella emersonii, Chlorella sorokiniana, Chlorella ellipsoidea, Chlorella sp., or Chlorella protothecoides.

20. The method of claim 1 , wherein the poly-3-hydroxybutrate biomass has an increased amount of poly-3-hydroxybutyrate production compared to that of wild-type organism.

21. The method of claim 1 wherein the heating is performed at a temperature of 230° C. to about 245° C. for no more than 5 minutes.