Biocatalytic methods to convert cyclohexane oxidation process waste streams to useful products

Patent metadata

Field	Value
Publication number	US-9783833-B2
Application number	US-201213715826-A
Country	US
Kind code	B2
Filing date	Dec 14, 2012
Priority date	Jun 17, 2011
Publication date	Oct 10, 2017
Grant date	Oct 10, 2017

Abstract

The invention relates to methods for enriching monomer content in a cycloalkane oxidation process mixed organic waste stream. In particular, the methods involve combining a biocatalyst with a mixed organic waste stream from a cycloalkane oxidation process, and enzymatically converting dimeric and/or oligomeric components of said waste stream into monomeric components. The methods may enrich the content of diacids, adipic acid, and/or other α,ω-difunctional C6 alkanes in the mixed organic waste stream. Additionally, the treated mixed organic waste streams may have improved burning efficiency.

First claim

What is claimed:

1. A method of hydrolyzing dimeric, oligomeric, or cyclic esters in a cycloalkane oxidation process mixed organic waste stream, the method comprising
contacting one or more isolated or extracellular recombinant enzymes having hydrolase activity with a mixed organic waste stream from a cycloalkane oxidation process; wherein the contacting results in hydrolysis of at least a portion of dimeric, oligomeric or cyclic esters of said waste stream into aliphatic monomeric components; and wherein
said one or more recombinant enzymes having hydrolase activity comprises one or more hydrolases that are classified under EC 3.1.1.- and are selected from the group consisting of a lipase classified under EC 3.1.1.3, an esterase classified under EC 3.1.1.1, a cutinase classified under EC 3.1.1.74, a polyhydroxyalkanoate (PHA) depolymerase classified under EC 3.1.1.75 or EC 3.1.1.76, a lactone hydrolase classified under EC 3.1.1.25, and a gluconolactonase classified under EC 3.1.1.17.

2. The method of claim 1 , wherein said one or more hydrolases comprises one or more isolated hydrolases, immobilized hydrolases, or hydrolases present in a cell lysate.

3. The method of claim 2 , further comprising contacting the mixed organic waste stream with an esterase from horse liver and either an esterase from Mucor miehei or an esterase from Rhizopus oryzae.

4. The method of claim 1 , wherein said waste stream is acidic, and said recombinant enzyme having a hydrolase activity is a hydrolase selected to be active at a pH less than 6 or wherein said waste stream is alkaline, and said recombinant enzyme having a hydrolase activity is a hydrolase selected to be active at a pH greater than 8.

5. The method of claim 4 , wherein said hydrolase is active at a pH less than 6 and is from Kurtzmanomyces sp. I-11, Aspergillus niger, Picrophilus torridus , or Pyrobaculum calidifontis , or said hydrolase is active at a pH greater than 8 and is from Streptomyces diostotochromogenes, Acinobacter sp. RAG-1, an Alcaligenes sp., Bacillus alcalophilus, B. lichenigormis strain H1, B. subtilis 168 , B. thermoleoverans CCR11 , Pseudomonas aerugionosa, P. fluorescens; Aspergillus carneus, Penicillum nitroaeducens, Ricinus communis , or Scorpio maurus.

6. The method of claim 1 , further comprising burning the treated mixed organic waste stream for fuel value or to produce a syngas.

7. The method of claim 1 , further comprising one or more steps selected from the group consisting of
(i) esterifying one or more components of the treated mixed organic waste stream to produce mixed esters or polyols,
(ii) hydrogenating one or more components of the treated mixed organic waste stream to produce diols,
(iii) oxidizing one or more components of the treated mixed organic waste stream to produce diacids,
(iv) reductively aminating one or more components of the treated mixed organic waste stream to produce amines,
(iv) sulfonating one or more components of the treated mixed organic waste stream to produce sulfonates or sulfonic acids, and
(v) treating one or more components of the treated mixed organic waste stream with NH 4 OH or polyamines to produce amidoamines or polyamides.

8. The method of claim 1 , further comprising contacting the mixed organic waste stream with a laccase classified under EC 1.10.3.2.

9. The method of claim 1 , further comprising recovering or separating said monomeric components, diacids, adipic acids, or other α,ω-difunctional C6 alkanes from the oxidation process.

10. The method of claim 9 , comprising esterifying the diacids mixture prior to separation into C4, C5, or C6 diacids.

11. The method of claim 10 , comprising crystallizing adipic acid from the mixture.

12. A method to increase the C 4 -C 6 diacids content of a cycloalkane oxidation process mixed organic waste stream, comprising:
a. contacting said mixed organic waste stream with one or more isolated or extracellular recombinant hydrolases capable of hydrolyzing dimeric, oligomeric or cyclic esters such that at least a portion of dimeric, oligomeric or cyclic esters in said stream are hydrolyzed into linear C4-C6 aliphatic monomers, wherein said hydrolases are classified under EC 3.1.1.-; and
b. contacting the mixed organic stream with a recombinant whole cell microbial biocatalyst having at least one exogenous nucleic acid encoding a polypeptide capable of oxidising linear C4-C6 mono-acids, hydroxy-acids and oxo-acids to corresponding diacids such that at least a portion of the linear C4-C6 mono-acids, hydroxy-acids and oxo-acids in said mixed organic waste stream are oxidized to the corresponding diacids.

13. The method of claim 12 , where the hydrolysis of dimeric, oligomeric or cyclic esters into linear aliphatic monomers is performed by one or more isolated or immobilized hydrolases prior to contacting said mixed organic waste stream with the whole cell biocatalyst.

14. The method of claim 12 , wherein one or more extracellular hydrolases secreted by the whole cell biocatalyst are used to hydrolyze at least a portion of the dimeric, oligomeric or cyclic esters in said waste stream into aliphatic monomeric components.

15. The method of claim 12 , wherein said recombinant whole cell biocatalyst that converts mono-acids, hydroxy-acids and oxo-acids to diacids via the oxo-acid has an endogenous or heterologous w-oxidation pathway which catalyzes one or more of the following conversions:
a. conversion of butyric acid, valeric acid, and/or caproic acid to succinic acid, glutaric acid, and/or adipic acid;
b. conversion of butyric acid, valeric acid, and/or caproic acid to 4-hydroxybutyric acid, 5-hydroxyvaleric acid, and/or 6-hydroxycaproic acid;
c. conversion of 4-hydroxybutyric acid, 5-hydroxyvaleric acid, and/or 6-hydroxycaproic acid to 4-oxobutanoic acid, 5-oxopentanoic acid, and/or 6-oxohexanoic acid; or
d. conversion of 4-oxobutanoic acid, 5-oxopentanoic acid, and/or 6-oxohexanoic acid to succinic acid, glutaric acid, and/or adipic acid.

16. The method of claim 15 , where the co-oxidation pathway of the recombinant host cell is comprised of one or more of:
a P450 cytochrome oxidase, an ω-hydroxylase, ω-oxygenase enzyme or alkane-1-monooxygenase from the class EC 1.14.15.3;
a fatty alcohol oxidase or an alcohol dehydrogenase from the class EC 1.1.1-.

17. The method of claim 16 , wherein the recombinant host further comprises an aldehyde dehydrogenase to convert the oxo-acids to diacids.

18. The method of claim 17 , wherein a recombinant host cell that converts at least a portion of the cyclic C6 components of the waste stream into 6-hydroxycaproic acid, 6-oxohexanoic acid or adipic acid has an endogenous or heterologous cyclohexanol and/or 1,2-cyclohexanediol degradation pathway which catalyzes one or more of the following conversions:
a) cyclohexanol to 6-oxohexanoic acid
b) 1,2-cyclohexanediol to 6-oxohexanoic acid, and
c) 6-oxohexanoic acid to adipic acid.

19. The method of claim 18 , wherein the cyclohexanol degradation pathway of the recombinant host cell comprises a cyclohenol dehydrogenase (ChnA) classified under EC 1.1.1.245; a cyclohexanone monooxygenase (ChnB) classified under EC 1.14.13.22; a 6-hexanolide hydrolase (ChnC) classified under EC 3.1.1.-; a 6-hydroxyhexanoate dehydrogenase (ChnD) classified under EC 1.1.1.258, and a 6-oxohexanoate dehydrogenase (ChnE) classified under EC 1.1.1.63.

20. The method of claim 19 , wherein the cyclohexane-1,2-diol degradation pathway of the recombinant host comprises a cyclohexane-1

Assignees

• Invista North America Sarl
• Invista North America Sarl

Inventors

• Pearlman Paul S
• Chen Changlin
• Botes Adriana Leonora

Classifications

• C12P1/02

  by using fungi · CPC title

• C12Y301/01003

  Triacylglycerol lipase (3.1.1.3) · CPC title

• C12P13/001

  Amines; Imines · CPC title

• C12P17/10

  Nitrogen as only ring hetero atom · CPC title

• C12P5/02

  acyclic {(C12P5/007 takes precedence)} · CPC title