# US 10,501,761 B2 · Processing biomass to obtain hydroxylcarboxylic acids

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- Number: US 10,501,761 B2
- Document ID: US10501761B2
- Status: Granted
- Kind: B2
- Application number: 14/786,388
- Filed: 2014-04-25
- Published: 2016-03-17
- Granted: 2019-12-10
- Earliest claimed: 2013-04-26
- Assignees: Xyleco, Inc.
- Applicants: Xyleco, Inc.
- Inventors: Marshall Medoff; Thomas Craig Masterman; Andrew Papoulis; Jaewoong Moon; Jihan Khan; Robert Paradis
- Web page: https://patentgrep.com/patent/US10501761B2

## CPC

- C12P 7/56: Lactic acid
- B01J 19/24: Stationary reactors without moving elements inside (B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02)
- C07C 67/28: by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C08G 63/06: derived from hydroxycarboxylic acids
- C08G 63/08: Lactones or lactides
- C08G 63/78: Preparation processes
- C08K 3/04: Carbon
- C08K 3/34: Silicon-containing compounds
- C08K 3/346: {Clay}
- C08K 3/36: Silica
- C08K 3/38: Boron-containing compounds
- C08K 5/06: Ethers; Acetals; Ketals; Ortho-esters
- C08K 5/11: of acyclic polycarboxylic acids
- C08L 1/02: Cellulose; Modified cellulose
- C08L 3/00: Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L 67/04: Polyesters derived from hydroxycarboxylic acids, e.g. lactones (C08L67/06 takes precedence)
- C08L 97/02: Lignocellulosic material, e.g. wood, straw or bagasse {(manufacture of articles made from lignocellulosic material by dry processes B27N)}
- C12P 7/42: Hydroxy-carboxylic acids
- C12P 7/46: Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid
- C12P 7/48: Tricarboxylic acids, e.g. citric acid
- C12P 7/625: Polyesters of hydroxy carboxylic acids
- B01J 2219/24: Stationary reactors without moving elements inside
- C08K 2003/387: {Borates}
- C12P 2201/00: Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
- C12P: FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE {(brewing of beer C12C; producing vinegar C12J; producing specific peptides or proteins C07K; producing enzymes C12N9/00; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification C12N15/00; measuring or testing processes involving enzymes or microorganisms C12Q; measuring or testing processes involving nucleic acid amplification reactions C12Q1/6844; fermentation processes to form a food composition, A21 or A23; compounds in general, see the relevant compound class, e.g. C01, C07)}
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Biomass (e.g., plant biomass, animal biomass, and municipal waste biomass) is processed to produce useful intermediates and products, such as hydroxy-carboxylic acids and hydroxy-carboxylic acid derivatives. A method includes treating a reduced recalcitrance lignocellulosic or cellulosic material with one or more enzymes and/or organisms (such as lactobacillus, Pediococcus, Rhizopus, Enterococcus) to produce an alpha, beta, gamma and/or delta hydroxycarboxylic acid (such as lactic acid, glycolic acid); and converting the alpha, beta, gamma and/or delta hydroxy-carboxylic acid to the product (such as esters, polymers, and copolymers).

## Claims

### Claim 1

A method for processing biomass comprising:
treating cellulosic or lignocellulosic material with an electron beam to provide a reduced recalcitrance lignocellulosic or cellulosic material;
treating the reduced recalcitrance lignocellulosic or cellulosic material with one or more enzymes to obtain a sugar solution comprising xylose and glucose;
fermenting the sugar solution with a thermophilic organism that selectively ferments glucose to lactic acid, while xylose is not significantly consumed, and
converting the lactic acid to a product, wherein the product is an ester or polymer.

### Claim 2 (depends on 1)

The method of claim 1, wherein converting comprises converting lactic acid to esters.

### Claim 3 (depends on 1)

The method of claim 1, further comprising purifying the one or more sugars utilizing a method selected from the group consisting of one or more of electrodialysis, distillation, centrifugation, filtration, and cation exchange chromatography.

### Claim 4 (depends on 1)

The method of claim 1, wherein converting comprises polymerizing the lactic acid to a polymer.

### Claim 5 (depends on 4)

The method of claim 4, wherein a polymerizing method is selected from the group consisting of direct condensation of the lactic acid, azeotropic dehydrative condensation of the lactic acid, and dimerizing the lactic acid to lactide followed by ring opening polymerization of the lactide.

### Claim 6 (depends on 5)

The method of claim 5, wherein the polymerization method is direct condensation and includes utilizing coupling agents and/or chain extenders to increase the molecular weight of the polymer.

### Claim 7 (depends on 6)

The method of claim 6, wherein the coupling agents and/or chain extenders are selected from the group consisting of triphosgene, carbonyl diimidazole, dicyclohexylcarbodiimide, diisocyanate, acid chlorides, acid anhydrides, epoxides, thiirane, oxazoline, orthoester, and mixtures thereof.

### Claim 8 (depends on 5)

The method of claim 5 wherein the polymerization method is azeotropic condensation.

### Claim 9 (depends on 4)

The method of claim 4, wherein catalysts and/or promoters are utilized which are selected from the group consisting of Lewis acids, Bronsted acids, H3PO4, H2SO4, methane sulfonic acid, p-toluene sulfonic acid, polymerically supported sulfonic acids, metals, Mg, Al, Ti, Zn, Sn, metal oxides, TiO2, ZnO, GeO2, ZrO2, SnO, SnO2, Sb2O3, metal halides, ZnCl2, SnCl2, SnCl4, Mn(AcO)2, Fe2(LA)3, Co(AcO)2, Ni(AcO)2, Cu(OA)2, Zn(LA)2, Y(OA)3, Al(i-PrO)3, Ti(BuO)4, TiO(acac)2, (Bu)2SnO, Sn(octoate)2, solvates of any of these, and mixtures thereof.

### Claim 10 (depends on 8)

The method of claim 8, further comprising conducting at least a portion of the polymerization at a temperature between about 100° C. and about 200° C.

### Claim 11 (depends on 8)

The method of claim 8, wherein at least a portion of the polymerization is performed under vacuum.

### Claim 12 (depends on 5)

The method of claim 5, wherein the polymerization method includes dimerizing the lactic acid to lactide followed by ring opening polymerization of the lactide.

### Claim 13 (depends on 12)

The method of claim 12, wherein the dimerization includes heating the lactic acid to between 100° C. and 200° C. under a vacuum of about 0.1 mmHg to about 100 mmHg.

### Claim 14 (depends on 12)

The method of claim 12, wherein the dimerization includes a catalyst selected from the group consisting of Sn octoate, Li carbonate, Zn diacetate dehydrate, Ti tetraisopropoxide, potassium carbonate, tin powder, and mixtures thereof.

### Claim 15 (depends on 12)

The method of claim 12, wherein a ring opening polymerization catalyst is utilized which is selected from the group of Bronsted acids, HBr, HCl, triflic acid, Lewis acids, ZnCl2, AlCl3, anions, potassium benzoate, potassium phenoxide, potassium t-butoxide, and zinc stearate, metals, Tin, zinc, aluminum, antimony, bismuth, lanthanide and other heavy metals, Tin (II) oxide and tin (II) octoate, tetraphenyl tin, tin (II) and (IV) halogenides, tin (II) acetylacetonoate, distannoxanes, Al(OiPr)3, other functionalized aluminium alkoxides, ethyl zinc, lead (II) oxide, antimony octoate, bismuth octoate, rare earth catalysts, yttrium tris(methyllactate), yttrium tris(2-N-N-dimethylamino ethoxide), samarium tris(2-N-N-dimethylamino ethoxide), yttrium tris(trimethylsilylmethyl), lanthanum tris(2,2,6,6-tetramethylheptanedionate), lanthanum tris(acetylacetonate), yttrium octoate, yttrium tris(acetylacetonate), yttrium tris(2,2,6,6-tetramethylheptanedionate), and mixtures thereof.

### Claim 16 (depends on 4)

The method of claim 4, wherein converting further includes blending the polymer with a second polymer.

### Claim 17 (depends on 16)

The method of claim 16, wherein the second polymer is selected from the group consisting of polyglycols, polyvinyl acetate, polyolefins, styrenic resins, polyacetals, poly(meth)acrylates, polycarbonate, polybutylene succinate, elastomers, polyurethanes, natural rubber, polybutadiene, neoprene, silicone, and combinations thereof.

### Claim 18 (depends on 4)

The method of claim 4, wherein a co-monomer is co-polymerized with the lactic acid.

### Claim 19 (depends on 18)

The method of claim 18, wherein the co-monomer is selected from the group consisting of elastomeric units, lactones, glycolic acid, carbonates, morpholinediones, epoxides, 1,4-benzodioxepin-2,5-(3H)-dione glycosalicylide, 1,4-benzodioxepin-2,5-(3H, 3-methyl)-dione lactosalicylide, dibenzo-1,5 dioxacin-6-12-dione disalicylide, morpholine-2,5-dione, 1,4-dioxane-2,5-dione glycolide, oxepane-2-one ε-caprolactone, 1,3-dioxane-2-one trimethylene carbonate, 2,2-dimethyltrimethylene carbonate, 1,5-dioxepane-2-one, 1,4-dioxane-2-one p-dioxanone, gamma-butyrolactone, beta-butyrolactone, beta-methyl-delta-valerolactone, 1,4-dioxane-2,3-dione ethylene oxalate, 3-[benzyloxycarbonyl methyl]-1,4-dioxane-2,5-dione, ethylene oxide, propylene oxide, 5,5′(oxepane-2-one), 2,4,7,9-tetraoxa-spiro[5,5]undecane-3,8-dione, and spiro-bis-dimethylene carbonate, and mixtures thereof.

### Claim 20 (depends on 4)

The method of claim 4, comprising combining the polymer with fillers.

### Claim 21 (depends on 20)

The method of claim 20, wherein the filler is selected from the group consisting of silicates, layered silicates, polymer and organically modified layered silicate, synthetic mica, carbon, carbon fibers, glass fibers, boric acid, talc, montmorillonite, clay, starch, corn starch, wheat starch, cellulose fibers, paper, rayon, non-woven fibers, wood flours, whiskers of potassium titanate, whiskers of aluminum borate, 4,4′-thiodiphenol, glycerol, and mixtures thereof.

### Claim 22 (depends on 20)

The method of claim 20, wherein combining further includes extrusion and/or compression molding.

### Claim 23 (depends on 4)

The method of claim 4, further comprising branching or cross linking the polymer.

### Claim 24 (depends on 23)

The method of claim 23, wherein a cross linking agent is utilized to cross link the polymer and the cross-linking agent is selected from the group consisting of 5,5′-bis(oxepane-2-one)(bis-8-caprolactone)), spiro-bis-dimethylene carbonate, peroxides, dicumyl peroxide, benzoyl peroxide, unsaturated alcohols, hydroxyethyl methacrylate, 2-butene-1,4-diol, unsaturated anhydrides, maleic anhydride, saturated epoxides, glycidyl methacrylate, and combinations thereof.

### Claim 25 (depends on 4)

The method of claim 4, further comprising processing the polymer by a method selected from injection molding, blow molding and thermoforming.

### Claim 26 (depends on 4)

The method of claim 4, further comprising combining the polymer with a dye or pigment.

### Claim 27 (depends on 4)

The method of claim 4, wherein converting further includes blending the polymer with a plasticizer.

### Claim 28 (depends on 27)

The method of claim 27, wherein the plasticizer is selected from the group consisting of triacetin, tributyl citrate, polyethylene glycol, acetic acid ester of a monoglycerides, and diethyl bishydroxymethyl malonate, and mixtures thereof.

### Claim 29 (depends on 4)

The method of claim 4, further comprising grafting a molecule to the polymer.

### Claim 30 (depends on 29)

The method of claim 29, wherein the molecule is a monomer or a polymer.

### Claim 31 (depends on 29)

The method of claim 29, further including treating the polymer with a peroxide, heating above about 120° C., irradiation, or combinations thereof.

### Claim 32 (depends on 4)

The method of claim 4, further comprising shaping, molding, carving, extruding and/or assembling the polymer into a product.

### Claim 33 (depends on 32)

The method of claim 32, wherein the product is selected from the group consisting of personal care items, tissues, towels, diapers, green packaging, compostable pots, consumer electronics, laptop casings, mobile phone casings, appliances, food packaging, disposable packaging, food containers, drink bottles, garbage bags, waste compostable bags, mulch films, controlled release matrices, controlled release containers, containers for fertilizers, containers for pesticides, containers for herbicides, containers for nutrients, containers for pharmaceuticals, containers for flavoring agents, containers for foods, shopping bags, general purpose film, high heat film, heat seal layer, surface coating, disposable tableware, plates, cups, forks, knives, spoons, sporks, bowls, automotive parts, panels, fabrics, under hood covers, carpet fibers, clothing fibers, fibers for garments, fibers for sportswear, fibers for footwear, surgical sutures, implants, scaffolding and drug delivery systems.

### Claim 34 (depends on 1)

The method of claim 1, where prior to treating the cellulosic or lignocellulosic material with the electron beam the biomass size is reduced by cutting, grinding, shearing, pulverizing, and/or chopping.

### Claim 35 (depends on 1)

The method of claim 1, wherein after treating the cellulosic or lignocellulosic material with the electron beam, and before saccharification, the biomass is heat treated at a temperature of 95° C. to 160° C.

### Claim 36 (depends on 35)

The method of claim 35, wherein the biomass is heat treated at a temperature of 100° C. to 150° C.

### Claim 37 (depends on 35)

The method of claim 35, wherein the biomass is heat treated at a temperature of 110° C. to 140° C.

### Claim 38 (depends on 35)

The method of claim 35, where the heat treated biomass step comprises an aqueous mixture with the biomass 10 to 90 wt. % of the entire mixture.

### Claim 39 (depends on 1)

The method of claim 1 where converting comprises chemically converting.

### Claim 40 (depends on 39)

The method of claim 39, wherein converting comprises converting lactic acid to esters by treating with an alcohol and an acid catalyst.

### Claim 41 (depends on 1)

The method of claim 1, wherein the fermenting step occurs at a temperature of above 50° C.

### Claim 42 (depends on 1)

The method of claim 1, further comprising isolating the lactic acid from the xylose.