hydroxycarboxylic acid processing method

专利摘要:
abstract processing of hydroxycarboxylic acids for biomass polymers (eg plant biomass, animal biomass and municipal waste biomass) is processed to produce useful intermediates and products such as aliphatic hydroxycarboxylic acids and hydroxycarboxylic acid derivatives. These aliphatic hydroxycarboxylic acids are in turn polymerized. The polymerization is performed using a thin film evaporator or a thin film polymerization / devolatilization device. The conversion of lactic acid to polylactic acid is an especially useful product for this process. 1/1
公开号:BR112015026766B1
申请号:R112015026766-1
申请日:2014-04-25
公开日:2019-10-29
发明作者:Medoff Marshall；Paradis Robert；Craig Masterman Thomas
申请人:Xyleco Inc；
IPC主号:

专利说明:

“METHOD OF PROCESSING HYDROXYCARBOXYLIC ACIDS” [0001] This order incorporates by reference the complete disclosure of the following provisional copending order: US No. 61 / 816,664, filed on April 26, 2013 and the copying provisional order: US No. 61 / 941,771 deposited on February 19, 2014.
BACKGROUND OF THE INVENTION [0002] Many potential lignocellulosic raw materials are available today, including agricultural waste, woody biomass, municipal waste, oil or seed masses and macroalgae, to name a few. At the moment, these materials are often underutilized, being used, for example, as animal feed, organic composting materials, burned in cogeneration establishments or even landfilled.
[0003] Lignocellulosic biomass includes crystalline cellulose fribbles embedded in a hemicellulose matrix, surrounded by lignin. This produces a compact matrix that is difficult to access by enzymes and other chemical, biochemical and / or biological processes. Cellulosic biomass materials (for example, biomass materials from which substantially all of the lignin has been removed) are more accessible to enzymes and other conversion processes, but even so, naturally occurring cellulosic materials often have low yields (with respect to theoretical yield) when in contact with hydrolysis enzymes. Lignocellulosic biomass is even more recalcitrant to enzyme attack. In addition, each type of lignocellulosic biomass has its own specific composition of cellulose, hemicellulose and lignin.
SUMMARY [0004] In general, this publication relates to methods and processes for converting a material, such as a biomass raw material, for example, cellulosic materials, with starch or lignocellulosics, into useful products, such as
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2/125 example, hydroxycarboxylic acids (for example, alpha, beta, gamma and delta hydroxycarboxylic acids) and hydroxycarboxylic acid derivatives (for example, esters). Then, in turn, the hydroxycarboxylic acid is polymerized to hydroxycarboxylic polyacids. Such hydroxycarboxylic acids can be hydroxycarboxylic polyacids, for example: di-, tri-, tetra-, penta-, hexa-, hepta-, and carboxylic octa acids. Polycarboxylic acid can be replaced by other groups, for example: by alkyl groups. The carbon chain of the carboxylic acid can be linear, branched, cyclic or alicyclic.
[0005] Among the important products that can be produced from lignocellulosic biomass are hydroxycarboxylic acids. These acids, for example, substituted alpha, beta and gamma hydroxy acids can be polymerized to produce important polymers. Alpha substituted methyl acid, D-lactic acid and / or L-lactic acid are commercially produced and polymerized to polylactic acid. This polymer is important because it can be produced in forms that allow it to be swelled in fibers, extruded into solid products and other products that require processing of the complex polymer. Since polylactic acid and other alpha, beta, gamma and delta hydroxycarboxylic acid polymers are biodegradable, they provide target polymers for the bioprocessing industry. The most striking process for producing polylactic acid involves converting lactic acid to an oligomer, depolymerizing it to obtain lactide dimer and polymerizing that molecule. There is also a need for processing that involves a more direct synthesis of the polymerized product without isolating the intermediates.
[0006] Method for making a high molecular weight polymer or copolymer, for example, from an oligomer, the method comprising evaporating water while it is formed during the condensation of a hydroxycarboxylic acid polymer, for example, an oligomer or a polymer while it
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3/125 passes through the surface of a thin film polymerization / devolatilization device. Where hydroxycarboxylic acid has stereocenter, stereocenter can be maintained during the polymerization process. In some cases, hydroxycarboxylic acid is an aliphatic hydroxycarboxylic acid. For example, D-lactic acid and / or L-lactic acid become polymers of D-lactic acid and / or polymers of L-lactic acid, respectively, with little loss of stereointegrity. It is understood that the process described here preserves stereochemistry where biochemistry and chemical processes preserve stereochemistry. If both the D isomer and the L monomer are listed, it is understood that the D isomer monomer will become a D polymer and the L isomer monomer will become a D polymer. When a hydroxycarboxylic acid is listed without its stereochemistry, it is understood that mixtures D, L, meso and / or mixtures are assumed.
[0007] In another embodiment, a copolymer of a hydroxycarboxylic polymer can be a copolymer of hydroxycarboxylic acid monomers or other compatible monomers. The copolymer can be a copolymer of different hydroxycarboxylic acid monomers, for example, a mixture of lactic acid and another 3-hydroxybutyric acid. The copolymer can also be obtained from copolymerizing oligomers of different hydroxycarboxylic acids.
[0008] In a specific embodiment, a method for making aliphatic hydroxycarboxylic polyacids by converting a crude aliphatic hydroxycarboxylic monomer to aliphatic hydroxycarboxylic polyacids, comprising the following steps:
a) supplying a monomer source such as aliphatic hydroxycarboxylic acid in a hydroxy medium;
b) concentration of the aliphatic hydroxycarboxylic acid in a hydroxy medium by evaporating a substantial portion of the hydroxy medium to form a concentrated acid solution;
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c) aliphatic hydroxycarboxylic acid oligomerization to obtain an aliphatic hydroxycarboxylic acid oligomer with an oligomerization degree of approximately 5 to approximately 50;
d) adding a polymerization catalyst for the hydroxycarboxylic acid oligomer;
e) polymerization of aliphatic hydroxycarboxylic acid and aliphatic hydroxycarboxylic acid oligomer to obtain an aliphatic hydroxycarboxylic acid with a degree of polymerization of approximately 35;
f) transferring the aliphatic hydroxycarboxylic polyacid to a thin film polymerization / devolatilization device to obtain a degree of polymerization of approximately 300 to approximately 20,000;
g) isolation of the aliphatic hydroxycarboxylic polyacid and where for steps d, e, f the cyclic dimers derived from an aliphatic hydroxycarboxylic acid have less than 10% by weight percentage based on the total mass of the aliphatic monomer, oligomers and polymers . The thin film polymerization / devolatilization device is configured so that the fluid polymer is transported to the device so that the fluid polymer film is less than 1 cm thick and provides means for volatilizing the water formed in the reaction and other volatile components . The temperature of the thin film evaporator and the polymerization / devolatilization device is from 100 to 240 ° C and the device pressure is from 0.000014 to 50 kPa. A full vacuum can be used in the evaporator device. The pressures can be, for example, less than 0.01 torr, alternatively less than 0.001 torr and optionally less than 0.0001 torr.
[0009] The polymerization steps c, e, and f are three stages of polymerization, 1, 2 and 3, of the polymerization of aliphatic hydroxycarboxylic acids.
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5/125 [0010] The thin-film evaporator or thin-film polymerization / devolatilization device is also convenient for adding other components to the aliphatic hydroxycarboxylic polyacids. Such other components may include other monomers, including aliphatic hydroxycarboxylic acids, aliphatic hydroxycarboxylic acid homologues, diols, dicarboxylic acids, alcoholic amines, diamines and similar reactive species. Reactive components such as peroxides, glycidyl acrylates, epoxides and the like can also be added at this stage of the process.
[0011] An extruder can also be in fluid contact or in fluid communications with the thin-film evaporator and / or thin-film polymerization / devolatilization device and can be used to recycle the polymer and / or to provide the means to process the hydroxycarboxylic polyacid for the process isolation portion. The extruder is also a convenient device for adding other components and reagents listed above and discussed below, especially if they would be volatilized in the thin film polymerization / devolatilization device. In one aspect, the disclosure relates to a method for making a product that includes treating a reduced recalcitrance biomass (for example, lignocellulosic or cellulosic materials) with one or more enzymes and / or one or more organisms to produce an acid hydroxycarboxylic acid (for example, an alpha, beta, gamma or delta hydroxycarboxylic acid) and convert hydroxycarboxylic acid into a product.
[0012] Optionally, the raw material is previously treated with at least one method selected from irradiation (for example, with an electron beam), heat treatment, sonication, oxidation, pyrolysis and vapor explosion, for example, to reduce the recalcitrance of lignocellulosic or cellulosic material. In a certain application of the method, hydroxycarboxylic acid is converted chemically, for example, by converting lactic acid and / or lactic acid into
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6/125 esters by treatment with an alcohol and an acid catalyst. Other methods for chemical conversion that can be used include polymerization, isomerization, esterification, oxidation, reduction, disproportion and combinations thereof. Some examples of hydroxycarboxylic acids that can be produced and then converted include glycolic acid, lactic acid, malic acid, citric acid and tartaric acid (disubstituted), 3-hydroxybutyric acid (beta-substituted), 4-hydroxybutyric acid (gamma-substituted), 3- hydroxyvaleric (beta-substituted), gluconic acid (tetra-substituted in alpha, beta, gamma and delta carbons with an additional hydroxy in epsilon carbon).
[0013] In some other implementations, the lignocellulosic or cellulosic material is treated with one or more enzymes to release one or more sugars; for example, to release glucose, xylose, sucrose, maltose, lactose, mannose, galactose, arabinose, fructose, dimers thereof, such as cellobiosis, heterodimers thereof, such as sucrose and oligomers thereof, and mixtures thereof. Optionally, treatment may further include (for example, subsequent to the release of sugars) the use (for example, by contact with sugars and / or biomass) of one or more organisms to produce hydroxycarboxylic acid. For example, sugars can be fermented by a sugar fermentation organism to hydroxy acid. The sugars that are released from the biomass can be purified (for example, before fermentation) using, for example, a method selected from electrodialysis, distillation, centrifugation, filtration, cation exchange chromatography and combinations of these in any order.
[0014] In some implementations, the conversion comprises the polymerization of hydroxycarboxylic acid to a polymer in successive steps of increasing conversion as measured by the degree of polymerization. The degree of polymerization is based on the numerical average of the molecular weight, Mn. The polymerization can be in a molten state (for example, without a solvent and above the melting point
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7/125 of the polymer), it can be in a solid state, or it can be a solution (for example, with an added solvent).
[0015] Optionally, when the polymerization method is by direct condensation, the polymerization may include the use of coupling agents and / or chain extenders to increase the molecular weight of the polymer. For example, coupling agents and / or chain extenders can include triphosgene, carbonyldiimidazole, dicyclohexicarbodiimide, diisocyanide, acid chlorides, anhydride acids, epoxides, thyrane, oxazoline, orthoester and mixtures thereof. Alternatively, the polymer may have a comonomer that is a polycarboxylic acid or polyols or a combination thereof.
[0016] Optionally, polymerizations can be done using catalysts and / or activators. The catalyst can be added after a desired degree of polymerization has been achieved. For example, protonic acids and Lewis acids can be used. Examples of acids include sulfonic acids, H3PO4, H2SO4, sulfonic acids, for example, methane sulfonic acid, p-toluene sulfonic acid, Nafion® NR 50 H + in the form of DuPont, Wilmington DE (sulfonic acid supported / bonded to a polymer which can optionally have a main support of tretrafluoroethylene), acids supported on or attached to polymers, metals, Mg, Al, Ti, Zn, Sn, metal oxides, TiO2, ZnO, GeO2, ZrO2, SnO, SnO2, Sb2O3, halides metallic, ZnCl2, SnCl2, AlCl3 SnCl4, Mn (AcO) 2, Fe2 (LA) 3, Co (AcO) 2, Ni (AcO) 2, Cu (OA) 2, Zn (LA) 2, Y (OA) 3 , Al (/ - PrO) 3, Ti (BuO) 4, TiO (acac) 2, (Bu) 2SnO, tin octoate, solvates of any of these and mixtures of these can be used. For example, p-toluene sulfonic acid and tin octoate or tin chloride can be used together.
[0017] Polymerizations can be carried out at a temperature between approximately 100 and approximately 260 ° C, such as between approximately 110 and approximately 240 ° C or between approximately 120 and approximately
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200 ° C. Optionally, at least a part of the polymerizations can be carried out in a vacuum (for example, between approximately 0.005 to 300 kPa).
[0018] After the polymerization has reached the desired molecular weight, it may be necessary to deactivate and / or remove the catalyst from the polymer. The catalyst can be reacted with a variety of compounds, including silica, functionalized silica, alumina, clays, functionalized clays, amino, carboxylic acids, phosphites, acetic anhydride, functionalized polymers, EDTA and similar chelating agents.
[0019] As long as it is not theoretically linked to those catalysts such as extraneous systems, if the added compound can occupy multiple spaces in the tin it can become inactive for polymerization (and depolymerization). For example, a compound like EDTA can occupy several places in the sphere of coordination of the stranger and, in turn, interfere in the catalytic places in the sphere of coordination. Alternatively, the added compound can be of sufficient size and the catalyst can adhere to its surface, so that the absorbed catalyst can be filtered out of the polymer. These added compounds, such as silica, may have sufficient acidic / basic properties so that the silica absorbs the catalyst and is filterable.
[0020] In implementations where the polymers are made from Lactic acid and / or L-lactic acid or other hydroxycarboxylic acids, the methods may also include mixing the polymer with a second polymer. For example, a second polymer can include polyglycols, polyvinyl acetate, polyolefins, styrenic resins, polyacetals, poly (meth) acrylates, polycarbonates, polybutylene succinate, elastomers, polyurethanes, natural rubber, polybutadiene, neoprene, silicone and combinations thereof. This mixture is intended to create a physical mixture of polymers. The mixing can be carried out in the thin film polymerization / devolatilization device by adding the second polymer to the recycling circuit or using an optional extruder. After the
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9/125 mixing is complete, crosslinking means can be made to crosslink the polymers with crosslinking additives or the crosslinking processes described below. Peroxides can be added to facilitate crosslinking.
[0021] In other implementations in which polymers are made from hydroxycarboxylic acid, a comonomer can be copolymerized with hydroxycarboxylic acid. For example, the comonomer may include elastomeric units, lactones, glycolic acid, carbonates, morpholiniones, epoxides, glycosalicilide 1,4benzodioxepine-2,5- (3H) -dione, lactosalicilide 1,4-benzodioxepine-2,5- (3H, 3-methyl) dione, disalicilide dibenzo-1,5 dioxacin-6-12-dione, morpholine-2,5-dione, glycolide 1,4dioxane-2,5-dione, oxepano-2-one ε-caprolactone, trimethylene carconate 1,3-dioxane2-one, 2,2-dimethyltrimethylene carbonate, 1,5-dioxepane-2-one, 1,4-dioxane-2-one pdioxanone, gamma-butyrolactone, beta-butyrolactone, beta-me-delta -valerolactone, ethylene oxalate 1,4-dioxane-2,3-dione, 3- [methyl benzyloxycarbonyl] -1,4-dioxane-2,5dione, ethylene oxide, propylene oxide, 5.5 '(oxepano- 2-one), 2,4,7,9-tetraoxaspospiro [5.5] undecane-3,8-dione spiro-bi-dimethylene caronate and mixtures thereof.
[0022] Polymers of hydroxycarboxylic polyacids are polyesters. These polymers can be modified by adding aromatic alcohols and / or aromatic carboxylic acids during one of these stages in the polymerization process. An optional place to add these alcohols and / or carboxylic acids is in the processing by the thin film polymerization / devolatilization device. An optional combination of alcohols and carboxylic acids is the addition of almost equimolar amounts of diols and dicarboxylic acids to hydroxycarboxylic polyacids. By maintaining the ratio of diols to equimolar dicarboxylic acids, the resulting increased molecular weight polymer will have properties similar to those of parent hydroxycarboxylic polyacids, but with the advantage of the increased molecular weight of the polymer. Optionally, proportion of
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10/125 aliphatic or aromatic diols and / or aliphatic or aromatic carboxylic diacids is 0.95 to 1.05 or 0.975 to 1.025.
[0023] Trisubstituted polyols and / or trisubstituted carboxylic acids can also be added to the hydroxycarboxylic polyacid to obtain a cross-linked material. The molar ratio of these tri-substituted additives must be less than 10 moles percentage, optionally less than 5 moles percentage or optionally, still less than 2 moles percentage based on the total number of units of monomers of hydroxycarboxylic polyacids. These tri-substitutes can be processed / added to the polymer melt in the thin film polymerization / devolatilization device or they can be processed / added to the polymer melt in the extruder.
[0024] Diol and dicarboxylic acids and triol and / or trisubstituted carboxylic acids can be added to any of steps c, e and f described above.
[0025] In general, in order to achieve high molecular weights of hydroxycarboxylic acid, the molar totality of the alcohol groups and the carboxylic acid groups must be controlled close to the equimolar amounts of the alcohol and carboxylic acid groups. The equimolar difference must be greater than 0.90 and not more than 1.10 molar ratio of alcohol to carboxylic acid. In addition, the ratio is greater than 0.95 and not more than 1.05 and, optionally, greater than 0.98 and not more than 1.02. The calculation of alcohol and carboxylic acid should include all di and tri-substituted compounds described above.
[0026] When di and / or tri-substituted reagents are included in polymerization steps 1, 2 and 3 or especially in steps 2 and 3, the resulting polymer can be a block polymer of the hydroxycarboxylic polyacid units separated by the di and / or monomers or tri-substituted added.
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11/125 [0027] The diol / triol and the diacid / tracid additives can be controlled based on the monomer units of the hydroxycarboxylic polyacid. In one embodiment, the molar totality of the diol / triol and the diacid / tracid additives may be less than 10 mole percent of the hydroxycarboxylic polyacid monomer units. For example, for the monomer D-lactic acid and / or L-lactic acid, the molecular weight of Mn is divided by 72 to determine the number of monomer units. The number 72 is obtained from the molecular weight 90 of D-lactic acid and / or L-lactic acid minus water (molecular weight 18) which is a by-product of each condensation step.
[0028] In any implementation in which polymers are made, the method may also include the branching or crosslinking of the polymer. For example, polymers can be treated with a crosslinking agent, including 5.5 'bis (oxepane-2-one) (bis-s-caprolactone)), spiro-bis-dimethylene carbonate, peroxides, dicumyl peroxide, benzoyl peroxide, unsaturated alcohols, hydroxymethyl methacrylate, 2-butene-1,4-diol, unsaturated anhydrides, maleic anhydride, saturated epoxides, glycidyl methacrylate, irradiation and combinations thereof. Optionally, a molecule (for example, a polymer) can be grafted to the polymer. For example, the graft can be performed by treating the polymer with irradiation, peroxide, crossing agents, oxidants, heating or any method that can generate a cation, anion or radical in the polymer.
[0029] In any implementation where polymers are processed, processing can include injection molding, blow molding, fiber expansion and thermoforming.
[0030] In any implementation in which polymers are made, polymers can be combined with fillers (for example, by extrusion and / or compression molding). For example, some fillers that can be used include silicates, layered silicates, organic or polymer modified layered silicate, synthetic mica, carbon, carbon fiber, fiber
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12/125 glass, boric acid, talc, montmorillonite, clay, starch, corn starch, wheat starch, cellulose fiber, paper, rayon, non-woven fibers, wood flour, potassium titanate yarn, borate yarn aluminum, 4,4'-thiodiphenol, glycerol and mixtures thereof.
[0031] In any implementation where polymers are processed, polymers can be combined with a dye and / or a fragrance. For example, dyes that can be used include blue 3, blue 356, brown 1, orange 29, violet 26, violet 93, yellow 42, yellow 54, yellow 82 and combinations thereof. Examples of fragrances include wood, evergreen, brazilwood, mint, cherry, strawberry, peach, lime, mint, cinnamon, anise, basil, bergamot, black pepper, camphor, chamomile, citronella, eucalyptus, pine, fir, geranium , ginger, grapefruit, jasmine, juniper berry, lavender, lemon, mandarin, marjoram, musk, myrrh, orange, patchouli, rose, rosemary, sage, sandalwood, tea tree, thyme, wintergreen, ylang ylang, vanilla, new car or mixtures of these fragrances. Fragrances can be used in any quantity, for example, between about 0.005% by weight and about 20% by weight (for example, between about 0.1% and about 5% by weight, between about 0, 25% by weight and about 2.5%).
[0032] In any implementation where polymers are processed, the polymer can be mixed with a plasticizer. For example, plasticizers include triacetin, tributyl citrate, polyethylene glycol, GRINDSTED® SOFT-N-SAFE (from Danisco, DuPont, Wilmington DE, bishhydroxymethyl diethyl malonate) and mixtures thereof.
[0033] In any implementations in which polymers are produced, polymers can be further processed or processed by forging, molding, etching, extruding and / or assembling the polymer within the product.
[0034] In another aspect, the invention relates to products made by the methods discussed above. For example, products include a converted hydroxycarboxylic acid in which hydroxycarboxylic acid is produced by
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13/125 fermentation of sugars derived from biomass (eg glycolic acid, Lactic acid and / or L-lactic acid, D-malic acid, L-malic acid, citric acid and tartaric acid, L-tartaric acid and meso- tartaric acid). Biomass includes cellulosic and lignocellulosic materials and these can release sugars by acidic or enzymatic saccharification. In addition, biomass can be treated, for example, by irradiation.
[0035] Products, for example, include polymers, including one or more hydroxy acids in the main polymer support and, optionally, non-hydroxy carboxylic acids in the main polymer support. Optionally, the polymers can be crosslinking or graft copolymers. Optionally, the polymer can be mixed with a second polymer, mixed with a plasticizer, mixed with an elastomer, mixed with a fragrance, mixed with a dye, mixed with a pigment, mixed with a filler or mixed with a combination of these.
[0036] Some of the products described here, for example, D-lactic acid and / or L-lactic acid, can be produced by chemical methods. However, fermentative methods can be much more efficient, providing high biomass conversion, selective conversion and high production rates. In particular, fermentative methods can produce D or L isomers of hydroxycarboxylic acids (for example, lactic acid) in almost 100% chiral purity or mixtures of these isomers, whereas chemical methods typically produce racemic mixtures of D and L isomers. When a hydroxycarboxylic acid is listed without its stereochemistry, it is understood that mixtures D, L, meso and / or mixtures are assumed.
[0037] The methods described here are also advantageous due to the fact that in this document they are also advantageous, since the raw materials (for example, sugars) can be derived completely from biomass (for example, cellulosic and lignocellulosic materials). In addition, some of the products described here, such as
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14/125 polymers of hydroxycarboxylic acids (for example, polylactic acid) are compostable, biodegradable and / or recyclable. Consequently, the methods described here can supply materials and products from renewable sources (for example, biomass), in which the products themselves can be reused or simply returned to the environment in a safe manner.
[0038] For example, some products that can be produced using the methods, systems or equipment described here may include personal hygiene items, handkerchiefs, towels, diapers, eco-friendly packaging, compostable vases, consumer electronics, laptop covers, covers for cell phones, handsets, food packaging, disposable packaging, food containers, drink bottles, garbage bags, compostable waste bags, cover films, controlled release matrices, controlled release containers, fertilizer containers, containers for pesticides, herbicide containers, nutrient containers, drug containers, flavoring agent containers, food containers, shopping bags, general purpose film, high heat resistant films, heat resistant sealing adhesive, surface coatings, disposable tableware, plates, glass s, forks, knives, spoons, sporks, bowls, auto parts, panels, fabrics, undercoat covers, carpet fibers, clothing fibers, underwear fibers, sports clothing fibers, shoe fibers, surgical sutures , implants, scaffolding and drug delivery systems.
[0039] Other characteristics and advantages of the publication will become apparent from the detailed description below, as well as from the claims.
DESCRIPTION OF THE FIGURE [0040] The precedent will become apparent from the following more detailed description of exemplary modalities of the publication, as illustrated in this
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12/155 accompanies it. The figures are not necessarily on an adequate scale, emphasizing, instead, the illustration of the modalities of the present disclosure.
[0041] FIG. 1 shows a generalized scheme for the polymerization process with the thin film polymerization / devolatilization device.
[0042] A FIG. 2a shows a schematic diagram of one unit in polymerization that has an example in one device in polymerization / devolatilization and an extruder. [0043] A FIG. 2b shows a cut of device in
thin-film polymerization / devolatilization with an inclined surface over which the molten polymer flows.
[0044] FIG. 3 is a flowchart that shows processes for manufacturing products from biomass raw materials.
[0045] FIG. 4 is a schematic diagram showing some of the possible chemical pathways for the production of lactic polyacid.
[0046] FIG. 5 is a batch of lactic acid production in a 1.2 L Bioreactor.
[0047] FIG. 6 is a batch of lactic acid production in a 20 L Bioreactor.
[0048] FIG. 7 is a batch of GPC data for lactic polyacid.
[0049] FIG. 8 shows the chemical structures of some exemplary hydroxy acids.
[0050] FIG. 9a shows a small scale polymerization unit having an example of a laboratory film thin film polymerization / devolatilization device.
[0051] FIG. 9b shows a section of the thin film polymerization / devolatilization device with an inclined surface over which the molten polymer flows.
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16/125 [0052] FIG. 10 shows a schematic diagram of a tubular and cupped heat exchanger with molten polymer flow through the inner surface of the tubes.
DETAILED DESCRIPTION [0053] Using the equipment, methods and systems described here, cellulosic and lignocellulosic raw material materials, for example, which can be extracted from biomass (eg plant biomass, animal biomass, paper, biomass of this document, cellulosic or lignocellulosic raw materials, for example, that can be extracted from biomass (eg vegetable biomass, animal biomass, paper and biomass from municipal waste) and that are often readily available, but are difficult to process, can be transformed into useful products such as sugars and hydroxycarboxylic acids. Included are equipment, methods and systems for chemically converting hydroxycarboxylic acid products produced from biomass into a secondary product, such as polymers (for example, polyacid hydroxycarboxylic) and derivative polymers (for example, composites, elastomers and copol mer).
[0054] Hydroxycarboxylic acids can be subjected to condensation reactions to obtain polyester polymers. Since hydroxycarboxylic acids and polymeric products are derived from biomass, they are a renewable product.
[0055] In one embodiment, the method for making a high molecular weight polymer or copolymer from an oligomer, the method comprising evaporating water while it is formed during the condensation of a hydroxycarboxylic acid oligomer, for example, an acid aliphatic hydroxycarboxylic acid from a thin film evaporator. Water, as a by-product of condensation, needs to be removed from the high molecular weight polymer or copolymer to maximize
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17/125 conversion to higher molecular weight materials and minimize the undesirable reverse reaction where water re-adds and releases a monomer unit, a dimer unit or an hydroxycarboxylic acid oligomer.
[0056] In another modality, the operation of the thin film evaporator unit is described in more detail and the polymerization process is denoted in three stages or stages for the conversion into high molecular weight polymers. Fig. 1 shows a schematic diagram of the polymerization process with the three indicated polymerization steps. A recycling circuit that takes the product from the polymerization / devolatilization device with thin / evaporative film and recycles it at the entrance of the polymerization / devolatilization device with thin / evaporative film. The product flow from the evaporative / thin film polymerization / devolatilization device can be divided between recycling and sending a portion of the product flow to collect the product.
[0057] First, excess water is removed from hydroxylcarboxylic acid. Since the acid is derived from biomass processing, it is likely to be in an aqueous solvent. The condensation process to make the polyester produces water and so the excess water must be removed. Removal can be done in a batch or in a continuous process, with or without vacuum and at temperatures to achieve effective water removal rates. Some condensation can occur to form ester bonds during step 1 and low molecular weight oligomers can be formed.
[0058] After the excess water is removed, additional heating and additional vacuum processing to remove more water. At this stage in the process, the results of converting hydroxycarboxylic acid to an oligomerization degree is approximately 5 to approximately 50 based on the average molecular weight number of the oligomer / polymer.
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18/125 [0059] The polymerization catalyst is added to the oligomer / polymer system. The catalyst (s) of the candidate polymer is / are described above and described in more detail below. The catalyst can be added by any convenient means. For example, the components of the catalyst can be dissolved / dispersed in the hydroxycarboxylic acid and added to the oligomer / polymer with an oligomerization degree of approximately 5 to 50.
[0060] With the catalyst present, more conversion of the oligomer / polymer mixture takes place to obtain a degree of polymerization of approximately 35 to approximately 500. This is achieved by the catalytic action of the added catalyst and a combination of more heating and higher vacuums.
[0061] Then, the thin film polymerization / devolatilization device is used to obtain polymers with a degree of polymerization of approximately 300 to approximately 20,000. The thin film is less than 1 cm thick, optionally less than 0.5 cm or even less than 0.25 cm, additionally less than 0.1 cm.
[0062] During the entire process and when the catalyst is added the cyclic dimers derived from hydroxycarboxylic acid are less than 10 percentage weights based on the total mass of the monomers, oligomers and polymers (and copolymers) of hydroxycarboxylic acids. The thin film polymerization / devolatilization device is configured so that the fluid polymer is transported to the device so that the fluid polymer film is less than 1 cm thick and the device provides means for volatilizing the water formed in the reaction and other volatile components. The type of polymerization is characterized as polymerization in the melting phase. The thin film polymerization / devolatilization device and the film evaporator described here are similar in that they perform the same function. When hydroxycarboxylic acid is D-lactic acid and / or L-lactic acid, the cyclic dimer is
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19/125 denoted as lactide, although lactide may generally refer to these cyclic dimers. For lactic acid, the lactide is 3,6-dimethyl-1,4-dioxane-2,5-dione, without denoted stereochemistry.
[0063] Optionally, the cyclic dimers of hydroxycarboxylic are less than 5% by weight based on the total mass of the hydroxycarboxylic monomers, oligomers and polymers (copolymers). In another embodiment, the cyclic hydroxycarboxylic dimers are less than 2.5 based on the total weight of the percentage weight of the monomers, oligomers and polymers of hydroxycarboxylic acids.
[0064] The hydroxyl medium can be water, mixtures of water and compatible solvents such as methanol, ethanol and alcohols with low molecular weight, such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and similar alcohols .
[0065] The temperature of the thin film polymerization / devolatilization device is from 100 to 260 ° C. Optionally, the temperature of the thin film polymerization / devolatilization device is 120 to 240 ° C. Additionally, the temperature is between 140 and 220 ° C.
[0066] The thin film polymerization / devolatilization device can operate in high vacuum with pressures of 0.0001 torr or less. The thin film polymerization / devolatilization device can operate, for example, at 0.001 torr or less; or 0.01 torr or less. During some stages of operation, operating pressures can be considered low and medium vacuum; from 760 to 25 torr and 25 to 0.001 torr, respectively. The device can operate at a pressure of 100 to 0.0001 torr, or, alternatively, from 50 to 0.001 torr, or optionally from 25 to 0.001 torr.
[0067] The thin film polymerization / devolatilization device can optionally include a recycling circuit in which the melted polymerization product is the entry point of the thin film polymerization / devolatilization device. It can also be coupled to an extrusion device. The product of
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20/125 molten polymerization can be processed from the thin film polymerization / devolatilization device to an extruder that can pass the product to the finished product area. Alternatively, the flow from the extruder outlet can be directed back to the thin film polymerization / devolatilization device. The flow can be divided between the product and the recycled. The extruder system is a convenient place to add additives to the melt polymerization product for recycling and subsequent reaction or to mix in a polymer stream before transferring the product to the finished product area. The additives are described above and below. The addition of the additive includes compounds that react within the polymer, in the polymer or physically mix with the polymer.
[0068] FIG. 2a is a schematic diagram of a system for polymerizing hydroxycarboxylic acid. The thin-film evaporator or thin-film polymerization / devolatilization device (200), an extruder (optional) (202) for product isolation or recycling back to the thin-film evaporator or film-polymerization / devolatilization device a heated circuit (204), a heated condenser (206), a cooled condenser (208) to condense water and other volatile components, a collection container (210), a fluid transfer unit (212) to removing condensed water and volatile components {this effluent can be taken to another unit operation to recover the volatile components useful for recycling back to step 1} and a product isolation device (214). The thin film evaporator or thin film polymerization / devolatilization device comprises step 3 in the description of the process discussed above. The fluid transfer unit is shown as a pump.
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21/125 [0069] FIG. 2 is a section of the thin film polymerization / devolatilization device. The rectangular angled part (250) is the optionally heated surface where the molten polymer flows. The new flow of molten polymer (252) flows on the surface and is shown as an ellipse (258) of fluid polymer flowing to the outlet of the device at (254). The volatiles are removed at (256).
[0070] The internal parts of the thin-film evaporator or thin-film polymerization / devolatilization device can be in different configurations, but they must be configured to ensure that the polymer fluid flows in a thin film through the device. This is to facilitate the volatilization of water that is found in the polymer fluid or is formed by a condensation reaction. For example, the surface can be tilted at an angle relative to the straight sides of the device. The surface can be heated separately so that the surface is 0 to 40 ° C hotter than the polymer fluid. With this heated surface it can be heated up to 300 ° C, reaching 40 ° C higher than the total temperature of the device.
[0071] The thickness of the polymer fluid flowing along the part with the thin film of the device is less than 1 cm, optionally less than 0.5 cm or alternatively less than 0.25 cm.
[0072] The thin film polymerization / devolatilization device and the thin film evaporator have similar functions. Other devices similar in function should be considered to have the same function as these. Descriptively, these include scraped film evaporators, short path evaporators, a tubular or shell heating exchanger and the like. For each of these evaporator configurations, a dispenser can be used to ensure thin film distribution. The limitation to which they must be able to operate under the conditions described above.
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22/125 [0073] Optionally, the catalyst can be removed from the molten polymer. The removal of the catalyst can be carried out only before, during or after the thin film evaporator / thin film polymerization / devolatilization device. The catalyst can be filtered out of the molten polymer by using a filter system similar to a tamis. Since the molten polymer is flowing around the thin film evaporator / thin film polymerization / devolatilization device, a filtration system can be added.
[0074] To facilitate the removal of the catalyst, a neutralizing or chelating chemical can be added. Candidate compounds include phosphites, anhydrides, carboxylic polyacids, polyamines, hydrazides, EDTA (and similar compounds) and the like. These neutralizing and / or chelating compounds can be insoluble in the molten polymer, leading to easy filtration. Carboxylic polyacids include acrylic polyacids and methacrylic polyacids. The latter can be in a random, blocking and graft polymer configuration. Amines include ethylene diamine, ethylene diamine oligomers and other similar polyamines, such as methyl bis-3-amino, propane.
[0075] Another option to remove the catalyst includes adding solid materials to the polymer melt. Examples of added materials include silica, alumina, aluminum silicates, clays, diatomaceous earth, polymers and similar solid materials. Each of these can optionally be functionalized to react with / bind to the catalyst. When the catalyst bonds / bonds to these structures, it can be filtered out of the polymer.
[0076] The (co) polymer product is isolated when the desired conversion / physical properties (s) are (are) obtained. The product can be transported to a colleague / product isolation area. Optionally, a final devolatilization step can be performed just before the product is isolated. The types of equipment
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23/125 to isolate the product from the (co) polymer may include lozenge system and similar systems in which the product is cooled to obtain a product in a usable form.
[0077] Analysis when the product can be sent for product isolation may include taking samples and measuring important parameters, such as molecular weight and polydispersity. Optionally, a continuous measurement can be used, such as the inclusion of an in-line viscometer that can measure intrinsic viscosity.
[0078] The thin film evaporator and the thin film polymerization / devolatilization device can be made of any material normally used for chemical processing equipment. Since hydroxycarboxylic acids can be corrosive, the thin film evaporator can be covered or coated with corrosion resistant metals such as tantalum, alloys like Hastelloy ™, a trademark alloy from Haynes International, and the like. It can also be coated with polymeric coatings with high inert temperature, such as Teflon ™ by DuPont, Wilmington De. The corrosivity of the hydroxycarboxylic acid system may not be surprising, since the lactic acid pKa is 0.8 less than the of acetic acid. In addition, water undoubtedly hydrates the acid and the acidic end of the polymer. When these hydration waters are removed, the acidity can be much higher, as it is not leveled by the hydration waters.
[0079] FIG. 9a is a schematic diagram of a pilot scale polymerization system for polymerizing hydroxycarboxylic acid. The thin-film evaporator or thin-film polymerization / devolatilization device (900), a heated elevator (902), a cooled condenser (904) for condensing water and other volatile components, a collection container (906), a fluid transfer unit (908) to recycle the polymer fluid shown as a
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24/125 pump. The connecting piping is not shown for clarity. The pump outlet (916) is connected to the inlet (910), the device outlet (912) is connected to the pump inlet (914). The isolation section of the product is not shown. The inside of the thin film polymerization / devolatilization device is an inclined surface. The polymer fluid is fluid to the inlet with configuration so that the polymer fluid flows on the sloped surface. This inclined surface can be heated separately, as described above.
[0080] FIG. 9b is a section of the thin film polymerization / devolatilization device. The rectangular angled part (950) is the optionally heated surface where the molten polymer flows. The new flow of molten polymer (952) flows on the surface and is shown as a trapezoid (956) of fluid polymer flowing to the outlet of the device at (954).
[0081] An alternative thin film evaporator / devolatilization can be a tubular and cupped heat exchanger. A schematic diagram is shown in FIG. 10. The shell (1002) and the tube (1008) with only one of the tubes labeled. The flow of molten polymer (1006) is represented by entering the left side of each tube, but a distributor could also be present to distribute the polymer flow over the inner surface of the tubes to ensure that the thickness of 1 cm of the thin film is obtained. The collection of the polymer flow is at 1004.
[0082] To facilitate the removal of water, a stripping gas can be included in the system, especially towards the exit of the thin film evaporator or the thin film polymerization / devolatilization device. The vacuum capacity must accommodate the use of stripping gas.
[0083] Additives can be added before, during and after the thin film evaporator or the thin film polymerization / devolatilization device. These additives may include, but are not limited to, polymers for mixing,
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25/125 reactive polymers, reactive monomers, other condensation monomers, catalyst stabilizing agents, antioxidant peroxides for crosslinking polymer chains. These additives are more fully described below.
PROCESSING OF BIOMASS TO PRODUCE HYDROXICARBOXYLIC ACIDS.
[0084] Hydroxycarboxylic acid is prepared from biomass. For example, lignocellulosic materials include different combinations of cellulose, hemicellulose and lignin. Cellulose is a linear polymer of glucose. Hemicellulose is any one of several heteropolymers, such as xylan, glucuronoxylan, arabinoxylans and xyloglucan. The primary sugar monomer present (for example, present in greater concentration) in hemicellulose is xylose, although other monomers, such as mannose, galactose, rhamnose, arabinose and glucose, are also present. Although all lignins show variation in their composition, they have been described as an amorphous dendritic network polymer of phenyl propene units. The amounts of cellulose, hemicellulose and lignin in a specific biomass material depend on the source of the biomass material. For example, biomass material derived from wood may contain about 38-49% cellulose, 7-26% hemicellulose and 23-34% lignin, depending on the type. Grasses usually have 33-38% cellulose, 24-32% hemicellulose and 17-22% lignin. Lignocellulosic biomass clearly constitutes a large class of substrates.
[0085] Biomass-destroying enzymes and organisms that break down biomass, such as cellulose, hemicellulose and / or the lignin portions of the biomass, as described above, contain or manufacture various cellulosic enzymes (cellulases), ligninases, xylanases, hemicellulases or several small molecule biomass-destroying metabolites. A cellulosic substrate is initially hydrolyzed by endoglycanases at random locations producing oligomeric intermediates. Those
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26/125 intermediates are then substrates for exo-dividing glucanases such as cellobiohydrolase to produce cellobiose from the ends of the cellulose polymer. Cellobiosis is a water-soluble 1,4-linked dimer of glucose. Finally, celobiase is divided into cellobiosis to generate glucose. In the case of hemicellulose, a xylanase (for example, hemicellulase) acts on this biopolymer and releases xylose as one of its possible products.
[0086] FIG. 3 is a flowchart showing manufacturing processes and a diagram showing manufacturing processes for hydroxycarboxylic acids from a raw material (eg cellulosic or lignocellulosic materials). In an initial stage (310), the method optionally includes the mechanical treatment of a cellulosic raw material and / or lignocellulosic material, for example, to reduce / reduce the size of the raw material. Before and / or after this treatment, the raw material can be treated with another physical treatment (312), for example, irradiation, heat treatment, sonication, vapor explosion, oxidation, pyrolysis or combinations of these, to reduce or further reduce plus your recalcitrance. A sugar solution, for example, including glucose and / or xylose, is formed by saccharifying the raw material (314). Saccharification can, for example, be carried out efficiently by the addition of one or more enzymes, for example, cellulases and / or xylanases (311) and / or one or more acids. A product or several products can be derived from the sugar solution, for example, by fermentation to a hydroxycarboxylic acid (316). After fermentation, the fermentation product (for example, or products, or a subset of fermentation products) can be further purified or further processed, for example, polymerized and / or isolated (324). Optionally, the sugar solution is a mixture of sugars and the body selectively ferment only one of the sugars. Fermentation of only one of the sugars in a mixture can be advantageous, as described in International Application No. PCT / US2014 / 021813 filed on March 7, 2014, the disclosure of which is incorporated into this document by reference in its
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12/27 totality. If desired, the steps for measuring the lignin content (318) and setting or adjusting the process parameters based on this measurement (320) can be performed at various stages of the process, for example, as described in US Patent 8,415,122, issued on 9 April 2013, the full disclosure of which is incorporated into this document by reference. Optionally, enzymes (for example, in addition to cellulases and xylanases) can be added in step (114), for example, a glucose isomerase can be used to isomerize glucose to fructose. Some relevant uses of isomerase are discussed in International Application No. PCT / US12 / 71093, filed on December 20, 2012, published as WO 2013/096700, the full disclosure of which is incorporated by reference in this document.
[0087] In some embodiments, liquids after saccharification and / or fermentation can be treated to remove solids, for example, by centrifugation, filtration, sweeping or vacuum filtration and rotary filtration. For example, some methods and equipment that can be used during or after saccharification are disclosed in US Order Serial No. 13 / 932,814, filed on July 1, 2013, published as US 2014/0004573; and International Order No. PCT / US2014 / 021584, filed on March 7, 2014, the full disclosures of which are hereby incorporated by reference. In addition, other separation techniques can be used in liquids, for example, to remove ions and discolor them. For example, chromatography, mobile bed chromatography and electrodialysis can be used to purify any of the solutions and / or suspensions described herein. Some of these methods are discussed in International Application No. PCT / US2014 / 021638, filed on March 7, 2014, and in International Application No.PCT / US2014 / 021815, filed on March 7, 2014, the full disclosures of which are incorporated herein. by reference. The solids that are removed during processing can be used in energy cogeneration,
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28/125 for example, as discussed in International Application No. PCT / US2014 / 021634, filed on March 7, 2014, the full disclosure of which is incorporated herein by reference. Optionally, the sugars released from biomass, as described in FIG. 3, for example, glucose, xylose, sucrose, maltose, lactose, mannose, galactose, arabinose, homodimers and heterodimers thereof (eg cellobiose, sucrose), trimers, oligomers and mixtures of these, can be fermented to hydroxycarboxylic acids, such as acids alpha, beta or gamma hydroxyls (eg, lactic acid). In some embodiments, saccharification and fermentation are carried out simultaneously, for example, using the thermophilic organism such as Bacilluscoagulans MXL-9, as described by S.L. Walton in J. Ind. Microbiol. Biotechnol. (2012) pg. 823-830.
[0088] Hydroxycarboxylic acids that can be produced by the methods, systems and equipment described herein include, for example, hydroxycarboxylic acids alpha, beta, gamma and delta. FIG. 8 shows the chemical structures of some hydroxy acids. That is, if there is only one hydroxyl group, it can be found in any of the alpha, beta, gamma or delta atoms in the carbon chain. The carbon chain can be a linear, branched or cyclic chain. Hydroxycarboxylic acid can also include fatty acids with a carbon chain length of 10 to 22 with the hydroxy substitute in alpha, beta, gamma or delta carbon.
[0089] Hydroxycarboxylic acids include those with multiple hydroxy substitutes, or in an alternative description, a carboxylic acid substituted with carboxylic acid. Such hydroxycarboxylic acids can be polyhydroxycarboxylic acids, for example, di-, tri-, tetra-, penta-, hexahepta- and octassubstituted hydroxycarboxylic acids. The carbon chain of the carboxylic acid can be linear, branched, cyclic or alicyclic. Examples of this are tartaric acid and its
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29/125 isomers, dihydroxy-3-methylpentanoic acid, 3,4-dihydroximandelic acid, gluconic acid, glucuronic acid and the like.
[0090] For example, glycolic acid, lactic acid (for example, D, L or mixtures of D and L), malic acid (for example, D, L and mixtures of D and L), citric acid, tartaric acid (for example example, D, L or mixtures of D and L), carmine, cyclobutyrol, 3dehydroquinic acid, diethyl tartrate, 2,3-dihydroxy-3-methylpentanoic acid, 3,4-dihydroximandelic acid, glycolic acid, homocitric acid, homoisocitric acid, beta acid -hydroxy beta-methylbutyric acid, 4-hydroxy-4-methylpentanoic acid, hydroxybutyric acid, 2-hydroxybutyric acid, beta-hydroxybutyric acid, gamma-hydroxybutyric acid, alpha-hydroxyglutaric acid, 5-hydroxyindoleacetic acid, 3-hydroxyisobutyric acid, 3-hydroxyisobutyric acid, 3-hydroxypropionic, hydroxypyruvic acid, gamma-hydroxyvaleric acid, isocitric acid, isopropylmalic acid, kunurenic acid, mandelic acid, mevalonic acid, monatin, myiocin, pamoic acid, pantoic acid, prefenic acid, shikimic acid, tartronic acid, threonic acid, tropic acid, vanilimandélico acid, xanthurenic acid, and mixtures thereof. For these listed hydroxy acids, all stereoisomers are included in the list. For example, tartaric acid includes the D, L isomers, mesoisomers and mixtures thereof.
PREPARATION OF HYDROXICARBOXYLIC ACID [0091] Organisms can use a variety of metabolic pathways to convert sugars to hydroxycarboxylic acid, and some organisms can selectively only use specific pathways. A well-studied example is lactic acid. Some organisms are homofermentative, while others are heterofermentative. For example, some paths are described in Journal of Biotechnology 156 (2011) 286-301. The path normally used by organisms to ferment glucose is the glycolytic path. Five-carbon sugars, such as xylose, can use the heterofermentative phosphoquetolase (PK) pathway. O
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30/125 path PK converts two of the 5 carbons in xylose to acetic acid in the remaining 3 to lactic acid (through pyruvate). Another possible path for five-carbon sugars is the pentose-phosphate (PP) / glycolytic pathway that produces only lactic acid.
[0092] Several organisms can be used to ferment sugars derived from biomass to lactic acid. The organisms can be, for example, lactic acid bacteria and fungi. Some specific examples nc uemRhizopus arrhízus, Rhízopus oryzae, (e.g. NRRL-395, ATCC 52311, NRRL 395, CBS 147.22, CBS 128.08, CBS 539.80, CBS 328.47, CBS 127.08 , CBS 321.35, CBS 396.95, CBS 112.07, CBS 127.08, CBS 264.28 / Enterococcus faecalis (for example, RKY1), Lactobacillus rhamnosus (for example, ATCC 10863. ATCC 7469, CECT-288 , NRRL B-445), Lactobacillus helveticus (for example, ATCC 15009, R211), Lactobacillus bulgaricus (for example NRRL B-548, ATCC 8001, PTCC 1332), Lactobacillus casei (for example, NRRL B-441), Lactobacillus plantarum (e.g. ATCC 21028, TISTR No. 543, NCIMB 8826), Lactobacillus pentosus (e.g. ATCC 8041), Lactobacillus amylophilus (e.g. GV6), Lactobacillus delbrueckii (e.g. NCIMB 8130, TISTR No. 326, Uc -3, NRRL-B445, IFO 3202, ATCC 9649), Lactococcus lactis sesp. Lactis (for example, IFO 12007), Lactobacillus paracasei No. 8, Lactobacillus amylovorus (ATCC 33620), Lactobacillus esp. (For example, RKY2), Lactoba cillus coryniformis sesp. torquens (e.g. ATCC 25600, B-4390), Rhízopus esp. (e.g. MK-96-1196), Enterococcus casseliflavus, Lactococcus lactis (TISTR No. 1401), Lactobacillus casei (TISTR No. 390), Lactobacillus thermophiles, Bacillus coagulans (e.g. MXL-9, 36D1, P4102B), Enterococcus mundtii (e.g. QU 25), Lactobacillus delbrueckii, Acremonium cellulose, Lactobacillus bifermentans, Corynebacterium glutamicum, L acetotolerans, L acidifarinae, L acidipiscis, L acidophilus, L agilis, L algidus, L alimentophusus, Lylari amylotrophicus, L amylovorus, L
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12/31 animalis, L. antri, L. apodemi, L. aviarius, L. bifermentans, L. brevis (e.g., B4527), L. buchneri, L. camelliae, L. casei, L. catenaformis, L. ceti , L. coleohominis, L. collinoides, L. composti, L. concavus, L. coryniformis, L. crispatus, L. crustorum, L. curvatus, L. delbrueckii subsp. Delbrieckii (for example, NRRL B-763, ATCC 9649), L. delbrueckii subsp. bulgaricus, L. delbrueckii subsp. lactis (for example, B-4525), L. dextrinicus, L. diolivorans, L. equi, L. equigenerosi, L. farraginis, L. farciminis, L. fermentum, L. fornicalis, L. fructivorans, L. frumenti, L. fuchuensis, L. gallinarum, L. gasseri, L. gastricus, L. ghanensis, L. graminis, L. hammesii, L. hamsteri, L. harbinensis, L. hayakitensis, L. helveticus, L. hilgardii, L. homohiochii, L. iners, L. ingluviei, L. intestinalis, L. jensenii, L. johnsonii, L. kalixensis, L. kefiranofaciens, L. kefiri, L. kimchii, L. kitasatonis, L. kunkeei, L. leichmannii, L. lindneri, L. malefermentans, L. mali, L. manihotivorans, L. mindensis, L. mucosae, L. murinus, L. nagelii, L. namurensis, L. nantensis, L. oligofermentans, L. oris, L. panis, L. pantheris, L. parabrevis, L. parabuchneri, L. paracollinoides, L. parafarraginis, L. parakefiri, L. paralimentarius, L. paraplantarum, L. pentosus, L. perolens, L. plantarum (for example, ATCC 8014), L. pontis, L. psittaci, L. rennini, L. reuteri, L. rhamnosus, L. rimae, L. rogosae, L. rossiae, L. ruminis, L. saerimneri, L. sakei, L. salivarius, L. sanfranciscensis, L. satsumensis, L. secaliphilus, L. sharpeae, L. siliginis, L. spicheri, L. suebicus, L. thailandensis, L. ultunensis, L. vaccinostercus, L. vaginalis, L. versmoldensis, L. vini, L. vitulinus, L. zeae, L. zymae, and Pediococcus pentosaceus (ATCC 25745).
[0093] Alternatively, the microorganism used for converting sugars to hydroxycarboxylic acids, including lactic acid, Lactobacillus casei, Lactobacillus rhamnosus, Lactobacillus delbrueckii subspecies delbrueckii, Lactobacillus plantarum, Lactobacillus corynusacisacisacillusacisacisacisifacis, Rhizopus
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32/125 oryzae, Enterococcus faecalis, Lactobacillus helveticus, Lactobacillus bulgaricus, Lactobacillus casei, lactobacillus amylophilus and mixtures of these [0094] Using the methods, equipment and systems described here, D or L isomers of lactic acid at approximately 100% optical purity (for example, at least approximately 80%, at least approximately 85%, at least approximately 90%, at least approximately 95%, at least approximately 99%) can be produced. Optionally, mixtures of isomers can be produced in any ratio, from 0% optical purity of any isomer to 100% optical purity of any isomer. for example, it is reported that the species, Lactobacillus delbrueckii (NRRL-B445) produces a mixture of D and L isomers, it is reported that Lactobacillus rhamnosus (CECT-28) produces the L isomer, while it is reported that Lactobacillus delbrueckii (IF 3202) produces the D isomer (Wang et al. in Bioresource Technology, June, 2010). As an additional example, organisms that predominantly produce the L (+) - isomer are L. amylophilus, L. bavaricus, L. casei, L. maltaromicus and L. salivarius, whereas L. delbrueckii, L. jensenii and L. acidophilus produce the D (-) - isomer or mixtures of both.
[0095] Genetically modified organisms can also be used. For example, genetically modified organisms (eg, lactobacillus, Escherichia coli) that are modified to express either L-Lactate dehydrogenase or D-lactate dehydrogenase to produce more L-lactic acid or D-lactic acid, respectively. In addition, some yeasts and Escherichia coli have been genetically modified to produce lactic acid from glucose and / or xylose.
[0096] Co-cultures of organisms, for example, selected from organisms such as those described here, can be used in the fermentation of sugars to hydroxycarbolic acid in any combination. For example, two or more bacteria, yeasts and / or fungi can be combined with one or more sugars
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33/125 (for example, glucose and / or xylose), where organisms ferment sugars together, selectively and / or sequentially. Optionally, an organism can be added first and fermentation takes place for a while, for example, until it stops fermenting one or more of the sugars, and then a second organism can be added to further ferment the same sugar or ferment a different sugar. Co-cultures can also be used, for example, to fine tune a desirable racemic mixture of D-lactic acid and L-lactic acid by combining a D-fermentable or L-fermentable organism in an appropriate proportion to form the desired racemic mixture.
[0097] In certain embodiments, fermentations using Lactobacillus are preferable. For example, the fermentation of glucose derived from biomass by Lactobacillus can be very efficient (for example, fast, selective and with high conversion). In other embodiments, the production of lactic acid using filamentous fungi is preferable. For example, the Rhizopus species can aerobically ferment glucose to lactic acid. In addition, some fungi (for example, R. oryzae and R. arrhizus) produce amylases, so that direct starch fermentation can be carried out without the addition of external amylases. Finally, some fungi (for example, R. oryzae) can ferment xylose, as well as glucose, where most lactobacillus are not efficient at fermenting sugars.
[0098] In some embodiments, some bioadditives (for example, components of the media) may be added during fermentation, for example, the bioadditives that can be used include yeast extract, rice bran, wheat bran, milhocine liqueur , final molasses, casein hydrolysis, plant extracts, milhocin solid, ram horn residues, peptides, peptone (eg, bactopeptone, polypeptone), pharmamedia, flower (eg, wheat flour, soy flour, flour cottonseed), malt extract, meat extract, tryptone, K2HPO4, KH2PO4, Na2HPO4, NaH2PO4, (NH4) 2PO4, NH4OH, NH4NO, urea, citrate
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34/125 ammonium, nitrilotriacetic acid, MnSO4'5H2O, MgSO47H2O, CaCl2,2H2O, FeSO47'H2O, B vitamins (for example, thiamine, riboflavin, niacin, niacinamide, pantothenic acid, pyridoxine, pyridoxal, pyridoxine, pyridoxine hydrochloride, pyridoxine, pyridoxine, pyridoxine, pyridoxine hydrochloride , folic acid), amino acids, sodium-L-glutamate, Na2 EDTA, sodium acetate, ZnSO 4 · 7H2O, ammonium molybdate tetrahydrate, CuCl2, CoCl2 and CaCO3 · Addition of protease can also be beneficial during fermentation. Optionally, surfactants like Tween 80 and antibiotics like Chloramphenicol can also be beneficial. Additional sources of carbon, for example, glucose, xylose and other sugars. Antifoam compounds, such as Antifoam 204, can also be used.
[0099] In some modalities, fermentation can take from approximately 8 hours to several days. For example, some batch fermentations can take from approximately 1 day to approximately 20 days (for example, from approximately 1 to 10 days, from approximately 3 to 6 days, from approximately 8 hours to 48 hours, from approximately 8 hours to 24 hours ).
[0100] In some embodiments, the temperature during fermentation is controlled, for example: the temperature can be controlled between approximately 20 ° C and 50 ° C (for example, between approximately 25 and 40 ° C, between approximately 30 and 40 ° Between approximately 35 and 40 ° C). In some case, thermophilic organisms are used that operate efficiently above approximately 50 ° C, for example, between approximately 50 ° C and 100 ° C (for example, between approximately 50-90 ° C, between approximately 50 and 80 ° C, between approximately 50 and 70 ° C).
[0101] In some embodiments, the pH is controlled, for example, by the addition of an acid or a base. The pH can optionally be controlled to be almost neutral (for example, between approximately 4-8, between approximately 5-7, between approximately 5-6). The acids, for example, can be protic acids, such as sulfuric, phosphoric, nitric, hydrochloride and acetic acids. Bases, for example, can
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35/125 include metal hydroxides (for example, sodium and potassium hydroxide), ammonium hydroxide and calcium carbonate. Phosphate and other dampers can also be used.
[0102] Fermentation methods include, for example, batch fermentation, fed batch, repeated batch or continuous reactors. Batch methods can often produce higher concentrations of lactic acids, whereas continuous methods can lead to higher productivity.
[0103] Feed batch methods may include the addition of medium components and substrates (for example, biomass sugars) while they are depleted. Optionally, products, intermediates, side products and / or waste products can be removed while they are being produced. In addition, a solvent (for example, water) can be added or removed to maintain the ideal amount for fermentation.
[0104] Options include cell recycling. For example, the use of a hollow fiber membrane to separate cells from medium components and products after fermentation is complete. The cells can then be reused in repeated batches. In other optional methods, cells can be sustained, for example, as described in US Order, Serial No. 13 / 293,971, filed Nov. 10. 2011 and in US patent no. 8,377,668, issued on February 19. 2013, whose full disclosures are hereby incorporated by reference.
[0105] The fermentation broth can be neutralized using calcium carbonate or calcium hydroxide, which can form calcium lactate. Calcium lactate is soluble in water (for example, approximately 7.9 g / 100mL). The calcium lactate broth can then be filtered to remove cells and other insoluble materials. In addition, the broth can be treated with a decolorizing agent, for example: the broth can be filtered through carbon. The broth is then
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36/125 concentrated, for example, by evaporation of water optionally in vacuum and / or gentle heating, and can be crystallized or precipitated. Acidification, for example, with sulfuric acid, releases lactic acid back into the solution, which can be separated (for example, filtered) from insoluble calcium salts, for example, calcium sulfate. The addition of calcium carbonate during fermentation can also serve as a way to reduce inhibition of the product since calcium lactate is not inhibitory or causes less inhibition of the product.
[0106] Optionally, reactive distillation can also be used to purify D-lactic acid and / or L-lactic acid. For example, methylation of D-lactic acid and / or L-lactic acid provides methyl ester, which can be distilled to pure ester, which can then be hydrolyzed to acid and methanol, which can be recycled. Esterification to other esters can also be used to facilitate separation. For example, reactions with alcohols for ethyl, propyl, butyl, hexyl, octyl or even esters with more than eight carbons can be formed and then extracted in a solvent or distilled.
[0107] Other alternative technologies for separating D-lactic acid and Lactic acid include adsorption, for example, from activated carbon, polyvinylpyridine, zeolite molecular sieves and ion exchange resins, such as basic resins. Other methods include ultrafiltration and electrodialysis.
[0108] The precipitation or crystallization of calcium lactate by the addition of organic solvents is another method of purification. For example, alcohols (for example, ethanol, propanol, butanol, hexanol), ketones (for example, acetone) can be used for this purpose.
[0109] Similar methods can be used for the preparation of other hydroxycarboxylic acids. For example, fermentative methods and procedures can be applicable to any of the hydroxycarboxylic acids described herein.
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POLYMERIZATION OF HYDROXICARBOXYLIC ACID [0110] Hydroxycarboxylic acid prepared as described here can be subjected to ester condensation to form dimers (for example, linear and cyclic), trimers, oligomers and polymers. When hydroxycarboxylic polyacid is a polylactic acid, it is consequently a condensed lactic acid polyester. PLA can be further processed (for example, grafted, treated or copolymerized to form side chains including ionizable groups). Both the D isomer and the L isomer of PLA can form polymers and / or can be copolymerized. The properties of the polymers depend on the amounts of lactic acid and L-lactic acid incorporated in the structure, as will be discussed later.
[0111] Polymers of hydroxycarboxylic polyacids are based on polyester methods. The balance between the hydroxycarboxylic acid component and the carboxylic acid component is preferably close to equimolar. For example, the limit of the molar ratio of the hydroxy / carboxylic groups can be in the range of 0.9 to 1.1, alternatively from 0.95 to 1.05, optionally from 0.98 to 1.02 or even from 0, 99 to 1.01. If a hydroxycarboxylic acid has an unequal amount of hydroxy substitutes relative to the carboxylic acid group, such as malic acid, then the additional amount of diol can be included to obtain a high molecular weight polymer, if desired.
[0112] PLA polymerization is done by the methods described above.
[0113] A method for producing high molecular weight PLA involves coupling PLA, for example, done as described above, using chain coupling agents, for example: hydroxyl-terminated PLA can be synthesized by condensation of D-lactic acid and / or L-lactic acid in the presence of small amounts of multifunctional hydroxyl compounds, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclohexanediol, 2
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38/125 butene-1,4-diol, glycerol, 1,4-butanediol, 1,6-hexanediol. Alternatively, the carboxyl-terminated PLA can be obtained by condensing lactic D-acid and / or lactic acid in the presence of small amounts of multifunctional carboxylic acids, such as maleic, succinic, adipic, itaconic and malonic acids. Aromatic diacids are also candidates.
[0114] These diols and diacids are additives and can be added to the melt flow only before the melt flow to the thin film evaporator or thin film polymerization / devolatilization device flows. In order to preserve the condensation parameters of the polymer, the diol and the diacid must be almost equimolar. If the molar ratio between alcohol and acid is too far from one, then finished polymers and / or finished oligomers will be obtained. Thus, the molar ratio of these diols and diacids is 0.95 to 1.05 or, optionally, 0.975 to 1.025. In addition, to preserve the polymer properties attributed to the hydroxycarboxylic polyacid, the dilution of the monomers with the diols and diacids must be minimal. Thus, optionally, the molar ratio of the sum of the aliphatic or aromatic dicarboxylic acid and the aliphatic or aromatic diol to the hydroxycarboxylic acid monomer of the hydroxycarboxylic acid is 0.1 or less. Alternatively, the limitation is 0.05 or less.
[0115] The punctual addition of the oligomers of alcohol or alpha or omega diacids can lead to a block polymer. This is especially true if the alcohols and diacids are added using the thin film evaporator or the thin film polymerization / devolatilization device. Examples of oligomers and dialcohols include low molecular weight polyethylene glycol, 1,2- and 1,3-propanoediol, 1,4-butanediol and the like.
[0116] The inclusion of small amounts of trisubstituted alcohols and tracids can also lead to a beneficial cross-linking of the hydroxycarboxylic polyacid. Amounts of less than 5% by weight, alternately less
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39/125 of 2.5% by weight or optionally less than 1% by weight can be used to produce a minimally branched polymer.
[0117] Other additives include chain extending agents that may have heterofunctional groups that couple to the final group of the PLA carboxylic acid or to the final group of the hydroxyl, for example: 6-hydroxycapric acid, mandelic acid, 4-hydroxybenzoic acid, 4-acetoxybenzoic.
[0118] Esterification promoting agents can also be combined with D-lactic acid and / or L-lactic acid to increase the molecular weight of PLA. For example, ester-promoting agents include phosgene, diphosgene, triphosgene dicyclohexicarbodiimide and carbonyldiimidazole. Some potentially undesirable side products can be produced by this method by adding purification steps to the process. After the final purification, the product can be very clean, free of catalyst and low molecular weight impurities.
[0119] The molecular weights of the polymer can also be increased by adding chain extender agents, such as (di) isocyanates, acid chlorides, anhydrides, epoxides, thyrane and oxazoline and orthoester.
[0120] Catalysts and promoters that can optionally be used include protonic acids, such as H3PO4, H2SO4, methane sulfonic acid, ptoluene sulfonic acid, NafionH + (sulfonic acid supported on / attached to a polymer that can optionally have a main structure of tetrafluoroethylene) , metal catalysts, for example, include Mg, Al, Ti, Zn, Sn. Some metal oxides that can optionally catalyze the reaction include TiO2, ZnO, GeO2, ZrO2, SnO, SnO2, Sb2O3. Metal iodides, for example, that can be beneficial include ZnCl2, SnCl2, SnCl4. Other catalysts that contain metals that can optionally be used include Mn (AcO) 2, Fe2 (LA) 3, Co (AcO) 2, Ni (AcO) 2, Cu (OA) 2, Zn (LA) 2, Y (OA ) 3, Al (/ PrO) 3, Ti (BuO) 4, TiO (acac) 2, (Bu) 2SnO. Combinations and mixtures of the above catalysts can also be used. For example, two or more catalysts can
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40/125 be added at a time or sequentially, as the polymerization progresses. The catalysts can also be removed, replenished and / or regenerated in the course of polymerization for repeated polymerizations. Some of the preferred combinations include protonic acids and one of the metals containing catalysts, for example, SnCl2 / p-toluenesulfonic acid. These catalysts are normally added between steps 2 and 3 of the polymerization process described above.
[0121] During step 1 of the polymerization process, for example, especially at the beginning of the polymerization, when the concentration of lactic acid is high and water is being formed at a high rate, the azeotropic mixture of lactic acid / water can be condensed and passed through molecular sieves to dehydrate the lactic acid, which is then returned to the reaction vessel.
[0122] Copolymers can be produced by adding monomers other than lactic acid during the azeotropic condensation reaction. For example, any of the carboxylic and hydroxyl compounds or heterofunctional compounds that can be used as coupling agents for low molecular weight PLA can also be used as comonomers in the azeotropic condensation reaction.
[0123] In addition to homopolymer, copolymerization with other cyclic monomers and non-cyclic monomers such as glycolide, caprolactone, valerolactone, dioxipenone, trimethyl carbonate, 1,4-benzodioxepine-2,5- (3H) dione, lactosalicinate 1, lactosalicinate 1, 4- benzodioxepine-2,5- (3H, 3-methyl) -dione, dibenzo1,5 dioxacin-6-12-dione, morpholine-2,5-dione, 1,4-dioxane-2,5-dione glycolide , εcaprolactone oxepano-2-one, trimethylene carbonate 1,3-dioxane-2-one, 2,2-dimethyltrimethylene carbonate, 1,5-dioxepan-2-one, p-dioxanone 1,4-dioxane-2- one, gamma-butyrolactone, beta-butyrolactone, beta-me-delta-valerolactone, ethylene oxalate 1,4-dioxane-2,3-dione, 3- [benzyloxycarbonyl meyl] -1,4-dioxane-2,5- diona, oxide
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41/125 ethylene, propylene oxide, 5.5 '(oxepane-2-one), 2,4,7,9-tetraoxaspospiro [5.5] undecane-3,8-dione, Spiro-bid- carbonate dimethylene can produce copolymers. Copolymers can also be produced by adding monomers such as multifunctional carboxylic and hydroxyl compounds or heterofunctional compounds that can be used as coupling agents for low molecular weight PLA.
[0124] Copolymers can also be formed with other hydroxycarboxylic acids. Comonomers include 3-hydroxyvalerate 4-hydroxybutyrate, which are gamma and delta hydroxycarboxylic acids, respectively. Another monomer that can be copolymerized is 3-hydroxybutyrate (beta-substituted). These monomers can be copolymerized or mixed as polymers with a polylactic acid polymer to form a polymer mixture.
[0125] In addition to the chemical method, D-lactic acid and / or L-lactic acid can be polymerized by enzymes and polymerizing organisms from LA.
STYLECHEMISTRY OF POLYHYDROXYL CARBOXYLIC [0126] The mechanical and thermal properties of the homopolymer of hydroxyl carboxylic acid are largely determined by the molecular weight and stereochemical composition of the main structure. For lactic acid, the stereochemical composition of the main structure can be controlled by the choice and proportion of the monomers; D-lactic acid, L-lactic acid or, alternatively, Dlactide, L-lactide or meso-lactide. This stereochemical control allows the formation of random or block stereocopolymers. The molecular weight of the polymers can be controlled, for example, as discussed above. The ability to control the stereochemical architecture allows, for example, precise control over the speed and degree of crystallinity, the mechanical properties and the melting point and glass transition temperatures of the material.
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42/125 [0127] The degree of crystallinity of the PLA influences the hydrolytic stability of the polymer, and therefore, the biodegradability of the polymer. For example, highly crystalline PLA can take months to years to degrade, whereas amorphous samples can degrade in a few weeks or months. This behavior is partly due to the impermeability of the crystalline regions of the PLA. Table 1 shows some of the thermal properties of some PLA of similarly treated samples. The information in Table 1 comes from polylactic acid: PLA Biopolymer Technoloqy and Applications, Lee Tin Sin, A. R. Rahmat, W. A. Rahman; Dec 31, 2012. The percentage of crystallinity can be calculated using data from the table and applying the equation.
[0128] Where AH _m is the melting enthalpy in J / g, ΔΗ ₀ is the enthalpy of crystallization in J / g and 93 is the enthalpy of crystallization of a fully crystalline sample of PLA in J / g.
[0129] As can be calculated from the data in the table, crystallinity is directly proportional to the molecular weight of pure L or D stereopolymer. The stereoisomer DL (for example, an atactic polymer) is amorphous.
Table 1: PLA thermal properties
Isomer Type of Mn x 10 ³ Mw / Mn Tg (° C) Tm (° C) ΔΗ(J / g) Tc (° C) ΔΗ(J / g) L 4.7 1.09 45.6 157.8 55.5 98.3 47.8 DL 4.3 1.90 44.7 - - - - L 7.0 1.09 67.9 159.9 58.8 108.3 48.3 DL 7.3 1.16 44.1 - - - - D 13.8 1.19 65.7 17.03 67.0 107.6 52.4 L 14.0 1.12 66.8 173.3 61 110.3 48.1 D 16.5 1.20 69.1 173.5 64.6 109.0 51.6 L 16.8 1.32 58.6 173.4 61.4 105.0 38.1
[0130] The calculated crystallinities are ordered from top to bottom: 8.2%, 0%, 11.3%, 0%, 15.7%, 13.8%, 14.0% and 25%.
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43/125 [0131] Heat treatment of samples, for example, melting rates, recrystallization, and calcination history, can partially determine the amount of crystallization. Consequently, comparisons of the thermal, chemical and mechanical properties of PLS polymers should generally be more significant for polymers with a similar thermal history.
[0132] L-PLA or pure D-PLA has a higher tensile strength and low elongation and, consequently, has a higher modulus than DL-PLA. The values for L-PLA vary greatly depending on how the material is made, for example, tensile forces from 30 to almost 400 MPa and tensile modules between 1.7 to approximately 4.5 GPa.
HYDROXICARBOXYL POLYACIDE COPOLYMERS, HALF AND GRAFT [0133] The variation of hydroxycarboxylic polyacids by copolymer formation as discussed above has a very large influence on the properties, for example, by interrupting and decreasing the crystallinity and modulating the transition temperatures for glass. For example, polymers with greater flexibility, improved hydrophilicity, better degradability, better biocompatibility, better tensile strengths, improved elongation properties can be produced.
[0134] The thin film polymerization / devolatilization device can be the process where these comonomers can be added to the melted polymer.
[0135] Comonomers to produce copolymers with hydroxycarboxylic acids. In many cases, the improvements are correlated with a decrease in the transition temperature to glass. A few monomers can increase the glass transition temperature of the hydroxylcarboxylic polyacid. For example, salicylic acid lactones can have temperatures of
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44/125 transition to homopolymer glass between about 70 and 110 ° C and copolymerize hydroxyl carboxylic acid.
[0136] Morfolinediones, which are half alpha hydroxycarboxylic acids and half alpha amino acids, copolymerize with lactide to generate random copolymers with high molecular weight with reduced glass transition temperatures (for example, following the Flory-Fox equation). For example, the morpholiniones composed of glycine and lactic acid (6-methyl-2,5-morpholinione), when copolymerized with lactide, can generate a polymer with glass transition temperatures of 109 and 71 ° C for a lactic acid of 50 and 75 mole%, respectively, in the polymer. Morfolinediones were synthesized using glycolic acid and lactic acid and most of the alpha-amino acids (eg, glycine, alanine, aspartic acid, lysine, cysteine, valine and leucine). In addition to reducing the transition temperature to glass and improving mechanical properties, the use of functional amino acids in the synthesis of morpholinoids is an effective way to incorporate functional pendant groups into the polymer.
[0137] As an example, glycolide and lactide copolymers may be useful as biocompatible surgical sutures due to improved flexibility and hydrophilicity. The highest melting point of 228 ° C and Tg of 37 ° C for polyglycolic acid can produce a range of amorphous copolymers with a lower glass transition temperature than lactic polyacid. Another example of copolymerization is copolymerization with e-caprolactone, which can yield hard polymers with properties ranging from wrinkled plastics to elastomeric rubbers and with tensile forces ranging from 80 to 7000 psi, and elongation at more than 400%. Beta-methyl-gamma-valerolactone copolymers reportedly produced rubber-like properties. Copolymers with polyethers, such as poly (ethylene oxide), poly (propylene oxide) and poly (tetramethylene oxide), are biodegradable, biocompatible and flexible polymers.
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45/125 [0138] Some additional useful monomers that can be copolymerized with lactide include 1,4-benzodioxepine-2,3 (H) -dione glycolsalicilide; lactosalicilide
1.3-benzodioxepine-2,5- (3H, 3-methyl) -dione; dibenzo-1,5 dioxacin-6-12dione disalicilide; morpholine-2,5-dione, glycolide 1,4-dioxane-2,5-dione; trimethylene oxepano-2-one carbonate; 2,2-dimethyltrimethylene carbonate; 1,5-dioxepane-2-one; pdioxanone 1,4-dioxane-2-one; gamma-butyrolactone; beta-butyrolactone; beta-methyldelta-valerolactone; beta-methyl-gamma-valerolactone; 1,4-dioxane-ethylene oxalate
2.3- dione; 3 - [(benzyloxycarbonyl) methyl] -1,4-dioxane-2,5-dione; ethylene oxide; propylene oxide; 5.5 ’(oxepane-2-one) and Spiro-bid-dimethylene undercane-3,8dione 2,4,7,9-tetraoxaspiro [5,5] caronate.
[0139] Hydroxycarboxylic acid polymers and copolymers can be modified by crosslinking additives. Crosslinking can affect thermal and rheological properties without necessarily deteriorating mechanical properties. For example, cross-linking of 0.2 mol% 5.5'-bis (oxepano-2-one) (bis-ε caprolactone)) and 0.1-0.2 mol% spiro-bis-dimethylene carbonate. Hydrogen abstraction reactions with free radicals and the subsequent recombination of the polymer radical is an effective way to induce crosslinking in a polymer. Radicals can be generated, for example, by a high-energy electron beam and other radiation (for example, between about 0.01 Mrad and 15 Mrad, for example, between about 0.015 Mrad, between about 0.1 -5 Mrad, between about 1 -5 Mrad). For example, irradiation methods and equipment are described in detail below.
[0140] Alternatively, or in addition, additive peroxides, such as organic peroxides, are effective producers of radical and crosslinking agents. For example, peroxides that can be used include hydrogen peroxide, dicumil peroxide; benzoyl peroxide; 2,5-Dimethyl-2,5-di (tert-butylperoxy) hexane; tert-butylperoxy 2-ethylexyl carbonate; tert-amyl peroxy-2-ethylhexanoate; 1,1-di (tercamylperoxy) cyclohexane; tert-amyl peroxyenedecanoate; tert-amyl peroxbenzoate;
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46/125 tert-amylperoxy 2-ethylhexyl carbonate; tert-amyl peroxyacetate; 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane; tert-butyl peroxy-2-ethylhexanoate; 1,1-di (tertbutylperoxy) cyclohexane; tert-butyl peroxyenedecanoate; tert-butyl peroxineoheptanoate; tert-butyl peroxyethylacetate; 1,1-di (tert-butylperoxy) -3,3,5trimethylcyclohexane; 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonan; di (3,5,5-trimethylhexanoyl) peroxide; tert-butyl peroxyisobutyrate; tert-butyl peroxy-3,5,5-trimethylhexanoate; di-tert-butyl peroxide; isopropyl tert-butylperoxy carbonate; tert-butyl peroxybenzoate; 2,2-di (tert-butylperoxy) butane; di (2-ethylhexyl) peroxydicarbonate; di (2-ethylhexyl) peroxydicarbonate; tert-butyl peroxyacetate; tert-butyl cumyl peroxide; tercamillhydroperoxide; 1,1,3,3-tetramethylbutyl hydroperoxide and mixtures thereof. The effective amounts may vary, for example, depending on the peroxide, the crosslinking conditions and the desired properties (for example, crosslinking amount). For example, crosslinking agents can be added from approximately 0.01 to approximately 10% by weight (for example, approximately 0.1-10% by weight, approximately 0.01-5% by weight, approximately 0.1- 1% by weight, approximately 1-8% by weight, approximately 4-6% by weight). For example, peroxides, such as dicumil peroxide of 5.25% by weight and benzoyl peroxide of 0.1%, are effective producers of radical and crosslinking agents for hydroxycarboxylic polyacids and derivatives of hydroxycarboxylic polyacids. Cross-linking agents can be added to polymers such as solids, liquids or solutions, for example, in water or organic solvents, such as mineral essences. In addition, radical stabilizers can be used.
[0141] Crosslinking can also be effectively carried out by incorporating or unsaturation into the polymer chain by: initiation with unsaturated alcohols, such as hydroxyethyl methacrylate or 2-butene-1,4-diol; post-reaction with unsaturated anhydrides, such as maleic anhydride, to transform the end of the
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47/125 hydroxyl chain; or copolymerization with unsaturated epoxides such as glycidyl methacrylate.
[0142] In addition to crosslinking, grafting functional groups and polymers to a hydroxycarboxylic acid polymer or copolymer is an effective method of modifying the polymer's properties. For example, radicals can be formed as described above and a monomer, functionalizing polymer or small molecule. For example, irradiation or treatment with a peroxide followed by extinction with a functional group containing an unsaturated bond can effectively functionalize the main structure of the hydroxycarboxylic polyacid.
[0143] The thin film polymerization / devolatilization device can be the process in which these crosslinking and / or graft components can be added to the molten polymer.
HYDROXICARBOXYLICMIXTURE POLYACIDE S [0144] Hydroxycarboxylic polyacids can be mixed with other polymers as miscible and immiscible compositions. For immiscible mixtures, the composition can be one with the minor component (for example, below 30% by weight) in the form of (for example, micron or submicron) domains in the main component. When a component is approximately 30 to 70% by weight, the mixture forms a co-continuous morphology (for example, lamellar hexagonal phases or amorphous continuous phases). The polymers to be mixed with the hydroxycarboxylic polyacids can be random, linear, copolymer, diblock, graft, star and branched polymers.
[0145] Mixing can be carried out by melt mixing above the glass transition temperature of the amorphous polymer components. The thin-film evaporator and thin-film polymerization / devolatilization device can be used to mix the polymers. In addition, screw extruders (eg single screw extruders, screw extruders
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48/125 corrotative twins, counter-rotating twin screw extruders) may be useful for this purpose. For hydroxycarboxylic acid polymers and copolymers, temperatures below approximately 200 ° C can be used to prevent thermal degradation (for example, below approximately 180 ° C) [0146] Polyethylene oxide (PEO) and polypropylene oxide ( PPO) can be mixed with hydroxycarboxylic polyacids. Glycols with lower molecular weights (300-1000 Mw) are miscible with hydroxycarboxylic polyacids, whereas PPO becomes immiscible at a higher molecular weight. These polymers, especially PEO, can be used to increase the water transmission and biodegradation index of hydroxycarboxylic polyacids. They can also be used as polymeric plasticizers to reduce the modulus and increase the flexibility of hydroxycarboxylic polyacids. The high molecular weight PEG (20,000) is miscible with hydroxycarboxylic polyacids up to approximately 50%, but above that level the PEG crystallizes, reducing the ductibility of the mixture.
[0147] Polyvinyl acetate (PVA) is miscible with hydroxycarboxylic polyacids in most concentrations. For PVA and lactic polyacid mixtures, only one Tg is observed in all proportions of the mixture, with a constant decrease of approximately 37 ° C at 100% PVA. The low levels of PVA (5-10%) increase the tensile strength and% elongation of hydroxycarboxylic polyacids while significantly reducing the mass loss index during biodegradation.
[0148] Mixtures of hydroxycarboxylic polyacids and polyefins (polypropylene and polyethylene) result in incompatible systems with poor physical properties due to poor interfacial compatibility and high interfacial energy. However, interfacial energy can be reduced, for example, by adding third-component compatibilizers, such as graft polyethylene glycidyl methacrylate (irradiation would probably work) Polystyrene and resins
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49/125 high-impact polystyrene is also non-polar and mixtures with hydroxycarboxylic polyacids are generally not compatible.
[0149] Hydroxycarboxylic polyacids and acetals can be mixed into compositions with useful properties. For example, these mixtures have good, high transparency.
[0150] In general, hydroxycarboxylic polyacids are miscible with polymethyl methacrylate and several other acrylates and copolymers of (meth) acrylates. The films removed from the polymethyl methacrylate / mixtures of hydroxycarboxylic polyacids can be transparent and have a high elongation.
[0151] Polycarbonate can be combined with hydroxycarboxylic polyacids to polycarbonate compositions of up to approximately 50% by weight. The compositions have high heat resistance, flame resistance and hardness and have applications, for example, in consumer electronics, such as laptops. Polycarbonate of approximately 50% by weight, processing temperatures approach the degradation temperature of hydroxycarboxylic polyacids.
[0152] Acrylonitrile butadiene styrene (ABS) can be mixed with hydroxycarboxylic polyacids, although the polymers are not miscible. This combination is of less fragile material than that of hydroxycarboxylic polyacids and provides a way to reinforce hydroxycarboxylic polyacids.
[0153] The poly (propylene carbonate) can be mixed with the hydroxycarboxylic polyacids to provide a biodegradable compound, since the two polymers are biodegradable.
[0154] Hydroxycarboxylic polyacids can also be mixed with poly (butylene succinate). Mixtures can give thermal stability and impact strength to hydroxycarboxylic polyacids.
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50/125 [0155] PEG, propylene polyglycol, poly (vinyl acetate) anhydrides (eg maleic anhydride) and fatty acid esters have been added to plasticizers and / or compatibilizers.
[0156] The mixing can also be carried out with the application of irradiation, including irradiation and extinction. For example, irradiation or irradiation and extinction as described herein applied to biomass can be applied to the irradiation of hydroxycarboxylic polyacids and copolymers of hydroxycarboxylic polyacids for any purpose, for example, before, during and / or after mixing. This treatment can help in processing, for example, making polymers more compatible and / or making / breaking bonds within the polymer and / or mixed additives (for example, polymer and plasticizer). For example, between about 0.1 Mrad and 150 Mrad, followed by the extinction of radicals by the addition of fluids or gases (eg, oxygen, nitrous oxide, ammonia, liquids), using pressure, heat, and / or the addition of radical removers. The extinction of the biomass that has been irradiated is described in Pat. No. 8,083,906 to Medoff, the full disclosure of which is incorporated herein by reference, and the equipment and processes described herein can be applied to hydroxycarboxylic polyacids and derivatives of hydroxycarboxylic polyacids. Irradiation or extrusion or transport of hydroxycarboxylic polyacids or copolymers of hydroxycarboxylic polyacids can also be used, for example, for the treatment of biomass, as described in US Order. Serial No. 13 / 099.51, filed on May 2, 2011, published as US Order 2011-0262985, the complete disclosure of which is hereby incorporated by reference.
HYDROXICARBOXYLIC POLYACIDE COMPOUNDS [0157] Polymers, copolymers and mixtures of hydroxycarboxylic polyacid can be combined with synthetic and / or natural materials. For example, hydroxycarboxylic polyacids and derivatives of hydroxycarboxylic polyacids (for example, copolymers of hydroxycarboxylic polyacids, mixtures of polyacids
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51/125 hydroxycarboxylics, hollow hydroxycarboxylic polyacids, cross-linked hydroxycarboxylic polyacids) can be combined with synthetic and natural fibers. For example, protein, starch, cellulose, vegetable fibers (for example, abaca fibers, leaf, skin, trunk, hibiscus hemp), inorganic fillers, linen, talc, glass, mica, saponite and carbon fibers. This can provide a material with, for example, improved mechanical properties (for example, strength, hardness, strength) and improved barrier properties (for example, lower permeability to water and / or gases).
[0158] compostocompositesNanocomposites can also be produced by dispersing inorganic or organic nanoparticles within a thermoplastic or thermoset polymer. Nanoparticles can be spherical, polyhedral, two-dimensional nanofibers or disk-shaped nanoparticles. For example, colloidal or microcrystalline silica, oxides of alumina or metal (for example, TiO2); carbon nanotubes; clay platelets.
[0159] Compound Compounds can be prepared in a similar way to polymer mixtures, for example, using screw extrusion and / or injection molding. Irradiation, as described here, can also be applied to compost compounds, during, after or before their formation. For example, irradiation of the polymer and the combination with synthetic and / or natural materials, or irradiation of the synthetic and / or natural materials and combination with the polymer, or irradiation of both the polymer and the synthetic / or natural material and then combine, or irradiate the compound after it has been combined, with or without further processing.
HYDROXICARBOXYL POLYACIDS WITH PLASTICIZERS AND ELASTOMERS
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52/125 [0160] In addition to the mixtures discussed above, hydroxycarboxylic polyacids and derivatives of hydroxycarboxylic polyacids can be combined with plasticizers.
[0161] For example, as described in J. Appl. Polym. Sci. 66: 15071513, 1997, the lactic polyacid can be mixed with monomeric and oligomeric plasticizers to enhance its flexibility and consequently overcome its inherent fragility. Monomeric plasticizers, such as tributyl citrate, and bishhydroxymethyl diethyl malonate, DBM, can dramatically decrease PLA Tg. The increase in molecular weight of plasticizers through the synthesis of oligoesters and oligoesteramides can result in mixtures with depressions of Tg slightly lower than those of monomeric plasticizers. Compatibility with hydroxycarboxylic polyacids may depend on the molecular weight of the oligomers and the presence of polar groups (for example, amide groups, hydroxyl groups, ketones and esters) that can interact with the hydroxycarboxylic polyacid chains. Materials can retain high flexibility and morphological stability for long periods of time, for example, when formed into films.
[0162] Citrate esters can also be used with plasticizers with hydroxycarboxylic polyacids. The films can be extruded, for example, using a single screw or double screw extruder with plasticizing contents (ester citrates and others described in this document) of between about 1 and 40% by weight (for example, approximately 5 -30% by weight, approximately 5-25% by weight, approximately 5-15% by weight). Plasticizers such as citrate esters can be effective in reducing the transition temperature to glass and in improving elongation at break. The plasticizing efficiency can be higher for plasticizers of intermediate molecular weight. The addition of plasticizers can modulate the enzymatic degradation of hydroxycarboxylic polyacids. For example, citrates of lower molecular weight
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53/125 can increase the rate of degradation of hydroxycarboxylic polyacids and the higher molecular hair citrates can decrease the rate of degradation compared to that of non-plasticized hydroxycarboxylic polyacids.
[0163] The preparation of hydroxycarboxylic polyacid / elastomer mixtures can also be done by the melt blending technique, for example, as described in Journal of Elastomers and Plastics, January 3, 2013; hydroxycarboxylic polyacids and biodegradable elastomer can be mixed by melting and molded in an injection molding machine. The melting temperature may decrease while the amount of elastomer increases. Additionally, the presence of elastomer can modulate the crystallinity of hydroxycarboxylic polyacids, for example, increasing crystallinity to approximately 1 and 30% (for example, between approximately 1 to 20%, between approximately 5 and 15%). The complex viscosity and storage module of the hydroxycarboxylic polyacid casting can decrease with the addition of the elastomer. Elongation at break may increase as elastomer content has increased while Young's modulus and tensile strength often decrease due to the addition of elastomer.
[0164] It was observed that the cold crystallization temperature of the mixtures decreased while the weight fraction of the elastomer increased, as well as the cold crystallization onset temperature changed to a lower temperature. For example, as reported in Journal of Polymer Research, February 2012, 19: 9818. In non-isothermal crystallization experiments, the crystallinity of the lactic polyacid increases with a decrease in the heating and cooling rates. Crystallization of the foundry, for example, of lactic polyacid appeared in the low refrigeration index (1, 5 and 7.5 ° C / min). The presence of small amounts of elastomer can also increase the crystallinity of the lactic polyacid. The DSC thermogram on a 10 ° C / min ramp demonstrated that crystallinity
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54/125 lactic polyacid maximum is 36.95% with 20% by weight of the elastomeric content in mixtures. In isothermal crystallization, the index of cold crystallization increased with increasing crystallization temperature in the mixtures. Avrami analysis showed that cold crystallization occurred in two-step processes and was clearly seen at low temperatures. The Avrami exponent (n) in the first stage was varying from 1.59 to 2.0, which described a one-dimensional crystallization growth with homogeneous nucleation, whereas in the second stage, it varied from 2.09 to 2.71, the that described the transitional mechanism for growth of three-dimensional crystallization with homogeneous nucleation mechanism. The equilibrium melting point of the lactic polyacid was also evaluated at 176 ° C.
[0165] Some examples of elastomers that can be combined with PLA include: NPEL001 elastomer, polyurethane elastomers (5-10%), functionalized polyolefin elastomers, Blendex® (eg 415, 360, 338), PARALOID ™ KM 334 , BTA 753, EXL 3691A, 2314, Ecoflex® Supersoft Silicone Bionolle® 3001, Pelleethane® 2102-75A, Kraton® FG 1901X, Hytrel® 3078 and mixtures thereof. Mixtures with any other elastomer, for example, as described herein, can also be used.
[0166] Some examples of plasticizers that can be combined with hydroxycarboxylic polyacids include: Triacetin, gicerol triacetate, tributyl citrate, polyethylene glycol, GRINDSTED® SOFT-N-SAFE (acetic acid monoglyceride ester) made from totally castor oil hydrogenated and combinations of these. Mixtures with any other plasticizer, for example, as described here, can also be used.
[0167] The main characteristic of elastomeric materials is the high elongation and the flexibility or high elasticity of these materials, against cracking or cracking.
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55/125 [0168] Depending on the distribution and degree of chemical bonds of the polymers, elastomeric materials may have properties or characteristics similar to thermosets or thermoplastics, so that elastomeric materials can be classified into: Thermoset elastomers (for example, do not melt when heated) and Thermoplastic Elastomers (for example, melt when heated). Some properties of elastomeric materials: they cannot melt, before melting they pass to a gaseous state; swell in the presence of certain solvents; in general, they are insoluble; they are flexible and elastic; less resistance to deformity than thermoplastic materials.
[0169] Examples of applications for elastomeric materials described here: possible substitutes or replacements for natural rubber (for example, material used in the manufacture of sealing plates, heels); possible substitutes or replacements for polyurethanes (for example, for use in the textile industry, in the manufacture of elastic clothing, for use as foam and for use in the manufacture of wheels); possible substitutes or replacements for polybutadiene (for example, elastomeric material used in wheels or in vehicle tires); possible substitutes or replacements for neoprene (for example, used in the manufacture of diving suits, wire insulation, industrial belts); possible silicone substitutes or replacements (eg, pacifiers, medical prostheses, lubricants). In addition, the materials described here can be used as substitutes for polyurethane and silica adhesives.
FLAVORS, FRAGRANCES AND COLORS [0170] Any of the products and / or intermediates described herein, for example, hydroxycarboxylic polyacids, derivatives of hydroxycarboxylic polyacids, polyhydroxycarboxylic hydroxycarboxylic polyacids, polyhydroxycarboxylic polyacid compounds, compounds grafted, mixtures of hydroxycarboxylic polyacids and other
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56/125 hydroxycarboxylic polyacids containing material prepared as described here) can also be combined with flavors, fragrances, colors and / or mixtures thereof. For example, one or more of (optionally, in conjunction with flavors, fragrances and / or colors) sugars, organic acids, fuels, polyols, such as sugar alcohols, biomass, fibers and compost-compounds, l-hydroxycarboxylic acids, lactic acid, polyacids hydroxycarboxylic acids, derivatives of hydroxycarboxylic polyacids can (s) be combined with (for example, formulated, mixed or reacted) or used (s) to make other products. For example, one or more of these products may be used in the manufacture of soaps, detergents, sweets, beverages (for example, cola, wine, beer, alcoholic beverages such as gin or vodka, sports drinks, coffee , teas), drugs, adhesives, bedding (for example, fabrics, nonwovens, filters, scarves) and / or compost-compounds (for example, plates). For example, one or more of these products can be combined with herbs, flowers, petals, spices, vitamins, aromatic sachets or candles. For example, formulated, mixed or reacted combinations may have grapefruit, orange, apple, raspberry, banana, lettuce, celery, cinnamon, vanilla, mint, mint, onion, garlic, pepper, saffron, ginger, milk flavors. , wine, beer, tea, lean meats, fish, clams, olive oil, coconut fat, pork fat, butter fat, broth, vegetables, potatoes, marmalade, ham, coffee and cheeses.
[0171] Flavors, fragrances and colors can be added in any quantity, such as between about 0.01% by weight to about 30% by weight, for example, between about 0.05 to about 10, between about 0.1% to about 5, or between about 0.25% by weight to about 2.5% by weight. These can be formulated, mixed and / or reacted (for example, with any product or intermediate described herein) by any means and in any order or sequence (for example, stirred, mixed, emulsified, gelled, infused, heated,
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57/125 sonicated and / or suspended). Fillers, binders, emulsifiers, antioxidants can also be used, for example, protein gels, gums and silica.
[0172] Flavors, fragrances and colors can be natural and / or synthetic materials. These materials can be one or more of a compound, composition or mixtures thereof (for example, a natural or formulated composition of several compounds). Optionally, flavors, fragrances, antioxidants and colors can be derived biologically, for example, from a fermentation process (for example, fermentation of saccharified materials as described herein). Alternatively, or in addition, these flavors, fragrances and colors can be harvested from an entire organism (for example, plant, fungus, animal, bacteria or yeast) or from a part of an organism. The organism can be collected and / or extracted to provide color, flavors, fragrances and / or antioxidants by any means, including using the methods, systems and equipment described here, hot water extraction, chemical extraction (for example, solvent extraction or reactive, including acids and bases), mechanical extraction (eg, pressure, comminution, filtration), using an enzyme, using a bacterium, in order to decompose a raw material, and combinations of these methods. The compounds can be derived by a chemical reaction, for example, the combination of a sugar (for example, with a production as described here) with an amino acid (Maillard reaction). The taste, fragrance, antioxidant and / or dye can be an intermediate and / or product produced by the methods, equipment or systems described herein, for example, an ester and a product derived from lignin.
[0173] Some examples of taste, fragrances and colors are polyphenols. Polyphenols are pigments responsible for the red, purple and blue coloring of many fruits, vegetables, cereal grains and flowers. Polyphenols can also have antioxidant properties and often taste bitter. The antioxidant properties make these preservatives important. In the polyphenols class are the
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58/125 flavonoids, such as anthrocyanins, flavonols, flavan-3-ools, flavones, flavanones and flavonoids. Other phenolic compounds that can be used include phenolic acids and their esters, such as chlorogenic acid and polymeric tannins.
[0174] Inorganic compounds, mineral or organic compounds can be used, for example, titanium dioxide, cadmium yellow (for example, CdS), cadmium orange (for example, CdS with some SE), alizarin red (for example , synthetic or non-synthetic rose granite), ultramarine blue (for example, synthetic ultramarine blue, natural ultramarine blue, synthetic violet-ultramarine), azulcobalt, cobalt yellow, cobalt green, viridian (eg oxide (hydrated chromium (III)), chalcophilite, conicalcite, cornubite, cornualite and liroconite.
[0175] Some flavors and fragrances that can be used include AZALEIA TBHQ, ACET C-6, ALIL AMIL GLICONATO, ALFA TERPINEOL, AMBRETOLIDA, AMBRINOL 95, ANDRANE, AFERMATO, APLELIDA, BACDANOL®, BERGAMAL, ÉPOXIDO DE BETA-IONONAÉ, ETER ISOBUTYLIC OF BETA NAFTIL, BICYCLONONALACTONE, BORNAFIX®, CANTOXAL, CASHMERAN®, CASHMERAN® VELUDO, CASSIFFIX®, CEDRAFIX, CEDRAMBER®, CEDRIL ACETATE, CELESTOLIT, CINNELLYL, CINNYLATE, CYLINDERYLIDE, CINNELLYL, , CITRONELIL ACETATE, PURE CITRONELIL ACETRATE, CITRONELIL FORMIATE, CLARYCET, CLONAL, CONIFERAN, PURE CONIFERAN, ALDEHYDE CORTEZ 50% PEOMOSA, CYCLABUTE, CYCLACET®, CYCLAPROXY, , CYCLACET DIIDRO, MIRCENOL DIIDRO, TERPINEOL DIIDRO, TERPINYL ACIDATE DIIDRO, DIMETHYL CYCLORMOL, DIMETHYL OCTANOL PQ, DIMIRCETOL, DIOLA, DIPENTENE, DULCINYL® RECRISTALIZED, FYCIDYL-ADHYLENYLATE, 3-GLYCEDYL FLORAL, FLORALOZONE, FLORIFFOL, FRAISTONE, FRUCTONA,
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GALAXOLIDE® 50, GALAXOLIDE® 50 BB, GALAXOLIDE® 50 IPM, GALAXOLIDE® UNDILUTED, GALBASCONA, GENERALDEHYDE, GERANIOL 5020, GERANIOL TYPE 600, GERANIOL 950, GERANIOL 980 (PURO), GANER COEUR, GERANIL ACETATE, PURE, GERANIL FORM, GRISALVA, GUAÍLA ACETATE, HELIONAL ™, HERBAC, HERBALIME ™, HEXADECANOLID, HEXALON, HEXENIL SALICILATO CIS-3, JACINTO BODY, JACINTO BODY. 3, HYDRATROPIC ALDEHYDE, HYDROXYL, INDOLAROME, INTRELEVEN ALDEHYDE, SPECIAL INTRELEVEN ALDEHYDE, ALPHA IONONE, BETA IONONA, CITRAL ISOCYCLE, GERANIAL ISOCYCLE, ISO AND SUPER®, JUICE, JUICE, KINEMALS KHUSINIL, KOAVONE®, KOHINOOL®, LIFFAROME ™, LIMOXAL, LINDENOL ™, LYRAL®, SUPER LYRAME, MANDARIN ALDEHYDE 10% TRI ETH, CITR, MARITIME, CHINESE MCK, MEIJIFF ™, MELAFLEUR, ANTHONYL, METALLONE, METAL, METAL METHYL IONONE GAMMA A, Methylionone GAMMA COEUR, Methylionone GAMMA PURE, METHYL LAUNDRY CETONA, MONTAVERDI®, MUGUESIA, ALDEHYDE MUGUET 50, ALMÍCAR Z4, ALDEHYDE MYRAC, ACETATE, MIRCENYLATE, NECTAR, NECTAR, NECTAR ORANGE FLOWER, ORIVONA, ORRINIFF 25%, OXASPIRANE, OZOFLEUR, PAMPLEFLEUR®, PEOMOSA, PHENOXANOL®, PICONIA, PRECYCLEMONE B, PRENYL ACETATE, PRISMANTOL, RESPOND, ROSALY, ROSALYRUS, ROSALFAR, TERPINEOL, TERPINOLENO 20, TE RPINOLENE 90 PQ, TERPINOLENE RECT., TERPINYL ACETATE, JAX TERPINYLACETATE, TETRAYDRO, MUGUOL®, MIRCENOL TETRAYRID, TETRAMERAN, TIMBERSILK ™, TOBACAROL, TRIMOFIX® TR, TRXO, TRXO, TRX, TRX, TRX, TRX, TRX, TRX, TRX, TRX, TRX VERTENEX®, VERTENEX® HC, VERTOFIX® COEUR,
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VERTOLIFF, VERTOLIFF ISO, VIOLIFF, VIVALDIE, ZENOLIDE, ABS INDIA 75 PCT MIGLYOL, ABS MOROCCO 50 PCT DPG, ABS MOROCCO 50 PCT TEC, ABSOLUTE FRENCH, ABSOLUTE INDIA, ABSOLUTE MD 50PCT BB, ABSOLUTE BROWN, TINY 20, CONTENT AMBERGRIS, ABSOLUTE AMBARETTE, AMBERET SEED OIL, ARTEMISIA OIL 70 PCT TUIONA, ABSOLUTE MAJERICÃO GRAND VERT, BASIL ABS GRAND VERT MD, BASIL OIL GRAND VERT, VERYNESS OIL, VERY VERY VERY HAPPY, DETERPENIZED BAY, ABS BEE WAX NG, ABSOLUTE BEE WAX, BENZOINE RESINOID SIÃO 50 PCT DPG, BENZOINE SIINO RESINIDE 50PCT PG, BENZOINE RESINIDE SIÃO 70.5 PCT TECTON NEGRA 65 PCT PG, ABS BLACK CURRANT BUTTON MD 37 PCT TEC, ABS BLACK CURRANCY BUTTON MIGLYOL, ABSOLUTE BURGUNDY BLACK CURRANT BUTTON, ROSE BOIS OIL, ABSOLUTE WHITE, WHITE RESINOID, ABSOLUTE BROOM ITALIAN, CO2EXTRATO CARDAMOMO GUATEMALTECO, CARDAMOMO OIL GUATEMALTECO, INDIAN CARDAMOMO OIL, CARROT HEART, ABSOLUTE EGYPTIAN ACACIA, ABSOLUTE ACACIA MD 50 PCT IPM, CASTOREUM ABS 90 PCT TEC, ABSORBER CASTOLE DE CASTOREUM, CASTOREUM RESINOID 50 PCT DPG, CEDROL, CEDRENO, REDIST ATLAS CEDER OIL, ROMAN CHAMOMILE OIL, WILD CHAMOMILE OIL, WILD CHAMOMILE OIL WITH LOW LIMONENE, CANEOUS OIL, CANEOE OIL, CANEOIL OIL CYST, ABSOLUTE CYLINDER, CITRONELLA OIL. ASIAN WITHOUT IRON, ABS CIVET 75 PCT PG, ABSOLUTE CIVET, CIVET DYE 10 PCT, ABS OF SAVAGE FRENCH CLARINE DECOL, ABSOLUTE OF SAVAGE CLARITY
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FRENCH, SALVIA CLARATE COLORLESS 50 PCT PG, SALVIA OIL FRENCH CLARIFY, COPAÍBA BALM, COPAÍBA BALAM, OIL, CYPRESTED OIL, CYPRESTED OIL, ORGANIC ORGANIC OIL, CYRUS, OIL , GALBAN OIL, GALBAN RESINOID, GALBAN RESINOID 50 PCT DPG, HERCOLINBHT GALBAN RESINOID, TEC BHT GALBAN RESINOID, ABSOLUTE GENCIAN MD 20 PCT BB, CONCRETE GENCIANIUM, GERANIUM ABSORBER, EGYPTIAN GYNIUM, EGYPTIAN CHINESE GERANIUM, EGYPTIAN GERANIUM OIL, GINGER OIL 624, SOLUBLE RECTIFIED GINGER OIL, GUIACO WOOD HEART, ABSOLUTE HAY MD 50 PCT BB, ABSOLUTE HAY, ABSOLUTE HAY, 50 PCT ORGANIC HISSOPO, ABS IMMORTELLE YUGO MD 50 PCT TEC, ABSOLUTE IMMORTELLE SPAIN, ABSOLUTE IMMORTELLE YUGO, ABS INDIAN JASMINE MD, ABSOLUTE EGYPTIAN JASMINE, ABSOLUTE INDIAN JASMINE, ABSOLUTE JASMINE ROCQUINO, ABSOLUTE JASMINE AMBAC, ABS JUNQUILO MD 20 PCT BB, ABSOLUTE JUNGILLE FRENCH, ZIMBER BERRY OIL FLG, SOLID RECTIFIED ZINBER BERRY OIL, 50PCT TEC LABD RESIDENTIAL, LID RESIDIDES, LID RESIDIDES LÁDDANO RESINOID MD 50 PCT BB, ABSOLUTE LAVANDINE H, ABSOLUTE LAVANDINE MD, LAVANDINE OIL ORGANIC LAVANDINE, LAVANDINE OIL, LAVANDINE OIL, LAVANDINE OIL, LAVANDINE OIL SUPER, ABSOLUTE, LAUNDRY OIL, ABSOLUTE LAVANDA WITHOUT CUMARINE, LAVANDA OIL WITHOUT ORGANIC CUMARINA, LAVANDA OIL MAILLETTE ORGANIC, LAVANDA OIL MT, ABSOLUTE MACE BB, LOW METHYL OF FLOWER OIL
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MAGNOLIA OIL, MAGNOLIA OIL AND FLOWER, MD MAGNOLIA FLOWER OIL, MAGNOLIA LEAF OIL, MANDARINE OIL MD, MANDARINE OIL MD BHT, ABSOLUTE MATE BB, ABSOLUTE TREE MOSS, ABS TEXTILE MEXICO, TEXT MUSEUM 42 DE CARVALHO MD TEC IFRA43, ABSOLUTE MOSS OF OAK IFRA 43, ABSOLUTE MOSS OF TREE MD IPM IFRA 43, RESINIDIDE OF BB MIRRA, RESINIDIDE OF MIRRA TEC, RESINIDIDE OF TEC IRON, LUMINARY OIL, MIRTILEO OIL, MIRTILEO OIL OIL TYLON OIL OIL, MOLDING OIL. , ABS NARCISSE MD 20PCT BB, ABSOLUTE FRENCH NARCISSE, TUNISIAN NEROLI OIL, DETERPENIZED FLYED WALNUT OIL, OEILLET ABSOLUTE, OLYBANE RESINOID, BB OLYMPUS RESIN, OLYDIC RESIN MD, OLÍBANO RESINOID MD 50 PCTDPG, OLÍBANO RESINOID TEC, OPOPONAX TEC RESINOID, OLIVE ORANGE OIL MD BHT, OLIVE ORANGE OIL MD SCFC, TUNISIAN ORANGE FLOWER ABSOLUTE, TUNISIAN ORANGE FLOWER NISIANA, ABSOLUTE ORANGE LEAF, ABSOLUTE ORANGE FLOWER WATER, TUNISIANA ABSOLUTE, ORRIS ITALIANA, ORRIS CONCRETA 15PCT IRONA, ORRIS CONCRETA 8 PCT IRONA, NATURAL ORRIS, NATURAL ORCHID, NATURAL ORCHID, PCR 40 ABSOLUTE OSMANTO, ABSOLUTE OSMANTO MD 50 PCT BB, PATCHOULI HEART N ° 3, INDONESIAN PATCHOULI OIL WITHOUT IRON, PATCHOULI INDONESIO MD OIL, PATCHOULI OIL, PATCHOULI REDEO , PETITGRAIN TUNISIAN ORANGE-OLIVE OIL, PETITGRAIN CITRONNIER OIL, DETERPENIZED PARAGUAYAN PETITGRAIN OIL, DETERPENIZED STAB PETITGRAIN OIL, CHILI PEPPER OIL
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CHILI PEPPER, CHINESE RODINOLEX GERANIUM, BULGARIAN PINK ABS LOW METHYLENE, MOROCCAN PINK ROSE LOW METHYLENE, TURKISH ROSE LOW METHYL EUGENOL, ABSOLUTE ROSE, ABSOLUTE RUBBER ROSE, ABSOLUTE ROSE, ABSOLUTE ROSE, ABSOLUTE ROSE ABSOLUTE ROSE MOROCCAN, ABSOLUTE ROSE TURKISH, BULGARIAN ROSE OIL, LOW METHYLENE ROSE DAMASCENE OIL, TURKISH ROSE OIL, ORGANIC HANDLED OIL, INDIAN TUNNISH OIL, TANDALIAN OIL, TANDALIAN OIL , SANTALOL, SCHINUS MOLLE OIL, CIPO DE SÃO JOÃO 10 PCT, STYRAX RESINOID, TAGETE OIL, TREE TREE HEART, TONKA BEAD ABS 50 PCT SOLVENTS, TONKA BEAM ABSOLUTE, ABSOLUTE NARDOUS NARD EXTRA VETIVER, HAITIAN VETIVER OIL, HAITIAN VETIVER OIL MD, JAVANESE VETIVER OIL, JAVANESE VETIVER OIL MD, ABSOLUTE EGYPTIAN VIOLET LEAF ABSOLUTE, ABSOLUTE EGYPTIAN VIOLET LEAF FRENCH VIOLET SHEET, ABSOLUTE VIOLET SHEET MD 50 PCT BB, DETERPENIZED ALOSNA OIL, EXTRA YLANG OIL, YLANG III OIL and combinations thereof.
[0176] Dyes may be among those listed in the Color Index International by the Society of Dyers and Colourists. Dyes can include dyes and pigments and include those commonly used in the coloring of textile materials, paints, inks and inks for inkjet printing. Some of the dyes that can be used to be used include carotenoids, arylidium yellows, diarylidium yellows, β-naphthols, naphthols, benzimidalozones, diazo-type condensation pigments, pyrazolones, nickel-azo yellow, phthalocyanines, quinacridones, perylenes and perinones, indoline and isoindolinone pigments, triarylcarbonium pigments, diceto-pyrrole-pyrol pigments, thioindigoids. Carotenoids include, for example,
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64/125 alpha-carotene, beta-carotene, gamma-carotene, lycopene, Annatto extract of lutein and astaxanthin, dehydrated beet (powdered beet), canthaxanthin, caramel, β-Apo8'-carotenal, cochineal extract, carmine, sodium chlorophylline copper, flour roasted and partially defatted cotton seed, ferrous gluconate, ferrous lactate, grape-colored extract, grape skin extract (enocyanin), carrot oil, paprika, paprika oleoresin, pearly pigments based on mica, riboflavin, saffron, titanium dioxide, tomato lycopene extract, tomato lycopene concentrate, turmeric, turmeric oleoresin, Blue FD&C no. 1, Blue FD&C no. 2, Green FD&C no. 3, Orange B, Citrus Red no. 2, FD&C Red no. 3, Red FD&C no. 40, Yellow FD&C no. 5, Yellow FD&C no. 6, alumina (dry aluminum hydroxide), calcium carbonate, potassium-sodium-copper-chlorophylline (copper-chlorophylline complex), Dihydroxyacetone, bismuth oxychloride, ferric ammonium ferrocyanide, ferric ferrocyanide, chromium hydroxide green, green chromium oxide, guanine, pyrophyllite, talc, aluminum powder, bronze powder, copper powder, zinc oxide, D&C Blue no. 4, Green D&C no. 5, Green D&C no. 6, Green D&C no. 8, D&C Orange no. 4, Orange D&C no. 5, D&C Orange no. 10, D&C Orange no. 11, FD&C Red no. 4, D&C Red no. 6, D&C Red No. 7, D&C Red No. 17, D&C Red. No. 21, Red D&C 22, Red D&C No. 27, Red D&C No. 28, Red D&C No. 30, Red D&C No. 31, Red D&C No. 33, Red D&C No. 34, Red D&C No. 36, Red D&C No. 39, Violet D&C No. 2, Yellow D&C No. 7, Yellow D&C No. 7, Yellow D&C No. 8, Yellow D&C No. 10, Yellow D&C No. 11, Black D&C No. 2, Black D&C No. 3 (3), Marro D&C No. 1, Ext. D&C, chromium-cobalt aluminum oxide, ferric ammonium citrate, pyrogallol, Campeche extract, 1,4-Bis [(2-hydroxy-ethyl) amino copolymers ] -9,10-anthracenedione bis (2-propenoic) ester, 1,4-Bis [(2-methylphenyl) amino] -9,10-anthracenedione, anthraquinone copolymers 1,4-Bis [4 (2-methacryloxyethyl) phenylamino ], carbazole violet, chlorophyllin-copper complex, chromium-cobalt-aluminum oxide, CI Vat Orange 1, 2 - [[2,5-Diethoxy- 4 - [(4-methylphenyl) thiol]
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65/125 phenyl] azo] -1,3,5-benzenetriol, 16,23-dihydrodinafto [2,3-a: 2 ', 3'-i] naphtho [2', 3 ': 6,7] indole [ 2,3-c] carbazole- 5,10,15,17,22,24-hexone, N, N '- (9,10-Dihydro- 9,10-dioxo- 1,5 anthracenedyl) bisbenzamide, 7,16- Dichloro-6,15-dihydro-5,9,14,18-anthrazinetetrone, 16,17-Dimethoxydinafto (1,2,3-cd: 3 ', 2', 1'-1m) perylene-5,10-dione , poly (hydroxyethyl methacrylate) dye copolymers (3), Reactive Black 5, Reactive Blue 21, Reactive Orange 78, Reactive Yellow 15, Reactive Blue No. 19, Reactive Blue No. 4, CI Reactive Red 11, CI Reactive Yellow 86, CI Reactive Blue 163, CI Reactive Red 180, 4 - [(2,4-dimethylphenyl) azo] - 2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one (Solvent Yellow 18 ), 6-Ethoxy-2- (6-ethoxy-3-oxobenzo [b] thieno-2 (3H) - ilidene) benzo [b] thiophene3 (2H) -one, Phthalocyanine green, phthalocyanine green, reactive products vinyl alcohol / methyl methacrylate paint, CI Reactive Red 180, CI Reactive Black 5, CI Reactive Orange 78, CI Reactive Yellow 15, CI Reactive Blue 21, Disodium 1 amino-4 - [[4 - [(2-bromo-1-oxoalyl) amino] -2-sulfonatophenyl] amino] - 9,10-dihydro-9,10dioxoanthracene-2-sulfonate (Blue Reactive 69), Blue D&C No. 9, copper [hthalocyaninate (2)] and mixtures thereof.
[0177] A fragrance, for example, natural wood fragrance, can be combined with the resin used to make the compound. In some implementations, the fragrance is combined directly into the resin like an oil. For example, the oil can be combined in the resin using a two-cylinder mill, for example, a Banbury® mixer or an extruder, for example, a counter-rotating twin screw extruder. An example of a Banbury® mixer is the Banbury® Series F mixer, manufactured by Farrel, Ansonia, CT. An example of a twin screw extruder is the WP ZSK 50 MEGACOMPOUNDER ™, manufactured by Coperion, Stutgart, Germany. After the combination, the flavored resin can be added to the fibrous material and extruded or molded. Alternatively, batches of fragrance-filled resins are commercially available from International Flavors and Fragrances, under the trade name POLYIFF ™. In some
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66/125 embodiments, the amount of fragrance in the compound is between about 0.005% by weight and about 10% by weight, for example, between about 0.1% and about 5% or 0.25% and about 2.5%. Other natural wood fragrances include perennials and redwood. Other fragrances include mint, cherry, strawberry, peach, lime, mint, cinnamon, anise, basil, bergamot, black pepper, camphor, chamomile, citronella, eucalyptus, pine, fir, geranium, ginger, grapefruit, jasmine, juniper berry, lavender, lemon, mandarin orange, marjoram, musk, myrrh, orange, patchouli, rose, rosemary, sage, sandalwood, tea tree, thyme, wintergreen, ylang ylang, vanilla, new car or mixtures of these fragrances. In some embodiments, the amount of fragrance in the fragrance-fibrous material combination is between about 0.005% by weight and about 20% by weight, for example, between about 0.1% and about 5% or 0, 25% and about 2.5%. Even other fragrances and methods are described in U. S. Patent 8,074,910 issued on December 13, 2011, the disclosure of which is incorporated herein in its entirety by reference.
USES OF HYDROXICARBOXYLIC POLYACIDE AND HYDROXICARBOXYL POLYACIDE COPOLYMERS [0178] Some uses of lactic polyacid and materials containing lactic polyacid include: personal hygiene items (eg, handkerchiefs, towels, diapers), ecological packaging, garden (compostable pots), products consumer electronics (for example, laptop covers and cell phones), devices, food packaging, disposable packaging (for example, food containers and drink bottles), garbage bags (for example, compostable garbage bags), vegetation cover films, matrices and controlled release containers (for example, for fertilizers, pesticides, herbicides, nutrients, drugs, flavoring agents, foods), shopping bags, general purpose film, high heat resistant films, sealing adhesive heat resistant, surface coatings, disposable tableware (e.g. plates,
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67/125 glasses, forks, knives, spoons, sporks, bowls), auto parts (for example, panels, fabrics, covers under the hood), carpet fibers, clothing fibers (for example, underwear fibers, fibers for sportswear, fibers for footwear), biomedical devices (for example, surgical sutures, implants, scaffolding, drug delivery systems, dialysis equipment and engineering plastics.
[0179] Other industrial uses / sectors that can benefit from the use of lactic polyacid and derivatives of lactic polyacid (eg elastomers) include information technology and software, electronics, geoscience (eg oil and gas), engineering, aerospace (for example, armrests, seats, panels), telecommunications (for example, headphones), chemical manufacturing, transport, such as automobiles (for example, dashboards, panels, tires, wheels), materials and steel , consumer packaged goods, wires and cables.
OTHER ADVANTAGES OF POLYHYDROXICARBOXYLIC ACID AND POLYHYDROXICARBOXYLIC ACID COPOLYMERS [0180] Polyhydroxycarboxylic acids have a biological basis and can be composed, recycled and used as fuel (incinerated). Some of the degradation reactions include thermal degradation, hydrolytic degradation and biotic degradation.
[0181] For example, polylactic acid can be thermally degraded. For example, at high temperatures (for example, between about 200-300 ° C, about 230-260 ° C). The reactions involved in the thermal degradation of polylactic acid can follow different mechanisms such as thermo-hydrolysis, zipper-type polymerization (for example, in the presence of residual catalysts), thermo-oxidative degradation. Transesterification reactions can also act on the polymer causing breakage and / or promoting bonding.
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68/125 [0182] Polyhydroxycarboxylic acid can also undergo hydrolytic degradation. Hydrolytic degradation includes chain splits that produce smaller polymers, oligomers and eventually the monomer, the lactic acid monomer can be released. Hydrolysis can be associated with thermal and biotic degradation. Regarding the polylactic acid example, the process can be carried out by various parameters such as the structure of the polylactic acid, its molecular weight and distribution, its morphology (ie crystallinity), the sample format (for example, isolated thin samples or comminuted samples may degrade faster), thermal and mechanical history (eg processing) and hydrolysis conditions (eg temperature, agitation, comminution). The hydrolysis of polylactic acid begins with a water ingestion phase, followed by the hydrolytic division of the ester bonds. The amorphous parts of the polyesters can be hydrolyzed more quickly than the crystalline regions because of the increased water intake and mobility of chain segments in these regions. In a second stage, the crystalline regions of polylactic acid are hydrolyzed.
[0183] Polyhydroxycarboxylic acid can also undergo biotic degradation. This degradation can occur, for example, in a mammalian body, and has useful implications for degradable seams and can have detrimental implications for other surgical implants. Enzymes such as proteinase K and pronase can be used.
[0184] During composting, polyhydroxycarboxylic acid can undergo several stages of degradation. For example, an initial step may occur due to exposure to moisture where degradation is abiotic and poly hydroxy xarboxyl acid is degraded by hydrolysis. This stage can be accelerated by the presence of acids and bases and elevated temperatures. The first stage can lead to a weakening of the polymer, which can facilitate the diffusion of polyhydroxycarboxylic acid out of the polymers in bulk. Oligomers can then be attacked by
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69/125 microorganisms. Organisms can degrade oligomers and D-lactic acid and / or L-lactic acid, resulting in CO2 and water. The time of this degradation is in the order of about one to a few years, depending on the factors previously mentioned. The degradation time is faster by many orders of magnitude than that of typical petroleum-based plastics, such as polyethylene (for example, the order is hundreds of years).
[0185] Polyhydroxycarboxylic acid can be recycled. For example, poly polylactic acid can be hydrolyzed to D-lactic acid and / or L-lactic acid, purified and repolymerized. Unlike other recyclable plastics like polyethylene terephthalate and high-density polyethylene, PLA polylactic acid does not need to be downgraded to make a lower-value product (for example, from a bottle to cover decks or carpets). Polylactic acid can be recycled indefinitely in theory. Optionally, polylactic acid can be reused and demoted for several generations and then converted to lactic acid and re-polymerized.
[0186] Polyhydroxycarboxylic acid can also be used as a fuel, for example, for energy production. Polylactic acid can have a high heat content, for example, greater than about 8400 BTU. The incineration of pure polylactic acid releases only carbon dioxide and water. Combinations with other ingredients normally total less than 1ppm of non-polylactic acid residues (eg gray). In this way, the combustion of polylactic acid is cleaner than that of other renewable fuels, for example, wood.
[0187] Poly hydroxycarboxylic acid can have high gloss, high transparency, high clarity, high rigidity, can be UV stable, non-allergenic, have high flavor and aroma barrier properties, ease of mixing, ease of molding, ease shape, ease of recording, ease of printing, lightness, compostable.
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70/125 [0188] Poly hydroxycarboxylic acid can also be printed, for example, by lithographic printing, inkjet printing, laser printing, fixed type printing, printing by roll. Some poly hydroxycarboxylic acids can also be written, for example, using a pen.
[0189] Processing, as described in this document, may include radiation. For example, irradiation with radiation between about 1 and 150 Mrad (for example, any range as described in this document) can improve the compostability and recyclability of polyhydroxycarboxylic acid and materials containing poly hydroxycarboxylic acid.
ADDITION OF THE CATALYST BY DEACTIVATING THE AGENT AND SIMILAR ADDITIVES [0190] The polymerization of hydroxycarboxylic acids is carried out, most often, with a catalyst. This catalyst may persist in the final product of the polymer and, as such, may be able to catalyze a reverse reaction when water is present or, possibly, other harmful chemicals. The catalyst can be deactivated by adding deactivating agents such as anhydrides, phosphites, antioxidants or multifunctional carboxylic acids. The most effective multifunctional carboxylic acids are those in which two carboxylic acids have no more than six separate carbon atoms in which the counted carbon atoms include carbonyl carbon. Examples of polycarboxylic acids include dicarboxylic acids, such as tartaric acid, succinic acid, malic acid, fumaric acid and adipic acid and, if appropriate, stereoisomers. Another type of multifunctional carboxylic acid includes polycarboxylic acid that includes oligomers and polymers that contain three or more groups of carboxylic acid and a molecular weight greater than about 500. Especially preferred polycarboxylic acids include polyacrylic acid. Without being bound by theory, the carboxylic acids next to each other can be those that chelate the catalyst and leave them in a
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71/125 state in which its catalytic sites were occupied, thus reducing negative reactions.
[0191] Polymers of polycarboxylic acid can include polyacrylic acids and especially poly (meth) acrylic acids. The latter has the advantage that it can process the most soluble complexed catalyst in the polymer. It is important to note that polyacrylic and (meth) acrylic acids should be included as discrete polymers and not as (meth) acrylic acid. These poly (meth) acrylic acids have pendant carboxylic acids and non-carboxylic acids that are part of the polyester chain.
[0192] Phosphite antioxidants include Tris (2,4-ditherc-butylphenyl) phosphite and other tri-substituted phosphites. They can also be used to disable catalysts.
[0193] Compounds similar to ethylenediaminetetraacetic acid, commonly abbreviated as EDTA, can also be used to complex and / or disable the catalyst. EDTA-related compounds can also be used, such as N- (hydroxyethyl) -ethylenediamine triacetic acid, diethyl triamine pentaacetic acid and nitrilotriacetic acid.
[0194] Anhydrides include acetic anhydride, pivaloyl anhydride, maleic anhydride, succinic anhydride. When anhydrides are used at 2 to 60 molars, equivalents based on the moles of the catalysts can be used.
[0195] These additives for polyhydroxycarboxylic acids can be easily added just before, during or immediately after the polymer is processed in the thin film evaporator or thin film polymerization / devolatilization device. They can be described as stabilizers.
[0196] Compounds that are solid are also candidates for deactivating catalysts. Not only these bonds / links with the catalyst,
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72/125 they can be of a size that improves the filtration of the polymer catalyst. This includes hydroxyl media and similar compounds.
[0197] The combinations of these additives can also be used. For example, anhydrides can be used with solids. For example, acetic anhydride and alumina can be used to deactivate the catalyst and facilitate its removal by filtration.
[0198] The catalyst can be removed after complexing / reacting with / bonding / binding to the catalysts that disable the systems described above. Removal can be done just before / during / after the thin film evaporator system described above.
RADIATION TREATMENT [0199] The raw material (for example, cellulosic, lignocellulosic, PLA, PLA derivatives and combinations thereof) that can produce precursors for hydroxy-carboxylic acids can be treated with electron bombardment to modify its structure, for example , to reduce its resistance or by crossing the structures. Such treatment can, for example, reduce the average molecular weight of the raw material, change the crystalline structure of the raw material and / or increase the surface area and / or porosity of the raw material. The radiation can be, for example, an electron beam, ion beam, 100 nm to 28 nm ultraviolet (UV) light, gamma radiation or x-ray. Radiation treatments and treatment systems are discussed in US Patent No. 8,142,620 and US Patent Application Series No. 12 / 417,731, the full disclosures of which are incorporated into this instrument by reference.
[0200] Each form of radiation ionizes the biomass containing carbon through specific interactions, as determined by the radiation energy. Heavy charged particles mainly ionize matter through Coulomb dispersion; in addition, these interactions produce energetic electrons that can
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73/125 additionally ionize the matter. Alpha particles are identical to the nucleus of a helium atom and are produced by the alpha decline of several radioactive nuclei, such as isotopes of bismuth, polonium, astatin, radon, francium, radium, various actinides, such as actinium, thorium, uranium, neptunium , curium, californium, americium and plutonium. Electrons interact via Coulomb dispersion and bremsstrahlung radiation produced by changes in electron speed.
[0201] When particles are used, they can be neutral (no charge), positively charged or negatively charged. When charged, the charged particles can carry a single positive or negative charge, or multiple charges, for example, one, two, three or even four or more charges. In cases where a fission chain is desired to change the molecular structure of the carbohydrate-containing material, positively charged particles may be desirable, in part, due to their acidic nature. When particles are used, the particles can have the mass of an electron at rest, or greater, for example, 500, 1000, 1500, or 2000 or more times the mass of an electron at rest. For example, particles can have a mass of about 1 atomic unit to about 150 atomic units, for example, from about 1 atomic unit to about 50 atomic units, or from about 1 to about 25, for example, 1, 2, 3, 4, 5, 10, 12 or 15 atomic units.
[0202] Gamma radiation has the advantage of a significant depth of penetration into a variety of materials in the sample.
In modalities in which irradiation is carried out with electromagnetic radiation, electromagnetic radiation may have, for example, energy per photon (in electron volts) greater than 10 ² eV, for example, greater than 10 ³ , 10 ⁴ , 10 ⁵ , 10 ⁶ , or even greater than 10 ⁷ eV. In some modalities, electromagnetic radiation has energy per photon between 10 ⁴ and 10 ⁷ , for example, between 10 ⁵ and 10 ⁶ eV. Electromagnetic radiation can have a frequency of, for example, more than
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74/125 than 10 ¹⁶ Hz, more than 10 ¹⁷ Hz, 10 ¹⁸ , 10 ¹⁹ , 10 ²⁰ , or even more than 10 ²¹ Hz. In some embodiments, electromagnetic radiation has a frequency between 10 ¹⁸ and 10 ²² Hz, for example, between 10 ¹⁹ to 10 ²¹ Hz.
[0203] The electron bomber can be carried out using an electron beam device that has a nominal energy of less than 10 MeV, for example: less than 7 MeV, less than 5 MeV or less than 2 MeV, for example: approximately 0.5 to approximately 1.5 MeV, approximately 0.8 to 1.8 MeV or approximately 0.7 to 1 MeV. In some implementations, the nominal energy is approximately 500 to 800 keV.
[0204] The electron beam can have a relatively high total beam power (the beam power of all accelerator heads or, if multiple accelerators, all accelerators and all heads are used), for example: at least 25 kW, for example: at least 30, 40, 50, 60, 65, 70, 80, 100, 125 or 150, 250, 300 kW. In some cases, the power reaches 500 kW, 750 kW or even 1000 kW or more. In some cases, the electron beam has a beam power of 1200 kW or more, for example: 1400, 1600, 1800 or even 3000 kW. The electron beam can have a total beam power of 25 to 3000 kW. Alternatively, the electron beam can have a total beam power of 75 to 1500 kW. Optionally, the electron beam can have a total beam power of 100 to 1000 kW. Alternatively, the electron beam can have a total beam power of 100 to 400 kW.
[0205] This high total beam power is usually obtained by using multiple accelerator heads. For example, the electron beam device can include two, four, or more acceleration heads. The use of multiple heads, each of which has a relatively low beam power, prevents excessive temperature rise of the material, thus preventing burning of the material and also increasing the uniformity of the dose through the thickness of the material layer.
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75/125 [0206] It is generally preferred that the bed of biomass material has a relatively uniform thickness. In some embodiments, the thickness is less than about 1 inch (for example, less than about 0.75 inches, less than about 0.5 inches, less than about 0.25 inches, less than about 0, 1 inches, between about 0.1 and 1 inch, between about 0.2 and 0.3 inches).
[0207] It is desirable to treat the material as quickly as possible. In general, it is preferable that the treatment be carried out at a dose rate greater than approximately 0.25 Mrad per second, for example, greater than approximately 0.5, 0.75, 1, 1.5, 2, 5, 7 , 10, 12, 15, or even greater than about 20 Mrad per second, for example, about 0.25 to 30 Mrad per second. Alternatively, treatment is carried out at a dose rate of 0.5 to 20 Mrad per second. Optionally, treatment is carried out at a dose rate of 0.75 to 15 Mrad per second. Alternatively, treatment is carried out at a dose rate of 1 to 5 Mrad per second. Optionally, treatment is carried out at a dose rate of 1-3 Mrad per second or, alternatively, 1-2 Mrad per second. Higher dose rates allow for a higher flow rate to the target dose (for example , desired). Higher dose rates generally require higher speed lines to avoid thermal decomposition of the material. In one implementation, the accelerator is set to 3 MeV, 50 mA beam current and the line speed is 24 feet / minute, for a sample about 20 mm thick (for example, corn cob material ground with volume density 0.5 g / cm ³ ).
[0208] In some modalities, electron bombardment is performed until the material receives a total dose of at least 0.1 Mrad, 0.25 Mrad, 1 Mrad, 5 Mrad, for example: at least 10, 20, 30 or at least 40 Mrad. In some modalities, the treatment is carried out until the material receives a dose of approximately 10 Mrad to approximately 50 Mrad, for example:
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76/125 approximately 20 Mrad to approximately 40 Mrad, or from approximately 25 Mrad to approximately 30 Mrad. In some implementations, a total dose of 25 to 35 Mrad is preferred, ideally applied for a few passes, for example, at 5 Mrad / pass with each pass being applied for approximately one second. Refrigeration methods, systems and equipment can be used before, during, after and between radiation using, for example, a helical cooler conveyor and / or a refrigerated vibrating conveyor.
[0209] Using the multiple heads as previously discussed, the material can be treated in multiple passes, for example: two passes at 10 to 20 Mrad / pass, for example: 12 to 18 Mrad / pass, separated by a few seconds cooling or three passes of 7 to 12 Mrad / passage, for example: 5 to 20 Mrad / passage, 10 to 40 Mrad / passage, 9 to 11 Mrad / passage. As discussed in this document, treating the material with several relatively low doses, instead of a high dose, tends to prevent the material from overheating and also increases dose uniformity across the thickness of the material. In some implementations, the material is agitated or otherwise mixed during or after each pass and then spread on an even layer before the next pass, to further increase the uniformity of treatment.
[0210] In some modalities, electrons are accelerated to, for example, a speed of more than 75% of the speed of light, for example, more than 85, 90, 95 or 99% of the speed of light.
[0211] In some embodiments, any processing described here occurs on lignocellulosic material that remains dry as purchased or that has been dried, for example, using heat and / or reduced pressure. For example, in some embodiments, cellulosic and / or lignocellulosic material has less than 25% by weight of water retained, measured at 25 ° C and 50% relative humidity (for example,
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77/125 example, less than about 20% by weight, less than about 15% by weight, less than about 14% by weight, less than about 13% by weight, less than about 12 % by weight, less than about 10% by weight, less than about 9% by weight, less than about 8% by weight, less than about 7% by weight, less than about 6 % by weight, less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, less than about 2% by weight, less than about 1% by weight weight or less than about 0.5% by weight.
[0212] In some embodiments, two or more ionizing sources can be used, such as two or more electron sources. For example, samples can be treated, in any order, with an electron beam, followed by gamma radiation and UV light with wavelengths from about 100 nm to about 280 nm. In some embodiments, the samples are treated with three sources of ionizing radiation, such as an electron beam, gamma radiation, and energetic UV light. The biomass is transmitted through the treatment zone, where it can be bombarded with electrons.
[0213] It may be advantageous to repeat the treatment to totally reduce the recalcitrance of biomass and / or modify the biomass. In particular, the process parameters can be adjusted after a first pass (for example, second, third, fourth or more) depending on the recalcitrance of the material. In some embodiments, a carrier can be used that includes a circular system where the biomass is transported numerous times through the various processes described above. In some other modalities, various treatment devices (eg, electron beam generators) are used to treat biomass (eg, 2, 3, 4 or more) times. In still other embodiments, a single electron beam generator can be the source of multiple beams (for example, 2, 3, 4 or more beams) that can be used for the treatment of biomass.
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78/125 [0214] The effectiveness in changing the molecular / supermolecular structure and / or in reducing the resistance of the biomass containing carbohydrate depends on the energy of the electron used and the applied dose, while the exposure time depends on the power and the dose. In some embodiments, the dose rate and total dose are adjusted so as not to destroy (for example, carbonize or burn) the biomass material. For example, carbohydrates must not be damaged in processing, so that they can be released from biomass intact, for example, as monomeric sugars.
[0215] In some embodiments, treatment (with any electron source or a combination of sources) is carried out until the material receives a dose of at least approximately 0.05 Mrad, for example, at least approximately 0.1, 0.25, 0.5, 0.75, 1.0, 2.5, 5.0, 7.5, 10.0, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175 or 200 Mrad. In some embodiments, treatment is carried out until the material receives a dose between 0.1-100 Mrad, 1-200, 5-200, 10-200, 5-150, 50-150 Mrad, 5-100, 5- 50, 5-40, 10-50, 10-75, 15-50, 20-35 Mrad.
[0216] In some embodiments, relatively low doses of radiation are used, for example, to increase the molecular weight of a lignocellulosic or cellulosic material (with any radiation source or combination of sources described in this document). For example, a dose of at least about 0.05 Mrad, for example, at least about 0.1 Mrad or at least about 0.25, 0.5, 0.75. 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, or at least about 5.0 Mrad. In some embodiments, irradiation is carried out until the material receives a dose between 0.1 Mrad and 2.0 Mrad, for example, between 0.5 rad and 4.0 Mrad or between 1.0 Mrad and 3.0 Mrad .
[0217] It may also be desirable to irradiate multiple directions, simultaneously or sequentially, in order to achieve a desirable degree of
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79/125 radiation penetration into the material. For example, depending on the density and moisture content of the material, such as wood, and the type of radiation source used (for example, gamma rays or electron beam), the maximum radiation penetration into the material may be only about 0 , 75 inch. In such cases, a thicker section (up to 1.5 inches) can be irradiated by first irradiating the material on one side and then turning the material over and radiating on the other side. Multi-direction irradiation can be particularly useful with electron beam radiation, which radiates more quickly than gamma radiation, but typically does not reach a great depth of penetration.
RADIATION SOURCES [0218] The type of radiation determines the types of radiation sources used, as well as the radiation devices and associated equipment. The methods, systems and equipment described in this document, for example, to treat materials with radiation, can use sources as described in this document, as well as any other useful source.
[0219] Sources of gamma rays include radioactive nuclei, such as isotopes of cobalt, calcium, technetium, chromium, gallium, indium, iodine, iron, krypton, samarium, selenium, sodium, thallium and xenon.
[0220] X-ray sources include electron beam collision with metal targets, such as tungsten or molybdenum or alloys, or compact light sources, such as those commercially produced by Lyncean.
[0221] Alpha particles are identical to the nucleus of a helium atom and are produced by the alpha decline of various radioactive nuclei, such as isotopes of bismuth, polonium, astatin, radon, francium, radium, various actinides, such as actinium, thorium, uranium, neptunium, curium, californium, americium and plutonium.
[0222] Sources of ultraviolet radiation include deuterium or cadmium lamps.
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80/125 [0223] Sources of infrared radiation include ceramic sapphire, zinc or selenide lamps.
[0224] Microwave sources include klystrons, Slevin-type RF sources or atom beam sources that employ nitrogen, oxygen or hydrogen gases.
[0225] Accelerators used to accelerate particles can be electrostatic DC, electrodynamic DC, linear RF, linear magnetic induction or continuous wave. For example, cyclotronic type accelerators are available in IBA, Belgium, as the RHODOTRON ™ system, while DC type accelerators are available in RDI, now IBA Industrial, as DYNAMITRON®. Ions and ion accelerators are discussed in Introductory Nuclear Physics, Kenneth S. Krane, John Wiley & Sons, Inc. (1988), Krsto Prelec, FIZIKA B 6 (1997) 4, 177-206; Chu, William T., Overview of Light-Ion Beam Therapy, Columbus-Ohio, ICRU-IAEA Meeting, 18-20 March 2006; Iwata, Y. et al., Alternating-Phase-Focused IH-DTL for Heavy-Ion Medical Accelerators, Proceedings of EPAC 2006, Edinburgh, Scotland; and Leaner, CM. et al., Status of the Superconducting ECR Ion Source Venus, Proceedings of EPAC 2000, Vienna, Austria.
[0226] Electrons can be produced by radioactive nuclei that undergo beta decay, such as isotopes of iodine, technetium, cesium and iridium. Alternatively, an electron injector can be used as an electron source through thermionic emission and accelerated through an acceleration potential. An electron gun generates electrons, which are then accelerated through a large potential (for example, greater than approximately 500,000, greater than approximately 1 million, greater than approximately 2 million, greater than approximately 5 million, greater than approximately 6 million, greater than approximately 7 million, greater than approximately 8 million, greater than approximately 9 million, or even greater than 10 million volts) and then magnetically examined in the xy plane, where electrons are initially accelerated in
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81/125 direction Z throttle tube below and extracted through a blade window. Checking the electron beam is useful for increasing the irradiation surface when irradiating materials, for example, a biomass, which is transmitted through the examined beam. Scanning the electron beam also distributes the thermal charge evenly across the window and helps reduce breakage of the laminated window due to heating by the electron beam. The rupture of the laminated window is the cause of a significant interruption due to the necessary subsequent repairs and the reclosing of the electron injector.
[0227] Several other irradiation devices can be used in the methods exposed here, including field ionization sources, electrostatic ion separators, field ionization generators, thermionic emission sources, microwave discharge ion sources, accelerators recirculation or static, dynamic linear accelerators, van de Graff accelerators and tandem accelerators. Such devices are disclosed, for example, in Pat. US No. 7,931,784 to Medoff, the full disclosure of which is incorporated herein by reference.
[0228] An electron beam can be used as a radiation source. An electron beam has the advantages of high dose rates (for example, 1, 5 or even 10 Mrad per second), high throughput, less containment and less containment equipment. Electron beams can also have high electrical efficiency (for example, 80%), allowing for reduced energy use compared to other radiation methods, which can result in lower operating costs and reduced emission of greenhouse gases greenhouse corresponding to the lowest amount of energy used. The electron beams can be generated, for example, by electrostatic generators, by cascade generators, by transforming generators, by low-energy accelerators with scanning system, low-energy accelerators with linear cathode, linear accelerators and pulsed accelerators.
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82/125 [0229] Electrons can also be more efficient causing changes in the molecular structure of carbohydrate-containing materials, for example, by the chain's scission mechanism. In addition, electrons with energies of 0.5-10 MeV can penetrate low density materials, such as the biomass materials described in this document, for example, materials having a mass density of less than 0.5 g / cm ³ and a depth of 0.3 to 10 cm. Electrons as a source of ionizing radiation can be useful, for example, for materials of relatively thin cells, beds or layers, for example, less than approximately 0.5 inch, for example, less than approximately 0.4 inch, 0.3 inch, 0.25 inch or less than approximately 0.1 inch. In some embodiments, the energy for each electron in the electron beam is approximately 0.3 MeV to approximately 2.0 MeV (million electron volts), for example, approximately 0.5 MeV to approximately 1.5 MeV, or from approximately 0.7 MeV to approximately 1.25 MeV. Methods of irradiation of materials are discussed in Pub. do Ped. of Pat. US No. 2012/0100577 A1, filed on October 18, 2011, the full disclosure of which is incorporated herein by reference.
[0230] Electron beam irradiation devices can be purchased commercially from lon Beam Applications, Louvain-la-Neuve, Belgium NHV Corporation, Japan or Titan Corporation, San Diego, California. Typical electron energies can be 0.5 MeV, 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV or 10 MeV. Typical electron beam irradiation device power can be 1 KW, 5 KW, 10 KW, 20 KW, 50 KW, 60 KW, 70 KW, 80 KW, 90 KW, 100 KW, 125 KW, 150 KW, 175 KW, 200 KW, 250 KW, 300 KW, 350 KW, 400 KW, 450 KW , 500 KW, 600 KW, 700 KW, 800 KW, 900 KW or even 1000 KW.
[0231] The disadvantages when considering the power specifications of the electron beam irradiation device include capital cost, depreciation and device footprint. The disadvantages when considering dose levels of
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83/125 exposure of the electron beam irradiation would be the costs and concerns about the environment, safety and health (ESH). Typically, generators are housed in a cavity, for example, of lead or concrete, especially for production from X-rays that are generated in the process. The disadvantages when considering electron energies include energy costs.
[0232] The electron beam irradiation device can produce a fixed beam or a check beam. A scanning beam can be advantageous with long scan lengths and high scanning speeds, as this would effectively replace a wide, fixed beam width. In addition, available sweep widths of 0.5 m, 1 m, 2 m or more are available. The check beam is preferred in most of the modes described here because of the wider check width and reduced possibility of local heating and window failure.
ELECTRON CANNES - WINDOWS [0233] The extraction system for an electron accelerator can include two window blades. The cooling gas in the two-bladed window extraction system can be a purge gas or a mixture, for example, air or a pure gas. In one embodiment, gas is an inert gas such as nitrogen, argon, helium and or carbon dioxide. It is preferred to use a gas instead of a liquid, as energy losses to the electron beam are minimized. Pure gas mixtures can also be used pre-mixed or mixed in the line before the collision on the window or in the space between the windows. The refrigeration gas can be cooled, for example, using a heat exchange system (for example, a refrigerator) and / or using the evaporation of a condensed gas (for example, liquid nitrogen, liquid helium). The window panes are described in PCT / US2013 / 64332 filed on October 10, 2013, the full disclosure of which is incorporated by reference to this document.
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ELECTRON INJECTORS - BEAM SWITCHES [0234] In some embodiments, systems and methods include a beam stop (for example, a shutter). For example, the beam switch can be used to quickly interrupt or reduce material irradiation without turning off the electron beam device. Alternatively, the beam stop can be used while energizing the electron beam, for example, beam stop can stop the electron beam until a beam current of a desired level is achieved. The beam switch can be placed between a primary leaf window and a secondary leaf window. For example, the beam stop can be mounted so that it is movable, that is, so that it can be moved in and out of the beam path. Even a partial beam coverage can be used, for example, to control the radiation dose. The beam switch can be mounted on the floor, on a biomass conveyor, on a wall, on a radiation device (for example, on the scanning alarm) or on any structural support. Preferably the beam stop is fixed in relation to the check rod so that the beam can be effectively controlled close to the beam stop. The beam limiter can incorporate a hinge, a rail, wheels, grooves or other means, allowing its operation to move in and out of the beam. The beam switch can be made of any material that stops at least 5% of the electrons, for example: at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, at least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or even 100% of the electrons.
[0235] The beam switch can be made of a metal, including, but not limited to, stainless steel, iron, molybdenum, silver, gold, titanium, aluminum, foreign or alloys of these metals, or laminator (layered materials) made from these metals (for example, metallized ceramic, metallized polymer, metallized composite, multilayered metallic materials).
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85/125 [0236] The beam stop can be cooled, for example, with a refrigerant such as an aqueous solution or a gas. The beam switch can be partially or completely hollow, for example with cavities. The internal spaces of the beam switch can be used for refrigerant fluids and gases. The beam stop can be of any shape, including flat, curved, round, oval, square, rectangular, chamfered and probed.
[0237] The beam stop may have perforations in order to allow some electrons to pass, thus controlling (for example, reducing) radiation levels in the entire window area, or in specific regions of the window. The beam switch can be formed of a mesh, for example, of fibers or threads. The multiple beam switches can be used together or independently to control irradiation. The beam switch can be controlled remotely, for example, by radio signal or wired to a motor to move the beam in or out of position.
BEAM DEFLECTOR [0238] The modalities disclosed in this document may also include a beam deflector when using a radiation treatment. The function of a beam deflector is to safely absorb a beam of charged particles. Like a beam limiter, a beam deflector can be used to block the beam from charged particles. However, a beam deflector is much more robust than a beam limiter, and its intention is to block the full power of the electron beam for an extended period of time. They are often used to block the beam while the accelerator is being started.
[0239] Beam deflectors are also designed to accommodate the heat generated by such beams, and are normally made, and are usually made of materials such as copper, aluminum, carbon, beryllium, tungsten, or mercury. Deflectors
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86/125 beam can be cooled, for example, using a cooling fluid that can be in thermal contact with the beam deflector.
HEATING AND TRANSFER RATE DURING RADIATION TREATMENT [0240] Several processes can occur in biomass when electrons from an electron beam interact with matter in inelastic collisions. For example, ionization of the material, polymer chain fission in the material, crossing of polymers in the material, oxidation of the material, generation of X-rays (“Bremsstrahlung”) and excitation by vibration of the molecules (for example, generation of the phonon). Without being linked to a particular mechanism, the reduction in resistance can be attributed to these various effects of inelastic collision, for example: ionization, polymer chain fission, oxidation or phonon generation. Some of the effects (for example, especially the generation of X-rays) require protection and the construction of barriers, for example: the enclosure of irradiation processes in a concrete cavity (or other radiopaque material). Another effect of irradiation, excitation by vibration, is equivalent to heating the sample. Heating the sample by irradiation can help to reduce recalcitrance, but overheating can destroy the material, as explained below.
[0241] The adiabatic rise in temperature (AT) from the absorption of ionizing radiation is given by the equation: AT = D / Cp: where D is the average dose in kGy, Cp is the heat capacity in J / g ° C , and AT is the temperature change in degrees Celsius. A typical dry biomass material will have a heat capacity close to 2. Wet biomass will have a greater heat capacity, depending on the amount of water, since the heat capacity of the water is very high (4.19 J / g ° C). Metals have much lower heat capacities, for example: 304 stainless steel has a heat capacity of 0.5 J / g ° C. The temperature change
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87/125 due to the instantaneous absorption of radiation in a biomass and stainless steel for various radiation doses is shown in Table 1.
Table 1: Calculated temperature rise for biomass and stainless steel.
Dose (Mrad) Estimated Biomass ΔΤ (° C) Steel ΔΤ (° C) 10 50 200 50 250, decomposition 1000 100 500, decomposition 2000 150 750, decomposition 3000 200 1000, decomposition 4000
[0242] High temperatures can destroy and or modify biopolymers in biomass, so that polymers (eg cellulose) are unsuitable for further processing. Biomass subjected to high temperatures can become dark, sticky and generate odors that indicate decomposition. Viscosity can even make the material difficult to transport. Smells can be unpleasant and a safety issue. In fact, it has been found that keeping biomass below approximately 200 ° C is beneficial in the process described here (for example, below approximately 190 ° C, below approximately 180 ° C, below approximately 170 ° C, below approximately 160 ° C, below approximately
150 ° C, below approximately 140 ° C, below approximately
130 ° C, below approximately 120 ° C, below approximately
110 ° C, between approximately 60 ° C and
180 ° C, between approximately
60 ° C
160 ° C, between approximately
60 ° C
150 ° C, between approximately
60 ° C
140 ° C, between approximately
60 ° C
130 ° C, between approximately
60 ° C
120 ° C, between approximately
80 ° C
180 ° C, between approximately
100 ° C and
180 ° C, between approximately
120 ° C and
180 ° C, between approximately
140 ° C and
180 ° C, between approximately
160 ° C and
180 ° C, between approximately 100 ° C and 140 ° C, between approximately 80 ° C and 120 ° C).
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88/125 [0243] It has been found that irradiation greater than 10 Mrad is desirable for the processes described here (for example, for the reduction of resistance). A high flow is also desirable, so that irradiation does not become a limiting factor in the processing of biomass. The treatment is managed by a dose rate equation: M = FP / D-time, where M is the mass of the irradiated material (Kg), F is the fraction of power that is adsorbed (without unit), P is the power emitted (kW = Voltage in MeV x Current in mA), time is the treatment time (sec) and D is the adsorbed dose (kGy). In an exemplary process where the fraction of the absorbed power is fixed, the emitted Power is constant and the dosage established is the desired one, the yield (for example, M, the processed biomass) can be increased by increasing the irradiation time. However, increasing the irradiation time without allowing the material to cool can overheat the material, as exemplified by the calculations shown above. Since biomass has a low thermal conductivity (less than approximately 0.1 Wm^-1K^-1), heat dissipation is slow, unlike, for example, metals (greater than approximately 10 Wm 1K^-1) that can dissipate energy quickly as long as there is a heat sink to transfer energy to.
BIOMASS MATERIALS [0244] Lignocellulosic materials include, but are not limited to, wood (for example, softwood, softwood, softwood bark, softwood, softwood, hardwood, hardwood willow, poplar hardwood, birch hardwood, hardwood bark, hardwood trunks, pine cones and pine needles), particle board, chemical pulps, mechanical pulps, paper, paper waste, forest waste (eg sawdust, poplar wood, wood chips, leaves), grasses (eg wild grass, miscantum, tusk grass, ice grass, Coastal Bermuda grass), grain residues, (eg bark rice, oat hulls,
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89/125 wheat chaff, barley husks), agricultural residues (eg silage, canola straw, wheat straw, barley straw, oat straw, rice straw, jute, hemp, flax, bamboo, sisal, abaca, corn cob, soy stubble, corn fiber, alfalfa, hay, coconut fiber, nutshells, palm leaves and coconut oil by-products), cotton, cottonseed fibers, flax, processing waste sugar (eg bagasse, beet pulp, agave bagasse), algae, seaweed, seaweed, manure (eg solid cattle manure, pig waste), debris, carrot processing waste, washing molasses, alfalfa and mixtures of these materials.
[0245] In some cases, the lignocellulosic material includes ears of corn. Milled or mechanically ground corn cobs can be spread in a layer of relatively uniform thickness for irradiation and, after irradiation, are easy to disperse in the medium for further processing. To facilitate harvesting and collection, in some cases, the entire corn plant is used, including corn stalk, corn kernels, and in some cases, even the plant's root system.
[0246] Advantageously, no additional nutrients (except for a nitrogen source, for example, urea or ammonia) are required during the fermentation of corn cobs or cellulosic or lignocellulosic containing significant amounts of corn cobs.
[0247] Corn cobs, before and after comminution, are also easier to transport and disperse and are less likely to form explosive mixtures in the air than other cellulosic or lignocellulosic materials such as hay and grasses.
[0248] Cellulosic materials include, for example, paper, paper products, waste paper, cellulose, pigmented papers, loaded papers, coated papers, filled papers, magazines, printed matter (for example, books, catalogs, manuals, labels, calendars , postcards, brochures, prospectuses, newsprint),
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90/125 printer paper, multi-coated paper, cardboard, cardboard, cardboard, materials with a high content of cellulose, such as cotton and mixtures of any of these, for example, paper products described in US Order No. 13 / 396,365 (“ Magazine Feedstocks ”by Medoff et al., Filed on February 14, 2012), the full disclosure of which is incorporated here by reference.
[0249] Cellulosic materials may also include lignocellulosic materials, which have been partially or completely smoothed.
[0250] In some cases, other biomass materials can be used, for example: starchy materials. Starchy materials include starch itself, for example, corn starch, wheat starch, potato starch or rice starch, a starch derivative or a material that includes starch, such as an edible product or a crop. For example, the starchy material can be cassava, buckwheat, banana, barley, cassava, cudzu, hollow, sago, sorghum, regular domestic potatoes, sweet potatoes, taro, yams or one or more beans, such as broad beans, lentils or peas . Mixtures of two or more starchy materials are also starchy materials. Mixtures of starchy, cellulosic and or lignocellulosic materials can also be used. For example, biomass can be an entire plant, a part of a plant or different parts of a plant, for example, a wheat plant, cotton plant, a corn plant, rice plant or a tree. Starch-rich materials can be treated by any of the methods described in this document.
[0251] Microbial materials include, but are not limited to, any natural or genetically modified microorganisms or organisms that contain or are capable of providing a source of carbohydrates (eg cellulose), eg protists, eg protist animals ( for example, ameboid flagellated protozoa, ciliate and sporozoa) and plant protists (for example, algae such as Alveolates, Chlorarachnea, Cryptophyta, Euglenophyta, Glaucophyta, Haptophyta,
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91/125 red algae, stramenopiles and viridaeplantae). Other examples include algae, plankton (e.g., macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton and femtoplankton), phytoplankton, bacteria (e.g., gram positive bacteria, gram negative and extremophilic bacteria), yeast and / or mixtures thereof. In some cases, microbial biomass can be obtained from natural sources, for example, the ocean, lakes, bodies of water, for example, salt water or fresh water, or on land. As an alternative or, in addition, microbial biomass can be obtained from culture systems, for example, large-scale dry and wet culture and fermentation systems. In other embodiments, biomass materials, such as cellulosic, starchy and lignocellulosic materials, can be obtained by transgenic microorganisms and plants that have been modified in relation to a variety of wild type. Such modifications can be, for example, through the iterative steps of selection and reproduction to obtain desired characteristics in a plant. In addition, the plants may have had genetic material removed, modified, silenced or added with respect to the wild type variety. For example, genetically modified plants can be produced by recombinant DNA methods, where genetic modifications include introducing or modifying specific genes of parental varieties, or, for example, using transgenic breeders in which a specific gene or genes are introduced to a plant. a different species of plant and / or bacteria. Another way to create genetic variation is through mutation production in which new alleles are created artificially from endogenous genes. Artificial genes can be created in a variety of ways, including treating plants or seeds with, for example, chemical mutations (for example, using alkylating agents, epoxides, alkaloids, peroxides, formaldehydes), irradiation (for example, X-rays) , gamma rays, neutrons, beta particles, alpha particles, protons, deuterons, UV radiation) and thermal shocks or other external pressures and selection techniques
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Subsequent 92/125. Other methods of producing modified genes are through shuffling of PCR and DNA susceptible to error followed by the insertion of the desired modified DNA in the desired plant or seed. Methods of introducing the desired genetic variation in the seeds or plant include, for example, the use of a bacterial carrier, biolistics, calcium phosphate precipitation, electroporation, genetic splicing, genetic silencing, lipofection, microinjection and viral transporters. Additional genetically modified materials have been described in US Order Series No. 13 / 396,369 filed on February 14, 2012, the complete publication of which is hereby incorporated by reference. Some of the methods described here can be practiced with mixtures of all the biomass materials described here.
PREPARATION OF BIOMASS MATERIAL - MECHANICAL TREATMENTS [0252] Biomass can be in dry form, for example, with less than
about 35% of content in humidity (for example, any less in about 20%, any less in about 15%, any less in about 10%, any less in about 5%, any less in
approximately 4%, less than approximately 3%, less than approximately 2% or even less than approximately 1%). Biomass can also be distributed in a wet state, for example, as a wet solid, a paste or a suspension containing at least approximately 10% by weight of solids (for example, at least approximately 20% by weight, at least approximately 30% by weight at least approximately 40% by weight, at least approximately 50% by weight, at least approximately 60% by weight, at least approximately 70% by weight).
[0253] The processes disclosed here may use low volumetric density materials, for example: cellulosic or lignocellulosic raw materials
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93/125 that have been physically pretreated to have a volumetric density less than approximately 0.75 g / cm ³ , for example: less than approximately 0.7, 0.65, 0.60, 0.50, 0 , 35, 0.25, 0.20, 0.15, 0.10, 0.05 or less, for example: less than approximately 0.025 g / cm ³ . Bulk density is determined using ASTM D1895B. Briefly, the method involves filling a known volume measuring cylinder with a sample and obtaining a sample weight. Bulk density is calculated by dividing the sample weight in grams by the known volume of the cylinder in cubic centimeters. If desired, low apparent density materials can be densified, for example, by the methods described in U.S. Pat. US No. 7,971,809 to Medoff, the full disclosure of which is incorporated by reference here.
[0254] In some cases, pre-treatment processing includes sorting the biomass material. Screening can be through a mesh or perforated plate with a desired opening size, for example: less than approximately 6.35 mm (1/4 inch, 0.25 inch), (for example, less than approximately 3 .18 mm (1/8 inch, 0.125 inch), less than approximately 1.59 mm (1/16 inch, 0.0625 inch), is less than approximately 0.79 mm (1/32 inch) , 0.03125 inch), for example: less than approximately 0.51 mm (1/50 inch, 0.02000 inch), less than approximately 0.40 mm (1/64 inch, 0.015625 inch ), less than approximately 0.23 mm (0.009 inch), less than approximately 0.20 mm (1/128 inch, 0.0078125 inch), less than approximately 0.18 mm (0.007 inch), less than approximately 0.13 mm (0.005 inch) or even less than approximately 0.10 mm (1/256 inch, 0.00390625 inch) .In one configuration, the desired biomass falls through perforations or screen and therefore However, the biomass larger than the perforations or screen is not irradiated. These larger materials can be reprocessed, for example,
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94/125 by commutation, or they can simply be removed from processing. In another configuration, the material that is larger than the perforations is irradiated and the smallest material is removed by the process of sorting or recycling. In this type of configuration, the conveyor itself (for example, a part of the conveyor) can be perforated or made with a mesh. For example, in a specific modality the biomass material can be moist and the perforations or mesh allow water to drain from the biomass before irradiation.
[0255] The sorting of the material can also be by a manual method, for example, by an operator or mecanoid (for example, a robot equipped with a color, reflectivity or other sensor) that removes the unwanted material. The sorting can also be by magnetic sorting, in which a magnet is arranged close to the transported material and the magnetic material is removed magnetically.
[0256] Optional pretreatment processing may include heating the material. For example, a part of the conveyor carrying biomass or other material can be sent through the heated zone. The heated zone can be created, for example, by IR radiation, microwave, combustion (for example, gas, coal, oil, biomass), resistive heating and / or inductive coils. Heat can be applied from at least one side or more than one side, it can be continuous or periodic and it can be for just a part of the material or for the whole material. For example, a part of the transport channel can be heated using a heating liner. The heating can be, for example, for the purpose of drying the material. In the case of drying of the material, this can also be facilitated, with or without heating, by the movement of a gas (for example, air, oxygen, nitrogen, He, CO2, argon) over and / or through the biomass, as it is being transported.
[0257] Optionally, the pre-treatment process can include cooling the material. The cooling material is described in US Pat. No. 7,900,857 to
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95/125
Medoff, whose full disclosure is hereby incorporated by reference. For example, refrigeration can take place by supplying a refrigeration fluid, for example: water (for example, with glycerin) or nitrogen (for example, liquid nitrogen) at the bottom of the transport channel. Alternatively, a refrigerant gas, for example, refrigerated nitrogen, can be inflated over the biomass materials or under the transport system.
[0258] Another optional pre-treatment processing method may include adding a material for biomass or other raw materials. The additional material can be added, for example, by showering, dusting and / or by pouring the material over the biomass, as it is transported. Materials that can be added include, for example, metals, ceramics and / or ions as described in U.S. Pat. U.S. US No. 2010/0105119 A1 (filed October 26, 2009) and Pat. US No. 2010/0159569 A1 (filed December 16, 2009), the full disclosures of which are incorporated herein by reference. Optional materials that can be added include acids and bases. Other materials that can be added are oxidizers (for example, peroxides, chlorates), polymers, polymerizable monomers (for example, containing unsaturated bonds), water, catalysts, enzymes and / or organisms. Materials can be added, for example, in pure form, as a solution, in a solvent (for example, water or an organic solvent) and / or as a solution. In some cases, the solvent is volatile and can be evaporated, for example, by heating and / or blowing the gas as previously described. The added material can form a uniform layer over the biomass or be a homogeneous mixture of different components (for example, biomass and additional material). The added material can modulate the subsequent irradiation step, increasing irradiation efficiency, dampening irradiation or changing the effect of irradiation (for example, from electron beams to x-rays or heat). The method may have no impact on irradiation, but it can be useful for processing at
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96/125 additional downstream. The added material can help transport the material, for example, by decreasing dust levels.
[0259] Biomass can be delivered to the conveyor (for example, vibrating conveyors that can be used on the vaults described in this document) by a conveyor belt, a pneumatic conveyor, a screw conveyor, a funnel, a pipe, manually or by a combination of these. The biomass can, for example, be felled, poured and / or placed on the conveyor by any of these methods. In some embodiments, material is delivered to the conveyor using an embedded material distribution system to help maintain a low oxygen atmosphere and / or control dust and fines. Fine particles and biomass dust suspended in the air or elevated are undesirable, as they may pose an explosion hazard or damage the protective films of an electron gun (if such a device is used to treat the material).
[0260] The material can be leveled to form a uniform thickness between approximately 0.0312 and 5 inches (for example, between approximately 0.0625 and 2,000 inches, between approximately 0.125 and 1 inch, between approximately 0.125 and 0.5 inch, between approximately 0.3 and 0.9 inch, between approximately 0.2 and 0.5 inch, between approximately 0.25 and 1.0 inch, between approximately 0.25 and 0.5 inch, 0.100 and + / - 0.025 inch, 0.150 and +/- 0.025 inch, 0.200 and +/- 0.025 inch, 0.250 and +/- 0.025 inch,
0.300 and +/- 0.025 inch, 0.350 and +/- 0.025 inch, 0.400 and +/- 0.025 inch,
0.450 and +/- 0.025 inch, 0.500 and +/- 0.025 inch, 0.550 and +/- 0.025 inch,
0.600 and +/- 0.025 inch, 0.700 and +/- 0.025 inch, 0.750 and +/- 0.025 inch,
0.800 and +/- 0.025 inch, 0.850 and +/- 0.025 inch, 0.900 and +/- 0.025 inch,
0.900 and +/- 0.025 inch.
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97/125 [0261] Generally, it is preferred to transport the material as quickly as possible through the electron beam to maximize throughput. For example, material can be transported at rates of at least 1 foot / min, for example, at least 2 feet / min, at least 3 feet / min, at least 4 feet / min, at least 5 feet / min, at least at least 10 feet / min, at least 15 feet / min, 20, 25, 30, 35, 40, 45, 50 feet / min. The transport rate is related to the beam current, for example, for a thick biomass of% inch and 100 mA, the conveyor can move at approximately 20 feet / min to provide a useful irradiation dose, at 50 mA o conveyor can move at approximately 10 feet / min to provide approximately the same irradiation dosage.
[0262] After the biomass material has been transported through the radiation zone, optional post-treatment processing can be done. Optional post-treatment processing can, for example, be a process described in relation to pre-irradiation processing. For example, biomass can be screened, heated, cooled, or combined with bioadditives. Exclusively for post-irradiation, removal of radicals can occur, for example, extinction of radicals by the addition of liquids or gases (for example, oxygen, nitrous oxide, ammonia, liquids), using pressure, heat, and / or the addition of Neutralizers of radicals. For example, biomass can be transported out of the enclosed conveyor and exposed to a gas (for example, oxygen) where it is extinguished, forming carboxylated groups. In one embodiment, biomass is exposed during irradiation to reactive gas or fluid. The extinction of the biomass that has been irradiated is described in Pat. No. 8,083,906 to Medoff, whose full disclosure is hereby incorporated by reference.
[0263] If desired, one or more mechanical treatments can be used in addition to irradiation to further reduce the recalcitrance of material containing carbohydrates. These processes can be applied before, during or after irradiation.
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98/125 [0264] In some cases, mechanical treatment may include an initial preparation of raw material as received, for example, size reduction of materials, such as by comminution, for example, cutting, grinding, spraying or shearing. For example, in some cases, loose raw material (for example, recycled paper, starchy materials or wild grass) is prepared for shearing or fragmentation. Mechanical treatment can reduce the volumetric density of the carbohydrate-containing material, increase the surface area of the carbohydrate-containing material and / or decrease one or more of the dimensions of the carbohydrate-containing material.
[0265] Alternatively, or in addition, the raw material can be treated with another treatment, for example, chemical treatment, such as with an acid (HCl, H2SO4, H3PO4), a base (for example, KOH and NaOH), a chemical oxidant (eg peroxides, chlorates, ozone), irradiation, vapor explosion, pyrolysis, heat treatment, sonication, oxidation, chemical treatment. Treatments can be in any order and in any sequence and combinations. For example, the raw material material can first be physically treated by one or more treatment methods, for example, chemical treatment including and in combination with acid hydrolysis (for example, using HCl, H2SO4, H3PO4), radiation, sonication , oxidation, pyrolysis, steam explosion, and then mechanically treated. This sequence can be advantageous, since the materials treated by one or more of the other treatments, for example, irradiation or pyrolysis, tend to be more fragile and, therefore, may be easier to change the structure of the material by mechanical treatment. As another example, a raw material material can be transported through ionizing radiation using a carrier as described here and then mechanically treated. Chemical treatment can remove some or all of the lignin (for example, chemical pulp) and can partially or completely hydrolyze the material. The methods can also be used with
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99/125 previously hydrolyzed material. The methods can also be used with material that has not been pre-hydrolyzed. The methods can be used with mixtures of hydrolyzed and non-hydrolyzed materials, for example, with about 50% or more of non-hydrolyzed material, with about 60% or more of non-hydrolyzed material, with about 70% or more of material non-hydrolyzed, with about 80% or more non-hydrolyzed material or even 90% or more non-hydrolyzed material.
[0266] In addition to size reduction, which can be carried out initially and / or later in processing, mechanical treatment can also be advantageous for opening, tensioning, breaking or destroying materials containing carbohydrates, making the cellulose of the materials more susceptible to chain splitting and / or rupture of the crystalline structure during physical treatment.
[0267] Methods for mechanically treating carbohydrate-containing material include, for example, grinding or crushing. The grinding can be carried out using, for example, a hammer mill, ball mill, colloid mill, conical or cone mill, disc mill, Chilean mill, Wiley mill, cereal mill or other mill. The grinding can be carried out using, for example, an impact / cutting grinder. Some exemplary grinders include stone crushers, pin grinders, coffee grinders and drill grinders. The crushing or grinding can be produced, for example, by a corresponding pin or another element, as is the case with the pin mill. Other methods of mechanical treatment include mechanical rupture, other methods that apply pressure to the fibers and crushing of air friction. Additional appropriate mechanical treatments include any other technique that continues to disrupt the internal structure of the material that was initiated by the steps in the previous process.
[0268] Mechanical feed preparation systems can be configured to produce streams with specific characteristics, such as, for example,
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100/125 example, specific maximum size, specific width by width, or proportions of specific surface areas. Physical preparation can increase the rate of reactions, improve the movement of the material in a conveyor, improve the irradiation profile of the material, improve the uniformity of the radiation of the material or reduce the time required for the process to open the materials and make them more accessible to processes and / or reagents, such as reagents in a solution.
[0269] Bulk density of raw materials can be controlled (for example, increased). In some situations, it may be desirable to prepare a low density material, for example, by densifying the material (for example, densification can make it easier and less expensive to transport elsewhere) and then revert the material to a state of lower bulk density (for example, after transport). The material can be densified, for example, from less than approximately 0.2 g / cc to more than approximately 0.9 g / cc (for example, less than approximately 0.3 to more than approximately 0.5 g / cc, less than approximately 0.3 to more than approximately 0.9 g / cc, less than approximately 0.5 to more than approximately 0.9 g / cc, less than approximately 0.3 to more than approximately 0.8 g / cc, less than approximately 0.2 to more than approximately 0.5 g / cc). For example, the material can be densified by the methods and equipment disclosed in Pat. U.S. No. 7,932,065 to Medoff and International Publication No. WO 2008/073186 (which was filed on October 26, 2007, was published in English, and which designated the United States), the full disclosures of which are incorporated herein by reference. Densified materials can be processed by any of the methods described in this document, or any material processed by any of the methods described in this document can be further densified.
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101/125 [0270] In some embodiments, the material to be processed is in the form of a fibrous material that includes fibers produced by shearing a fiber source. For example, shearing can be performed with a rotary knife cutter.
[0271] For example, a fiber source, for example, that is resistant or that has had its resistance level reduced, for example, in a rotary knife cutter, to produce a first fibrous material. The first fibrous material is passed through a first screen, for example, having an average opening size of 1.59 mm or less (1/16 inch, 0.0625 inch), produces a second fibrous material. If desired, the fiber source can be cut before shearing, for example, with a shredder. For example, when a paper is used as a fiber source, the paper can be cut first into strips that are, for example, 1/4 to 1/2 inch wide, using a shredder, for example, a shredder with a screw counter-rotating, such as those manufactured by Munson (Utica, NY). As an alternative to shredding, the paper can be reduced in size by cutting to a desired size using a guillotine cutter. For example, the guillotine cutter can be used to cut paper into sheets that are, for example, 10 inches wide by 12 inches long.
[0272] In some embodiments, the shear of the fiber source and the passage of the first resulting fibrous material through a first screen are performed simultaneously. Shearing and passing can also be carried out in a batch process.
[0273] For example, a rotary cutter can be used to simultaneously shear the fiber source and protect the first fibrous material. A rotary knife cutter includes a funnel that can be loaded with a sheared fiber source prepared by shredding a fiber source.
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102/125 [0274] In some implementations, the raw material receives physical treatment before saccharification and / or fermentation. Physical treatment processes may include one or more of any of those described here, such as mechanical treatment, chemical treatment, irradiation, heat treatment, sonication, oxidation, pyrolysis or vapor explosion. Treatment methods can be used in combinations of two, three, four, or even all of these technologies (in any order). When more than one treatment method is used, the methods can be applied at the same time or at different times. Other processes that alter the molecular structure of the biomass raw material can also be used, alone or in combination with the processes disclosed in this document.
[0275] The mechanical treatments that can be used, and the characteristics of mechanically treated materials containing carbohydrates, are described in more detail in US Order Publication No. 2012/0100577 A1, filed on October 18, 2011, the entire disclosure of which is incorporated herein by reference.
[0276] The mechanical treatments described in this document can also be applied to the processing of hydroxyl-carboxylic polymers and materials based on hydroxyl-carboxylic polymers.
SONICATION, PYROLYSIS, OXIDATION, VAPOR EXPLOSION [0277] If desired, one or more processes of sonication, pyrolysis, oxidatives or vapor explosion can be used in addition to or in lieu of irradiation to reduce or additionally reduce the recalcitrance of the material containing carbohydrate. For example, these processes can be applied before, during or after irradiation. These processes are described in detail in Pat. No. 7,932,065 to Medoff, the full disclosure of which is incorporated herein by reference.
THERMAL TREATMENT OF BIOMASS
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103/125 [0278] Alternatively or additionally, biomass can be heat treated for up to twelve hours at temperatures in the range of approximately 90 ° C to approximately 160 ° C. Optionally, this heat treatment step is performed after the biomass has been irradiated with an electron beam. The amount of time for heat treatment is up to 9 hours, alternately up to 6 hours, optionally up to 4 hours and still up to approximately 2 hours. The treatment time can be up to 30 minutes when the mass can be heated effectively.
[0279] Heat treatment can be carried out at approximately 90 ° C to approximately 160 ° C or, optionally, at 100 to 150 or, alternatively, at 120 to 140 ° C. The biomass is suspended in water so that the biomass index is 10 to 75% by weight in water. In case the biomass is the irradiated biomass, water is added and the heating treatment is carried out.
[0280] The heat treatment is carried out in an aqueous suspension or mixture of biomass. The amount of biomass is 10 to 90% by weight of the total mixture, alternatively 20 to 70% by weight or, optionally, from 25 to 50% by weight. The irradiated biomass can have a minimum water content so that water must be added before heat treatment.
[0281] Since at temperatures above 100 ° C there will be pressure, it is necessary that the receptacle withstand pressure due to the vaporized water. The heat treatment process can be batch, continuous, semi-continuous or other reactor configurations. The continuous configuration of the reactor can be a tubular reactor and can include device (s) inside the tube that will facilitate the heat transfer and mixing / suspension of the biomass. Such tubular devices may include one or more static mixers. Heat can also be delivered to the system by direct steam injection.
USE OF TREATED BIOMASS MATERIAL
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104/125 [0282] Using the methods described here, an initial biomass material (for example, plant biomass, animal biomass, paper and municipal residual biomass) can be used as a raw material to produce useful intermediates and products such as acids organic, salts of organic acids, hydroxycarboxylic acids, (for example, lactic acid), anhydride acid, esters of organic acids and fuels, for example, fuels for internal combustion engines or raw materials for fuel cells. Systems and processes are described in this document that can use readily available cellulosic and / or lignocellulosic materials as raw material, but can often be difficult to process, for example, municipal waste streams and paper waste streams, such as streams that include newspaper, kraft paper, corrugated paper or mixtures thereof.
[0283] In order to convert the raw material into a form that can be easily processed, cellulose containing glucan or xylan in the raw material can be hydrolyzed to low molecular weight carbohydrates, such as sugars, by a saccharifying agent, for example, an enzyme or acid, a process known as saccharification. Low molecular weight carbohydrates can then be used, for example, in an existing manufacturing plant, such as a single-cell protein plant, an enzyme manufacturing plant or a fuel plant, for example, an ethanol plant.
[0284] The raw material can be hydrolyzed using an enzyme, for example, by combining the materials and the enzyme in a solvent, for example, in aqueous solution.
[0285] Alternatively, enzymes can be supplied by organisms that break down biomass, such as cellulose and / or lignin portions of biomass, contain or manufacture various cellulolytic enzymes (cellulases), ligninases or various biomass degradation metabolites with small molecules. These enzymes can be a complex of enzymes that act synergistically to
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105/125 degrade crystalline cellulose or the lignin portions of biomass. Examples of cellulotic enzymes: endoglucanases, cellobiohydrolases and cellobiases (beta-glucosidases).
[0286] During saccharification a cellulosic substrate can be initially hydrolyzed by endoglucanases at random locations, producing oligomeric intermediates. These intermediates are then substrates for exo-dividing glucanases such as cellobiohydrolase to produce cellobiosis from the ends of the cellulose polymer. Cellobiosis is a water-soluble 1,4-linked dimer of glucose. Finally, celobiase is divided into cellobiosis to generate glucose. The efficiency (for example, time to hydrolyze and / or hydrolysis completeness) of this process varies according to the recalcitrance of the cellulosic material.
LIGNIN DERIVED PRODUCTS [0287] The irradiated biomass (eg spent lignocellulosic material) from lignocellulosic processing by the described methods is expected to have a high lignin content and, in addition to being useful for the production of energy through combustion in a cogeneration plant, can have uses like other valuable products. The spent biomass can be a by-product of the hydroxycarboxylic acid monomer production process. For example, lignin can be used as captured as a plastic, or it can be synthetically enhanced for other plastics. In some cases, it can also be converted into lignosulfonates, which can be used as binders, dispersants, emulsifiers or as sequestrants.
[0288] When used as a binder, lignin or lignosultonate can be used, for example, in coal briquettes, in ceramics, to agglutinate soot, to agglutinate fertilizers and herbicides, as a dust inhibitor, to produce a slab particulate or plywood, to agglutinate foods of
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106/125 animals, as a fiberglass binder, as a linoleum paste binder and as a soil stabilizer.
[0289] As a dispersant, lignin or lignosulfonates can be used, for example, as mixtures of concrete, clay and ceramics, coloring pigments, leather tanning and plasterboard.
[0290] As an emulsifier, lignin or lignosulfonates can be used, for example, in asphalt emulsions, pigments and dyes, pesticides and wax.
[0291] As a scavenger, lignin or lignosulfonates can be used, for example, in micronutrient systems, cleaning compounds and water treatment systems, for example, for cooling and boiling systems.
[0292] For energy production, lignin generally has a higher energy content than holocellulose (cellulose and hemicellulose), since it contains more carbon than homocellulose. For example, dry lignin can have an energy content of between about 11,000 and 12,500 BTU per pound, compared to 7,000 to 8,000 BTU per pound of holocellulose. As such, lignin can be densified and converted into briquettes and pellets for burning. For example, lignin can be converted to pellets by any method described here. For a pellet or briquette with slower incineration, the lignin can be crossed, as by applying a radiation dose between approximately 0.5 Mrad and 5 Mrad. Crosslinking can become a slower burning form factor. The form factor, such as a pellet or briquette, can be converted to synthetic coal or pyrolysis coal in the absence of air, for example, between 400 and 950 ° C. Before pyrolysis, it may be desirable to cross-link lignin to maintain structural integrity.
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107/125 [0293] Cogeneration using spent biomass is described International Application No. PCT / US2014 / 021634 filed on March 7, 2014, the complete publication of which is incorporated by reference.
[0294] Products derived from lignin can also be combined with polyhydroxycarboxylic acid and products derived from polyhydroxycarboxylic acid. (for example, the polyhydroxycarboxylic acid that was produced as described in this document). For example, lignin and products derived from lignin can be beaten, grafted or otherwise combined and / or mixed with polyhydroxycarboxylic acid. Lignin can, for example, be useful for reinforcing, plasticizing or otherwise modifying polyhydroxycarboxylic acid.
SACARIFICATION [0295] In order to convert the raw material into a form that can be easily processed, cellulose containing glucan or xylan in the raw material can be hydrolyzed to low molecular weight carbohydrates, such as sugars, by a saccharification agent , for example, an enzyme or acid, a process known as saccharification. Low molecular weight carbohydrates can then be used, for example, in an existing manufacturing plant, such as a single-cell protein plant, an enzyme manufacturing plant or a fuel plant, for example, an ethanol plant.
[0296] The raw material can be hydrolyzed using an enzyme, for example, by combining the materials and the enzyme in a solvent, for example, in aqueous solution.
[0297] Alternatively, enzymes can be supplied by organisms that break down biomass, such as cellulose and / or parts of biomass lignin, contain or manufacture various cellulolytic enzymes (cellulases), ligninases or various biomass degradation metabolites with small molecules. These enzymes can be a complex of enzymes that act synergistically to
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108/125 degrade crystalline cellulose or the lignin portions of biomass. Examples of cellulotic enzymes: endoglucanases, cellobiohydrolases and cellobiases (beta-glucosidases).
[0298] During saccharification a cellulosic substrate can be initially hydrolyzed by endoglucanases at random locations, producing oligomeric intermediates. These intermediates are then substrates for exo-dividing glucanases such as cellobiohydrolase to produce cellobiosis from the ends of the cellulose polymer. Cellobiosis is a water-soluble 1,4-linked dimer of glucose. Finally, celobiase is divided into cellobiosis to generate glucose. The efficiency (for example, time to hydrolyze and / or hydrolysis completeness) of this process varies according to the recalcitrance of the cellulosic material.
[0299] In this way, the treated biomass materials can be saccharified, combining the material and a cellulase enzyme in a fluid medium, for example, an aqueous solution. In some cases, the material is boiled, dipped or cooked in hot water before saccharification, as described in Pat. US No. 2012/0100577 A1 by Medoff and Masterman, filed on April 26, 2012, the entire contents of which are incorporated herein by reference.
[0300] Saccharification can be done by inoculating a mixture of raw sugar produced by saccharification of a reduced resistant lignocellulosic material to produce a hydroxycarboxylic acid. Hydroxycarboxylic acid can be selected from the group glycolic acid, D-lactic acid, L-lactic acid, D-malic acid, L-malic acid, citric acid, D-tartaric acid, L-tartaric acid and mesotartaric acid. The raw sugar mixture can be the reduced resistant lignocellulosic material that has been processed by irradiating the lignocellulosic material with an electron beam.
[0301] The saccharification process can be partially or completely carried out in a tank (for example, a tank with a volume of at least 4000, 40,000, or 500,000 L) in a factory and / or can be partially or completely
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109/125 carried out in transit, for example, in a wagon, tanker, or a supertanker or hold of a ship. The time required for complete saccharification will depend on the conditions of the process and the material containing carbohydrate and enzyme used. If saccharification is carried out in a factory under controlled conditions, cellulose can be substantially and entirely converted to sugar, for example, glucose in approximately 12-96 hours. If saccharification is performed partially or completely in transit, saccharification may take longer.
[0302] It is generally preferred that the contents of the tank are mixed during saccharification, for example, using a mixing jet as described in International Application No. PCT / US2010 / 035331, deposited on May 18, 2010, which was published in English as WO 2010/135380 and designated the United States, the full disclosure of which is hereby incorporated by reference.
[0303] The addition of surfactants can increase the saccharification rate. Examples of surfactants include nonionic surfactants, such as a Tween® 20 or Tween® 80 polyethylene glycol surfactants, ionic surfactants or amphoteric surfactants.
[0304] It is generally preferred that the concentration of the sugar solution resulting from saccharification is relatively high, for example: greater than 40%, or greater than 50, 60, 70, 80, 90 or even greater than 95% by weight. Water can be removed, for example, through evaporation, to increase the concentration of the sugar solution. This reduces the volume to be sent and also inhibits microbial growth in the solution.
[0305] Alternatively, low concentration sugar solutions can be used, in which case it may be desirable to add an antimicrobial additive, for example, a broad spectrum antibiotic, in a low concentration, for example, 50 to 150 ppm. Other appropriate antibiotics include amphotericin B, ampicillin, chloramphenicol, ciprofloxacin, gentamicin, hygromycin B, kanamycin,
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110/125 neomycin, penicillin, puromycin, streptomycin. Antibiotics inhibit the growth of microorganisms during transport and storage and can be used in suitable concentrations, for example, between 15 and 1000 ppm by weight, for example, between 25 and 500 ppm or between 50 and 150 ppm. If desired, an antibiotic can be included, even if the sugar concentration is relatively high. Alternatively, other anti-microbial bioadditives with preservative properties can be used. Preferably the antimicrobial additive (s) are food grade.
[0306] A solution of relatively high concentration can be obtained by limiting the amount of water added to the biomass material with the enzyme. The concentration can be controlled, for example, by controlling how much saccharification occurs. For example, the concentration can be increased by adding more carbohydrate-containing material to the solution. In order to keep the sugar being produced in solution, a surfactant can be added, for example, one of those discussed above. Solubility can also be increased by increasing the temperature of the solution. For example, the solution can be kept at a temperature of 40-50 ° C, 60-80 ° C or even higher.
SACARIFICATION AGENTS [0307] Suitable cellulosic enzymes include cellulases of species in the genera Bacillus, Coprinus, Myceliophthora, Cephalosporium, Scytalidium, Penicillium, Aspergillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acrylic, especially Chryssosporium from Aspergillus species (see, for example, Pub. EP No. 0 458 162), Humicola insolens (reclassified as Scytalidium thermophilum, see, for example, US Patent No. 4,435,307), Coprinus cinereus, Fusarium oxysporum, Myceliophthora thermophila , Meripilus giganteus, Thielavia terrestris, Acremonium sp. (including, but not limited to, A. persicinum, A. acremonium, A. brachypenium, A.
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111/125 dichromosporum, A. obclavatum, A. pinkertoniae, A. roseogriseum, A. incoloratum and
A. furatum). Preferred strains include Humicola insolens DSM 1800, Fusarium oxysporum DSM 2672, Myceliophthora thermophila CBS 117,65, Cephalosporium sp. RYM-202, Acremonium sp. CBS 478.94, Acremonium sp. CBS 265.95, Acremonium persicinum CBS 169.65, Acremonium acremonium AHU 9519, Cephalosporium sp. 535.71 CBS, Acremonium brachypenium CBS 866.73, Acremonium dichromosporum CBS 683.73, Acremonium obclavatum CBS 311.74, Acremonium pinkertoniae CBS 157.70, Acremoniumroseogriseum CBS 134.56, Acremonium incoloratum CBS 146.62, and Acremonium furatum CBS 146.62 299.70H. Cellulosic enzymes can also be obtained from Chrysosporium, preferably a lucknowense strain of Chrysosporium. Additional strains that can be used include, but are not limited to, Trichoderma (particularly T. viride, T. reesei and T. koningii), Alkalophilic Bacillus (see, for example, US patent No. 3,844,890 and Pub. EP No. 0 458 162) and Streptomyces (see, for example, Pub. EP No. 0 458 162).
[0308] In addition to or in combination with enzymes, acids, bases and other chemical substances (eg oxidants) can be used to saccharify lignocellulosic and cellulosic materials. These can be used in any combination or sequence (for example, before, after and / or during the addition of an enzyme). For example, strong mineral acids can be used (for example, HCl, H2SO4, H3PO4) and strong bases (for example, NaOH, KOH).
[0309] In the processes described here, for example, after saccharification, sugars (for example, glucose and xylose) can be isolated. For example, sugars can be isolated by precipitation, crystallization, chromatography (for example, simulated moving bed chromatography, high pressure chromatography), centrifugation, extraction, any other isolation method known in the art and combinations thereof.
FERMENTATION
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112/125 [0310] Yeast and bacteria Zymomonas for example can be used for fermentation or conversion of sugar to alcohol (ois). Other microorganisms are discussed below. The ideal pH for fermentation is around pH 4 to 7. For example, the optimum pH for yeast is approximately pH 4 to 5, while the optimum pH for Zimomonas is approximately pH 5 to 6. Fermentation times typical are approximately 24 to 168 hours (eg 24 to 96 hours) with temperatures ranging from 20 ° C to 40 ° C (eg 26 ° C to 40 ° C), however thermophilic microorganisms prefer higher temperatures .
[0311] In some modalities, for example, when anaerobic organisms are used, at least part of the fermentation is conducted in the absence of oxygen, for example, under a blanket of an inert gas such as N2, Ar, He, CO2 or mixtures thereof . In addition, the mixture may have a constant purge of an inert gas flowing through the tank during part or all of the fermentation. In some cases, the anaerobic condition can be achieved or maintained by the production of carbon dioxide during fermentation and no additional inert gas is required.
[0312] In some embodiments, all or part of the fermentation process can be stopped before low molecular weight sugar is completely converted into a product (eg, ethanol). Intermediate fermentation products include sugar and carbohydrates in high concentrations. Sugars and carbohydrates can be isolated by any means known in the art. These intermediate fermentation products can be used in the preparation of food for human or animal consumption. Additionally or alternatively, intermediate fermentation products can be ground to a fine particle size in a stainless steel laboratory mill to produce a flour-like substance. The jet mixture can be used during fermentation, and in some cases saccharification and fermentation are carried out in the same tank.
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113/125 [0313] Nutrients for microorganisms can be added during saccharification and / or fermentation, for example, the food-based nutrient packs described in US order publication No. 2012/0052536, deposited as of July 15, 2011, the full disclosure of which is incorporated by reference here.
[0314] “Fermentation” includes the methods and products that are disclosed in International Order No. PCT / US2012 / 071093 filed on December 20, 2012 and in International Order No. PCT / US2012 / 071097 filed on December 12, 2012 , the contents of both being incorporated here by reference in their entirety.
[0315] Mobile fermenters can be used, as described in International Application No. PCT / US2007 / 074028 (which was filed on July 20, 2007, was published in English as WO 2008/011598 and designated the United States) and has a US issued patent No. 8,318,453, the contents of which are incorporated herein in their entirety. Similarly, saccharification equipment can be mobile. In addition, saccharification and / or fermentation can be performed in part or entirely during transit.
FERMENTATION AGENTS [0316] The microorganisms used in fermentation can be naturally occurring microorganisms and / or engineering microorganisms. For example, the microorganism can be a bacterium (including, but not limited to, for example, cellulolytic bacteria), a fungus, (including, but not limited to, for example, yeast), a plant, a protist, for example, a protozoan or a fungus-like manifestation (including, but not limited to, for example, a mud mold) or algae. When the organisms are compatible, mixtures of organisms can be used.
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114/125 [0317] Appropriate fermenting microorganisms have the ability to convert carbohydrates, such as glucose, fructose, xylose, arabinose, mannose, galactose, oligosaccharides or polysaccharides into fermentation products. Fermentation of microorganisms includes strains of the genus Saccharomyces spp. (including, but not limited to, S. cerevisiae (bread yeast), S. distaticus, S. uvarum), the genus Kluyveromyces, (including, but not limited to, K. marxianus, K. fragilis), the genus Candida (including, but not limited to, C. pseudotropicalis and C. brassicae), Pichia stipitis (a relative of Candida shehatae), Clavispora (including, but not limited to, C. lusitaniae and C. opuntiae), the genus Pachysolen (including , but not limited to, P. tannophilus), the genus Bretannomyces (including, but not limited to, for example,
B. clausenii (Philippidis, G. P., 1996, Cellulose bioconversion technology, in Handbook on Bioethanol: Production and Utilization, Wyman, C.E., ed., Taylor & Francis, Washington, DC, 179-212). Other suitable microorganisms include, for example, Zymomonas mobilis, Clostridium spp. (including, but not limited to, C. thermocellum (Philippidis, 1996, supra), C. saccharobutylacetonicum, C. tyrobutyricum
C. saccharobutylicum, C. Puniceum, C. beijernckii and C. acetobutylicum), Moniliella spp. (including, but not limited to M. pollinis, M. tomentosa, M. madida, M. nigrescens, M. oedocephali, M. megachiliensis), Yarrowia lipolytica, Aureobasidium sp., Trichosporonoides sp., Trigonopsis variabilis, Trichosporon sp., Moniliellaacetoabutans sp., Typhula variabilis, Candida magnoliae, Ustilaginomycetes sp., Pseudozyma tsukubaensis, yeast species of the genus Zygosaccharomyces, Debaryomyces, Hansenula and Pichia, and fungi of the dematioid genus Torula (for example, T.corallina).
[0318] Many of these microbial strains are publicly available, both commercially and through depositaries, such as the ATCC (American Type Culture Collection, Manassas, Virginia, USA), the NRRL (Agricultural Research Sevice Culture Collection, Peoria, Illinois, USA) or the DSMZ (Deutsche Sammlung von
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Mikroorganismen und Zellkulturen GmbH, Braunschweig, Germany), to name a few.
[0319] Commercially available yeasts include, for example, Red Star® / Lesaffre Ethanol Red (available from RedStar / Lesaffre, USA), FALI® (available from Fleischmann's Yeast, a division of Burns Philip Food Inc., USA), SUPERSTART® (available from Alltech, now Lalemand), GERT STRAND® (available from Gert Strand AB, Sweden) and FERMOL® (available from DSM Specialties)
DISTILLATION [0320] After fermentation, the resulting liquid can be distilled using, for example, a beer column to separate ethanol and other alcohols from most water and solid waste. The steam coming out of the beer column can be, for example, 35% by weight of ethanol and can be fed to a grinding column. A mixture of almost azeotropic ethanol (92.5%) and water from the rectification column can be purified to pure ethanol (99.5%) using molecular vapor phase sieves. The lower parts of the beer column can be sent for the first effect of a three-effect evaporator. The rectifying column reflux condenser can provide heat for this first effect. After the first effect, the solids can be separated using a centrifuge and dried in a rotary dryer. A portion (25%) of the centrifuge's effluent can be recycled for fermentation and the rest, sent to the second and third effects of the evaporator. Most of the condensate from the evaporator can be returned to the process as reasonably clean condensate, with a small separate portion for wastewater treatment to prevent the accumulation of low boiling compounds.
TRANSPORT SYSTEMS
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116/125 [0321] Various transport systems can be used to transport raw material materials, for example, to a cavity or under an electron beam in a cavity. Exemplary conveyors are belt conveyors, pneumatic conveyors, screw conveyors, cars, trains, trains or cars on rails, elevators, front loader, backhoes, cranes, various spatulas and shovels, trucks, and launching devices can be used. For example, vibrating conveyors can be used in various processes described here, for example, as described in International Application No. PCT / US2013 / 064332 filed on October 10, 2013, the full disclosure of which is incorporated herein by reference.
OTHER MODALITIES [0322] Any material, process or processed materials described here can be used to make products and / or intermediates such as composites, fillers, binders, plastic additives, absorbents and controlled release agents. The methods can include densification, for example, by applying pressure and heat to the materials, for example, the compounds can be made by combining fibrous materials with resin or polymer (for example, PLA). For example, the crosslinkable radiation resin (for example, a thermoplastic resin, PLA and / or PLA derivatives) can be combined with a fibrous material to produce a crosslinkable resin / fibrous material combination. These materials can, for example, be useful as other building materials, protective sheets, containers and other structural materials (for example, molded and / or extruded products). Absorbents can be, for example, in the form of pellets, chips, fibers and / or sheets. Adsorbents can be used, for example, as pet liners, packaging materials or pollution control systems. Controlled release matrices can also be in the form of, for example, pellets, chips, fibers or sheets. Controlled release arrays can
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117/125 be used, for example, to release drugs, biocides, fragrances. For example, composites, absorbents and release control agents and their uses are described in International Order No. PCT / US2006 / 010648, filed on March 23, 2006 and in Pat. US No. 8,074,910, filed November 22, 2011, the full disclosures of which are incorporated herein by reference.
[0323] In some cases, the biomass material is treated on a first level to reduce resistance, for example, using accelerated electrons to selectively release or more sugars (for example, xylose). The biomass can then be treated at a second level to release one or more sugars (for example, glucose). Optionally, the biomass can be dried between treatments. Treatments may include applying chemical and biochemical treatments to release sugars. For example, a biomass material can be treated at a level of less than approximately 20 Mrad (for example, less than approximately 15 Mrad, less than approximately 10 Mrad, less than approximately 5 Mrad, less than approximately 2 Mrad) and then treated with a sulfuric acid solution, containing less than 10% sulfuric acid (for example, less than approximately 9%, less than approximately 8%, less than approximately 7%, less than approximately 6 %, less than approximately 5%, less than approximately 4%, less than approximately 3%, less than approximately 2%, less than approximately 1%, less than approximately 0.75%, less than approximately 0.50%, less than approximately 0.25%) to release xylose. Xylose, for example, which is released in solution, can be separated from the solids and, optionally, the solids can be washed with some solvent / solution (for example, with water and / or acidified water).
[0324] Optionally, the solids can be dried, for example, in air and / or under vacuum, optionally with heating (for example, below
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118/125 approximately 150 ° C, below approximately 120 ° C) to a water content below approximately 25% by weight (below approximately 20% by weight, below approximately 15% by weight, below approximately 10% weight below approximately 5% by weight). The solids can then be treated to a level of less than approximately 30 Mrad (for example, less than approximately 25 Mrad, less than approximately 20 Mrad, less than approximately 15 Mrad, less than approximately 10 Mrad, less than than about 5 Mrad, less than about 1 Mrad or none at all) and then be treated with an enzyme (for example, a cellulase) to release glucose. Glucose (for example, glucose in solution) can be separated from the remaining solids. The solids can then be further processed, for example, used to make energy or the other products (for example, products derived from lignin).
EXAMPLES
L- Lactic acid production from saccharified corncob in Lactobacillus species.
Materials and methods
Lactic acid producing strains tested:
The lactic acid-producing strains that were tested are listed in Table 2
Table 2: Lactic acid producing strains tested
NRRL B-441 Lactobacillus casei NRRL B-445 Lactobacillus rhamnosus NRRL B-763 Lactobacillus delbrueckii subspecies delbrueckii ATCC 8014 Lactobacillus plantarum ATCC 9649 Lactobacillus delbrueckii subspecies delbrueckii B-4525 Lactobacillus delbrueckii subspecies lactis B-4390 Lactobacillus corniformis subspecies torquens B-227 Lactobacillus pentosus B-4527 Lactobacillus brevis ATCC 25745 Pediococcus pentosaceus NRRL 395 Rhízopus oryzae
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CBS 112.07 Rhizopus oryzae CBS 127.08 Rhizopus oryzae CBS 396.95 Rhizopus oryzae
Seed Culture [0325] Cells from a frozen cell bank (-80 ° C) were grown in a propagation medium (BD Difco ™ Lactobacilli Caldo MRS) at 37 ° C, with agitation of 150 rpm for 20 hours. This seed culture was transferred to a 1.2 L (or optionally 20 L) bioreactor loaded with the media described below.
Main Culture Media [0326] All media included ear of saccharified corn that was ground in a hammer mill and irradiated with approximately 35 Mrad of electron beam irradiation. For example, saccharified corncob can be prepared as described in International Application No. PCT / US2014 / 021796 filed on March 7, 2014, the complete publication of which is incorporated herein by reference.
[0327] Experiments were conducted with several additional media components using lactobacillus casei NRRL B-44 as the lactic acid producing organism. A 1.2 L bioreactor with 0.7 L of culture volume was used. One percent of a seed grown for 20 hours of lactobacillus casei NRRL B-441 was inoculated. No aeration was used. The temperature was maintained at approximately 37 ° C. Antifoam 204 was also added (0.1%, 1ml / L) at the beginning of the fermentation.
[0328] The results of these experiments are summarized in Table 3. The components of the media; the initial concentration of glucose, the sources of nitrogen, the concentration of yeast extract, calcium carbonate, metals and the size of the inoculum were tested for a lactic acid yeast or for the rate of lactic acid production. In addition to the components of the media, the physical conditions; temperature, agitation, autoclave time and heating (without autoclave) were tested for lactic acid yeast. For these media components and the conditions of the physical reactions, the tested scales, the preferred scales for
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120/125 the production of some lactic acids and the most preferred scales are shown in Table 3.
Table 3 - Production of L-lactic acid in a bioreactor with B-441
Media component Test Parameter Tested scale Scale- Optional Scale Initial glucose concentration Concentration of lactic acid 33-85 g / L 33-75 g / L 33-52 g / L Tested Nitrogen Sources Concentration of lactic acid Yeast extract, malt extract, millhocin, tryptone, peptone Yeast extract, tryptone, peptone Yeast extract Yeast Extract ^c Concentration of lactic acid 0-10 g / L 2.5-10 g / L 2.5 g / L Calcium carbonate Concentration of lactic acid 0-7% by weight /% by volume 3 - 7% by weight /% by volume 5% by weight /% by volume Metal Solutions Concentration of lactic acid With or without metals With or without metals Without metals Minor components: sodium acetate polysorbate 80 hydrogen dipotassium phosphate, triamonium citrate Concentration of lactic acid With or without minor components With or without minor components No minor components
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Inoculum Size Lactic acid production rate 0.1-5% by vol. 1 - 5% by vol. 1% by vol. Physical condition Test Parameter Tested scale Optional Scale Alternative scale Temperature Concentration of lactic acid 27-47 ° C 27 - 42 ° C 33-37 ° C Agitation (in 1.2 L reactor) Concentration of lactic acid 50-400 rpm 50-400 rpm 100-300 rpm Autoclave Time Concentration of lactic acid 25min145min 25min145min 25 min Heating (without autoclave) Concentration of lactic acid 50-70 ° C 50-70 ° C 50 - 70 ° C
^p The scales produced a yield of at least 80% based on the added sugars.
^b Optional scales produced close to 100% lactic acid (for example, between about 90 and 100%, between about 95 and 100%). ^c Fluka brand yeast extract was used.
[0329] The optional ranges were used for subsequent testing and the media is referred to as the optional media and the physical conditions are referred to as the optional physical conditions here.
Results with saccharified corn cob [0330] A 1.2 L bioreactor loaded with 0.7 L of media (saccharified corn cob, 2.5 g / L yeast extract). The bioreactor media and receptacle were autoclaved for 25 min and no additional heating was used for sterilization. In addition, a 20 L bioreactor was loaded with 10 L of medium. For sterilization, the media was stirred at 200 rpm while heated to 80 ° C for 10 min. When the media was cooled (approximately 37 ° C), the bioreactors were inoculated with 1 vol%. of the 20-hour culture. At
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122/125 fermentations were carried out under physical conditions (37 ° C, 200 rpm of agitation). No aeration was used. The pH remained between 5 and 6 using 5% (% by weight / vol. Throughout the fermentation. The temperature was maintained at approximately 37 ° C. Antifoam 204 was also added (0.1% by vol. At the beginning of the fermentation) Several varieties of Lactobacillus casei strains were tested (NRRL B-441, NRRL B-445, NRRL B-763 and ATCC 8014).
[0331] A graph of sugar consumption and lactic acid production for NRRL B-441 strain is displayed on the 1.2 L bioreactor shown in FIG. 7. After two days, all of the glucose was consumed, while the xylose was not consumed. Fructose and cellobiosis were also consumed. Lactic acid was produced at a concentration of approximately 42 g / L. Glucose, fructose and cellobiose consumed (42 g / L total) were almost equivalent to the lactic acid produced.
[0332] Similar data on fermentation results using the NRRL B-441 strain in the 20 L bioreactor are shown in FIG. 8. Glucose was completely consumed, while xylose was not consumed significantly. Lactic acid was produced at a final concentration of approximately 47-48 g / L.
[0333] The analysis of the enantiomer is summarized for all strains tested in Table 4. Lactobacillus casei (NRRL-B-441) and L. rhamnosus (B-445) produced more than 96% L-lactic acid. L. delbrueckii sub. Delbrueckii (B-763) showed more than 99% of D-lactic acid. L. plantarum (ATCC 8014) showed an approximate equal mixture of each enantiomer.
Table 4: Ratio of L- and D-Lactic Acid to Various Organisms
Fermentation
Strain L-Lactic Acid D-Lactic Acid L. casei (B-441) 96.1 3.9 L. rhamnosus (B-445) 98.3 1.7 L. delbrueckii sub.Delbrueckii (B-763) 0.6 99.4 L. plantarum (ATCC 8014) 52.8 47.2
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Comparative Example: Polymerization of lactic acid [0334] A 250 ml three-necked flask was equipped with a mechanical stirrer and a condenser that was connected with a vacuum system through a refrigerated capture. 100 grams of 90% by weight of the aqueous L-lactic acid were dehydrated at 150 ° C, first under atmospheric pressure for 2 hours, then at a reduced pressure of 90mmHg for 2 hours, and finally under a pressure of 20mmHg for another 4 hours. A clear viscous oligo liquid (L-lactic acid) was formed quantitatively.
[0335] 400 mg (0.4% by weight) of tin (II) chloride dihydrate and para-toluene sulfonic acid were added to the mixture and then heated to 180 ^o C for 5 hours at 8 mmHg. As the reaction continued, the system gradually became more viscous. The reaction mixture was cooled and then heated to 150 ^o C in a vacuum oven for an additional 19 hours.
[0336] The samples were removed from a mixture after 2 hours (A), 5 hours (B) and 24 hours (C) and the molecular weight was calculated using GPC using polystyrene standards in THF. FIG. 9 is a graph of the GPC data for samples A, B and C .__________________________________________________________________________
Reaction time (hours) Molecular weight,Mn Molecular weight,Mw Degree of Polymerization Retention time THE 2 4430 9630 62 20.3 B 5 7350 18100 102 19.3 Ç 24 18800 37500 261 18.3
[0337] Note that, after 24 hours, the degree of polymerization is ~ 250 units, well below the polymerization conversion obtained in the inventive process using a thin film polymerization / devolatilization device.
[0338] In addition to the examples presented here, or unless the contrary is expressly specified, all numerical scales, quantities, values and percentages, such as the quantities of materials, the contents of the elements, reaction times and temperatures, quantities of relationships, among others, in the following portion of the specification and the appended claims can be read as if
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124/125 preceded by the word approximately, even though the term approximately does not appear expressly with the value, quantity or scale. Thus, unless otherwise indicated, the numerical parameters set out in the specification below and in the appended claims are approximations that may vary according to the desired properties to be obtained by the present invention. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numeral parameter must at least be interpreted in the light of the number of significant digits reported and by the application of conventional rounding techniques.
[0339] Notwithstanding that the numerical ranges and parameters establishing the broad scope of the invention are approximations, the numerical values established in the specific examples are reported as precisely as possible. Every numerical value, however, inherently contains errors, necessarily resulting from the standard deviation found in their respective underlying test measures. In addition, when numeric ranges are established here, those ranges are, including the various endpoints mentioned (that is, endpoints can be used). When weight percentages are used here, the reported numerical values are relative to the total weight.
[0340] In addition, it should be understood that the entire numerical scale reported here is intended to include all subscales included here. For example, a scale of “1 to 10” is intended to include all subscales between (and including) the minimum reported value of 1 and the maximum reported value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. The terms “one,” (numeral) or “one” (indefinite article) as used here must include at least one or one or more, unless otherwise stated .
[0341] Any patent, publication or other disclosure material, in whole or in part, is referred to as incorporated herein by reference only so that the material
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125/125 incorporated does not conflict with existing definitions and statements or other disclosure materials made available in this publication. As such, and to the extent necessary, the publication, as explicitly set forth herein, replaces any conflicting material incorporated herein by reference. Any material, or part of it, that is said to be incorporated by reference in this document, but which conflicts with the definitions, statements, or other disclosure material contained herein will only be incorporated to the extent that there is no conflict between the material and the existing disclosure material.
[0342] When this invention is particularly shown and described with references to most preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details can be made therein without departing from the scope of the invention covered by the added claims .

权利要求:
Claims (14)
[1]
1. Method for processing hydroxycarboxylic acids CHARACTERIZED by the fact that it comprises:
producing a hydroxycarboxylic acid by fermenting sugars derived from biomass;
producing a polyhydroxycarboxylic acid from polyhydroxycarboxylic acid in the presence of a polymerization catalyst;
deactivating and / or stabilizing the polymerization catalyst with a catalyst deactivator;
transferring the polyhydroxycarboxylic acid to a surface of a thin-film evaporator and / or a thin-film polymerization / devolatilization device (200); and evaporate water as it is formed during condensation of the polyhydroxycarboxylic acid to provide a hydroxycarboxylic acid polymer as the polyhydroxycarboxylic acid passes through the surface of a thin film evaporator and / or a thin film polymerization / devolatilization device (200) , in which hydroxycarboxylic acid is selected from the monomer group consisting of glycolic acid, D-lactic acid, L-lactic acid, D-malic acid, L-malic acid, citric acid, L-tartaric acid, D-tartaric acid , betahydroxy beta-methylbutyric acid, 4-hydroxy-4-methylpentanoic acid, hydroxybutyric acid, 2-hydroxybutyric acid, beta-hydroxybutyric acid, gamma-hydroxybutyric acid, 3-hydroxybutyric acid, 3-hydroxypentanoic acid, 3-hydroxypropionic acid, alpha acid, alpha acid -hydroxyvaleric, gamma-hydroxivalic acid and deltahydroxyvaleric acid
[2]
2. Method according to claim 1, CHARACTERIZED by the fact that hydroxycarboxylic acid is selected from the monomer group consisting of glycolic acid, D-lactic acid, L-lactic acid, D-malic acid, L-malic acid , citric acid, L-tartaric acid and D-tartaric acid.
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2/3
[3]
3. Method according to claim 1, CHARACTERIZED by the fact that at least part of the thin film evaporator (200) and / or the thin film polymerization / devolatilization device operates at a temperature of 100 to 260 ° C and wherein at least part of the thin film evaporator and / or a thin film polymerization / devolatilization device (200) operates at a pressure of 0.0133 Pa (0.0001 torr) or less.
[4]
4. Method according to claim 1, CHARACTERIZED by the fact that the catalyst deactivator is added before the transfer of polyhydroxycarboxylic acid to the surface of the thin film evaporator and / or to the thin film polymerization / devolatilization device (200) .
[5]
5. Method according to claim 1, CHARACTERIZED by the fact that an aliphatic or aromatic dicarboxylic acid and an aliphatic or aromatic diol is added just before the transfer of the polyhydroxycarboxylic acid to the thin film evaporator and / or the polymerization device / thin film devolatilization (200).
[6]
6. Method, according to claim 5, CHARACTERIZED by the fact that the molar ratio of the aliphatic or aromatic dicarboxylic acid to the aliphatic or aromatic diol is from 0.95: 1 to 1.05: 1.
[7]
7. Method, according to claim 1, CHARACTERIZED by the fact that the polymerization catalyst is selected from the group consisting of metal oxides, TiO2, ZnO, GeO2, ZrO2, SnO, SnO2, Sb2O3 and solvates thereof.
[8]
8. Method according to claim 1, CHARACTERIZED by the fact that at least part of the thin-film evaporator and / or the thin-film polymerization / devolatilization device (200) operates at a pressure of less than 1.33 Pa (0.01 torr).
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[9]
Method according to any one of claims 1 to 8, CHARACTERIZED by the fact that it additionally comprises branching or cross-linking of polyhydroxycarboxylic acid.
[10]
Method according to any one of claims 1 to 9, CHARACTERIZED by the fact that it additionally comprises the combination of polyhydroxycarboxylic acid with a fragrance.
[11]
11. Method, according to claim 1, CHARACTERIZED by the fact that the catalyst deactivator is an anhydride, phosphite, antioxidant, multifunctional carboxylic acid and / or ethylene diaminetetraacetic acid.
[12]
12. Method according to claim 1, CHARACTERIZED by the fact that it comprises removing the deactivated / stabilized catalyst before, during or after the transfer step to the thin film evaporator and / or the thin film polymerization / devolatilization device (200).
[13]
13. Method, according to claim 1, CHARACTERIZED by the fact that it comprises the removal of the deactivated / stabilized catalyst by a filtration device.
[14]
14. Method according to claim 1, CHARACTERIZED by the fact that hydroxycarboxylic acid is selected from the monomer group consisting of glycolic acid, D-lactic acid, L-lactic acid, beta-hydroxy betamethylbutyric acid, 4-hydroxy-4-methylpentanoic acid, hydroxybutyric acid, 2-hydroxybutyric acid, beta-hydroxybutyric acid, gamma-hydroxybutyric acid, 3-hydroxybutyric acid, 3-hydroxypentanoic acid, 3-hydroxypropionic acid, alpha-hydroxyvalic acid, beta-hydroxyivalic acid, gamma-hydroxyivalic acid / or deltahydroxyvaleric acid.

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法律状态:
2017-11-14| B27A| Filing of a green patent (patente verde)|

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2017-12-05| B27B| Request for a green patent granted|

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2018-03-06| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2018-07-31| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2019-03-06| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2019-08-27| B09A| Decision: intention to grant|

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2019-10-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/04/2014, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/04/2014, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

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申请号 | 申请日 | 专利标题

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US201361816664P| true| 2013-04-26|2013-04-26|

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US201461941771P| true| 2014-02-19|2014-02-19|

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PCT/US2014/035469|WO2014176509A1|2013-04-26|2014-04-25|Processing hydroxy-carboxylic acids to polymers|

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