method to process biomass

专利摘要:
abstract biomass processing to obtain hydroxycarboxylic acids biomass (eg plant biomass, animal biomass and municipal waste biomass) is processed to produce useful intermediates and products such as hydroxycarboxylic acids and derived acids. 1/1
公开号:BR112015026760B1
申请号:R112015026760-2
申请日:2014-04-25
公开日:2018-11-13
发明作者:Marshall Medoff；Thomas Craig Masterman；Andrew PAPOULIS；Jaewoong MOON；Jihan Khan；Robert Paradis
申请人:Xyleco, Inc.；
IPC主号:

专利说明:

(54) Title: METHOD FOR PROCESSING BIOMASS (51) Int.CI .: C12P 7/02.
(30) Unionist Priority: 26/04/2013 US 61 / 816,664.
(73) Holder (s): XYLECO, INC ..
(72) Inventor (s): MARSHALL MEDOFF; THOMAS CRAIG MASTERMAN; ROBERT PARADIS; ANDREW PAPOULIS; JAEWOONG MOON; JIHAN KHAN.
(86) PCT Application: PCT US2014035467 of 25/04/2014 (87) PCT Publication: WO 2014/176508 of 10/30/2014 (85) Date of the Beginning of the National Phase: 10/21/2015 (57) Summary: SUMMARY BIOMASS PROCESSING TO OBTAIN HYDROXICARBOXYLIC ACIDS Biomass (eg plant biomass, animal biomass and municipal waste biomass) is processed to produce useful intermediates and products, such as hydroxycarboxylic acids and derived acids. 1/1
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METHOD FOR PROCESSING BIOMASS [0001] This application incorporates by reference the full disclosure of the following provisional co-pending application: USSN 61 / 816,664, filed on April 26, 2013.
BACKGROUND OF THE INVENTION [0002] Many potential lignocellulosic raw materials are currently available, including agricultural waste, woody biomass, municipal waste, oilseeds and macroalgae, to name a few. At the moment, such materials are often underutilized, being used, for example, as animal feed, organic composting materials, burned in cogeneration establishments or even landfilled.
[0003] Crystalline lignocellulosic biomass comprises crystalline cellulose fibrils incorporated into 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 enzymatic attack. In addition, each type of lignocellulosic biomass has its own specific composition of cellulose, hemicellulose and lignin.
SUMMARY [0004] In general, this invention relates to methods and processes for converting a material, such as biomass raw material, for example, cellulosic, starchy or lignocellulosic materials, into useful products, such as hydroxycarboxylic acids (for example,
Petition 870180063283, of 07/23/2018, p. 11/19
2/118 alpha, beta, gamma and delta hydroxycarboxylic acids) and derivatives of hydroxycarboxylic acids (eg esters). Such hydroxycarboxylic acids can be polyhydroxycarboxylic acids, for example, di-, tri-, tetra-, penta-, hexahepta- and octahydroxycarboxylic acids. Polyhydroxycarboxylic acid can be substituted with other groups, for example, alkyl groups. The carbon chain of carbolic acid can be linear, branched, cyclic or alicyclic.
[0005] In one aspect the invention relates to a method for producing a product including the treatment of reduced recalcitrant biomass (for example, lignocellulosic or cellulosic materials) with one or more enzymes and / or organisms to produce a hydroxycarboxylic acid (for example, example, an alpha, beta, gamma or delta hydroxycarboxylic acid) and convert hydroxycarboxylic acid into a product. Optionally, the raw material is previously treated with at least one method selected from irradiation (for example, with electron beam), sonication, oxidation, pyrolysis or vapor explosion, for example, to reduce the recalcitrance of the lignocellulosic or cellulosic material. Some examples of hydroxycarboxylic acids that can be produced and then further converted include glycolic acid, lactic acid, malic acid, citric acid and tartaric acid (substituted di), 3-hydroxybutyric acid (substituted beta), 4-hydroxybutyric acid (substituted range ), 3-hydroxyvaleric acid (substituted beta), gluconic acid (tetra substituted in alpha, beta, gamma and delta carbons with an additional hydroxy in epsilon carbon).
[0006] In a certain implementation of the method, hydroxycarboxylic acid is converted chemically, for example, when converting lactic acid to 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, disproportionation and combinations thereof.
[0007] In some other implementation, lignocellulosic or cellulosic material is treated with one or more enzymes to release one or more
3/118 sugars; for example, to release glucose, xylose, sucrose, maltose, lactose, mannose, galactose, arabinose, fructose, dimers thereof such as cellobiose, heterodimers thereof such as sucrose, oligomers thereof, and mixtures thereof. Optionally, treatment may also 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 hydroxyl acid. The sugars that are released from the biomass can be purified (for example, before fermentation) by, for example, a method selected from electrodialysis, distillation, centrifugation, filtration, cation exchange chromatography and combinations of these in any sequence.
[0008] In a certain implementation, the conversion comprises polymerization of lactic acid to polymer (for example, polymerization in a molten state such as without an added solvent). For example, polymerization methods can be selected from direct condensation of lactic acid, azeotropic dehydrating condensation of lactic acid, and lactic acid dimerization to lactide followed by lactide ring opening polymerization. The polymerization can be in a molten state (for example, without a solvent and above the melting point of the polymer) or it can be in a solution (for example, with an added solvent).
[0009] Optionally, when the polymerization method is 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, acyl chlorides, anhydride acids, epoxides, thyrane, oxazoline, orthoester and mixtures thereof. Alternatively, the polymer can have a comonomer that is a polycarboxylic acid or polyols or a combination
4/118 of these.
[0010] Optionally, polymerizations can be done using catalysts and / or activators. For example, Lewis and Bronsted acids (protonic) can be used equally. Examples of acids include H ₃ PO ₄ , H ₂ SO ₄ , methanesulfonic acid, p-toluenesulfonic acid, NAFION® NR 50 form DuPont H +, Wilmington DE, polymer-supported acids, metals, Mg, Al, Ti, Zn, Sn , metal oxides, TiO2, ZnO, GeO2, ZrO2, SnO, SnO2, Sb2O3, metal oxides, ZnCl2, SnCl2, SnCl4, Mn (AcO) 2, Fe2 (LA) 3, Co (AcO) 2, Ni (AcO) 2 , Cu (OA) 2, Zn (LA) 2, Y (OA) s, Al (/ - PrO) 3, Ti (BuO) 4, TiO (acac) 2, (Bu) 2SnO, tin octoate, solvates of all of these and mixtures of all of these can be used.
[0011] Polymerizations, or at least part of the polymerizations, can be carried out at a temperature between about 100 and about 200 ° C, such as, for example, between about 110 and about 170 ° C, between about 120 and about 160 ° C. Optionally at least part of the polymerizations can be carried out under vacuum conditions (for example, between about 0.1 mm Hg and 300 mm Hg).
[0012] In applications where the polymerization method includes lactic acid dimerization to lactide followed by lactide ring polymerization, dimerization may include heating the lactic acid to between 100 and 200 ° C under vacuum conditions of about from 0.1 to about 100 mmHg. Optionally, dimerization (for example, dimerization reaction) can include the use of a catalyst. Catalysts can, for example, include Sn octoate, Li carbonate, dehydrated Zn diacetate, Ti tetraisopropoxide, potassium carbonate, tin powder and mixtures thereof. Optionally, a ring opening polymerization catalyst is used. For example, the ring-opening polymerization catalyst can be chosen from protonic acids, HBr, HCl, triflic acid, Lewis acids, ZnCl2, AlCl3, anions, potassium benzoate, potassium phenoxide, potassium t-butoxide, and zinc stearate, metals, tin,
5/118 zinc, aluminum, antimony, bismuth, lanthanide and other heavy metals, tin (II) oxide and tin (II) octoate (eg 2ethylhexanoate), tetrafenyl tin, tin (II) and halides (IV), tin (II) acetylacetonate, distanoxanes (for example, hexabutyldistanoxane, R ₃ SnOSnR ₃ where groups R are alkyl or aryl groups), Al (OiPr) 3, other functionalized aluminum alkoxides, (for example, aluminum ethoxide, methoxide aluminum), zinc acetate, lead (II) oxide, antimony octoate, bismuth octoate, rare earth catalysts, yttrium tris (methyl lactate), yttrium (2-NN-dimethylamino ethoxide), samarium tris ( 2-NN-dimethylamino ethoxide), yttrium tris (trimethylsilyl methyl), marsh tris (2,2,6,6-tetramethylheptanedionate), marsh tris (acetylacetonate), yttrium octoate, yttrium tris (acetylacetate) , yttrium tris (2,2,6,6tetramethylheptanedionate), combinations thereof (eg, zinc acetate / aluminum isopropoxide) and mixtures thereof.
[0013] In applications where polymers are made from lactic acid, the methods may also include mixing a polymer with a second polymer. For example, a second polymer can include polyglycols, polyvinyl acetate, polyolefins, styrenic resins, polyacetals, polymethacrylates, polycarbonates, polybutylene succinate, elastomers, polyurethanes, natural rubber, polybutadiene, neoprene, silicone, and combinations thereof.
[0014] In other applications where polymers are made from lactic acid a comonomer can be co-polymerized with lactic acid or lactide. For example, the co-monomer can include elastomeric units, lactones, glycolic acid, carbonates, morpholiniones, epoxides, glycolsalicinate 1,4-benzodioxepin-2,5- (3H) -dione, lactosalicinate 1,4benzodioxepin-2,5- ( 3H, 3-methyl) -dione, dibenzo-1,5 dioxacin-6-12dione disalicylate, morfoline-2,5-dione, 1,4-dioxane-2,5-dione glycolide, ε-caprolactone oxepane-2-one , 1,3-dioxane-2-one trimethylene carbonate, 2,2-dimethyltrimethylene carbonate, 1,5-dioxepane-2-one, p-dioxanone 1,4-dioxane-2-one, gamma-butyrolactone, beta-butyrolactone , beta-me-delta-valerolactone, oxalate
6/118 ethylene 1,4-dioxane-2,3-dione, 3- [benzyloxycarbonyl meyl] -1,4-dioxane-2,5dione, ethylene oxide, propylene oxide, 5.5 '(oxepane-2 -one), 2,4,7,9 tetraoxa-spiro [5.5] undecane-3,8-dione, spiro-bid-dimethylene carbonate and mixtures thereof.
[0015] 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, fiberglass, boric acid, talc, montmorillonite, clay, starch , corn starch, wheat starch, cellulose fiber, paper, rayon, non-woven fibers, wood flour, potassium titanate yarn, aluminum borate yarn, 4,4'-thiodiphenol, glycerol and mixtures thereof.
[0016] In any implementation in which polymers are made, the method may also include branching or crosslinking of the polymer. For example, polymers can be treated with a crosslinking agent including 5.5'bis (oxepane-2-one) (bis- ε -caprolactone)), spiro-bis-dimethylene carbonate, peroxides, dicumyl peroxide, peroxide benzoyl, 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.
[0017] In any implementation where polymers are processed, processing may include injection molding, blow molding and thermoforming.
[0018] In every implementation where polymers are processed,
7/118 polymers can be combined with a dye and / or 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% by weight).
[0019] 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-NSAFE (from Danisco, DuPont, Wilmington DE, bishhydroxymethyl diethyl malonate) and mixtures thereof.
[0020] In any implementation in which polymers are produced, polymers can be processed or further processed by forging, molding, carving, extruding and / or building the polymer within the product.
[0021] 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 fermenting sugars derived from biomass (eg glycolic acid, D-lactic acid and / or L-lactic acid, D-malic acid L-malic , citric acid and D-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.
8/118 [0022] Products, for example, include polymers, including one or more hydroxy acids on the polymer backbone and, optionally, non-hydroxyl carboxylic acids on the polymer backbone. 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.
[0023] In yet another embodiment, the invention relates to a system for polymerization including a reaction vessel, a screw extruder and a condenser. The system also includes a recirculating fluid flow path from a reaction vessel outlet to a screw extruder inlet and from a screw extruder outlet to a reaction vessel inlet. In addition, the system includes a fluid flow life from a second outlet from the reaction vessel to a condenser inlet. Optionally, the system also includes a vacuum pump in fluid connection with the second fluid access port so that a vacuum is produced in the second fluid flow port. Also optionally, the system can include a control valve that, in a first position, provides an uninterrupted flow in the flow path of the recirculation fluid and in a second position provides a second flow path. In some implementations, the second path of fluid flow is from the outlet of the reaction vessel to an inlet of a granulator. In other implementations, the second path of fluid flow is from the outlet of a reaction vessel to an inlet of the extruder and from the outlet of an extruder to the inlet of a granulator.
[0024] Some of the products described in this document, for example, 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
In particular, fermentative methods can produce D or L isomers of hydroxycarboxylic acids (eg, 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.
[0025] The methods described in this document are also advantageous since the raw materials (for example, sugars) can be derived entirely from biomass (for example, cellulosic and lignocellulosic materials). In addition, some of the products described in this document, such as polymers hydroxycarboxylic acids (eg, polylactic acid) are compostable, biodegradable and / or recyclable. Consequently, the methods described in this document can provide useful 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.
[0026] For example, some products that can be produced using the methods, systems or equipment described in this document may include personal hygiene items, handkerchiefs, towels, diapers, eco-friendly packaging, compostable vases, consumer electronics, laptop cases, cell phone covers, devices, food packaging, disposable packaging, food containers, drink bottles, garbage bags, compostable waste bags, mulch films, controlled release matrices, controlled release containers, fertilizer containers, pesticide containers, 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, cups, gar fos, knives, spoons, sporks, bowls, pieces
10/118 automobiles, panels, fabrics, undercoat covers, carpet fibers, fibers for clothing, fibers for underwear, fibers for sportswear, fibers for shoes, surgical sutures, implants, scaffolding and drug delivery systems .
[0027] Other features and advantages of the invention will become apparent from the detailed description below, and from the claims.
DESCRIPTION OF THE FIGURE [0028] The foregoing will become apparent from the following more detailed description and exemplary modalities of the invention, as illustrated in the accompanying one. The figures are not necessarily in an adequate proportion, with the emphasis placed instead on illustrating modalities of the present invention.
[0029] FIG. 1 is a flow chart showing processes for manufacturing products from biomass raw materials [0030] FIG. 2 is a schematic diagram showing some biochemical pathways for the fermentation of sugars to lactic acid.
[0031] FIG. 3 is a schematic diagram showing some of the possible products derived from lactic acid.
[0032] FIG. 4 is a schematic diagram showing some of the chemical pathways for the production of polylactic acid.
[0033] FIG. 5 is a schematic view of a reactive system for the polymerization of lactic acid.
[0034] FIG. 6A is a top view of a first embodiment of a reciprocating scraper. FIG. 6B is a front view in relief of the first modality of a reciprocating scraper. FIG. 6A is a top view of a second embodiment of a reciprocating scraper. FIG. 6B is a front relief view of the second embodiment of a reciprocating scraper.
[0035] FIG. 7 is a batch of lactic acid production in a
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Bioreactor 1.2 L.
[0036] FIG. 8 is a batch of lactic acid production in a 20 L Bioreactor.
[0037] FIG. 9 is a batch of GPC data for polylactic acid.
[0038] FIG. 10 shows the chemical structures of some exemplary hydroxyl acids.
DETAILED DESCRIPTION [0039] Using the equipment, methods or systems described in this document, cellulosic or lignocellulosic raw materials, for example, which can be extracted from biomass (eg plant biomass, animal biomass, paper and municipal waste biomass) and which are often readily available but difficult to process, can be turned into useful products such as sugars and hydroxycarboxylic acids. Included are equipment, methods and systems for chemically converting primary products produced from biomass to secondary products such as polymers (for example, polylactic acid) and polymer derivatives (ie compounds, elastomers and copolymers).
[0040] Biomass is a complex raw material. For example, lignocellulosic materials include different combinations of cellulose, hemicellulose and lignin. Cellulose is a linear polymer of glucose. Hemicellulose is one of several heteropolymers, such as xylan, glucuronoxylan, arabinoxylan 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, material
12/118 biomass derived from wood can present about 38-49% cellulose, 7-26% hemicellulose and 23-34% lignin, depending on the type. Grasses are typically 33-38% cellulose, 24-32% hemicellulose and 17-22% lignin. Lignocellulosic biomass clearly constitutes a large class of substrates.
[0041] Biomass-destroying enzymes and organisms that break down biomass, such as cellulose, hemicellulose and / or the lignin parts of biomass, as described above, contain or manufacture various cellulosic enzymes (cellulases), ligninases or various metabolites destroying biomass small molecule biomass. A cellulosic substrate is 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 glucose dimer with 1,4 bonds. Finally, celobiase cleaves cellobiosis to produce glucose. In the case of hemicellulose, a xylanase (for example, hemicellulase) acts on this biopolymer and releases xylose as one of its possible products.
[0042] FIG. 1 is a flowchart showing processes for manufacturing hydroxycarboxylic acids from a raw material (for example, cellulosic or lignocellulosic materials). In an initial stage (110) the method optionally includes the mechanical treatment of a cellulosic raw material and / or lignocellulosic material, for example, to reduce / decrease the size of the raw material. Before and / or after this treatment, the raw material can be treated with another physical treatment (112), for example, irradiation, sonication, vapor explosion, oxidation, pyrolysis or combinations of these, to further reduce or reduce its recalcitrance. A sugar solution, for example, including glucose and / or xylose, is formed by saccharifying the raw material (114). Saccharification can, for example, be accompanied efficiently by the addition of one or more enzymes, for example, cellulases and / or xylanases (111)
13/118 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. (116) After fermentation, the fermentation product (for example, or products, or a subset of fermentation products) can be purified or further processed, for example, polymerized and / or isolated (124). 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 Patent Application No. PCT / US2014 / 021813 filed on March 7, 2014, the disclosure of which is incorporated in this document in its entirety by reference. If desired, the steps for measuring the lignin content (118) and configuring or adjusting the process parameters based on this measurement (120) can be performed at various stages of the process, for example, as described in US Patent No. 8,415,122 filed on April 9, 2013, the entire disclosure of which is incorporated herein 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 PCT Patent Application No. PCT / US12 / 71093, filed on December 20, 2012, published as WO 2013/096700, and the disclosure of which is incorporated herein in its entirety by reference.
[0043] 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 International Application No. PCT / US2013 / 048963 filed on July 1, 2013, and International Application No. PCT / US2014 / 021584, filed on 7 March 2014, the disclosures of which are incorporated into this document in its
11/148 totalities by reference. In addition, other separation techniques can be used in liquids, for example, to remove ions and discolor them. For example, chromatography, moving bed chromatography and electrodialysis can be used to purify any of the solutions and / or suspensions described in this document. 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 disclosures of which are incorporated in this document. in their entirety by reference. The solids that are removed during processing can be used in energy cogeneration, for example, as discussed in International Application No. PCT / US2014 / 021634, filed on March 7, 2014, the disclosure of which is incorporated in this document in its entirety by reference.
[0044] Optionally, the sugars released from the biomass as described in FIG. 1, for example, glucose, xylose, sucrose, maltose, lactose, mannose, galactose, arabinose, homodimers and heterodimers thereof (eg cellobiose, sucrose), trimers, oligomers and mixtures thereof, can be fermented to hydroxycarboxylic acids such as acids alpha, beta or gamma hydroxyls (for example, lactic acid). In some embodiments, saccharification and fermentation are carried out simultaneously, for example, using the thermophilic organism such as bacillus-coagulans MXL-9 as described by S.L. Walton in J. Ind. Microbiol. Biotechnol. (2012) pg. 823-830.
[0045] Hydroxycarboxylic acids that can be produced by the methodological systems and equipment described in this document include, for example, hydroxycarboxylic alpha, beta, gamma and delta acids. FIG. 10 shows the chemical structures of some hydroxyl acids. That is, if there is only one hydroxyl group, it can be found in any of the alpha, beta, gamma or delta carbon atoms in the carbon chain. The carbon chain can be a linear, branched or cyclic system. The acid
Hydroxycarboxylic 15/118 may also include fatty acids of carbon chain length between 10 and 22 with the hydroxy substitute in alpha, beta, gamma or delta carbon.
[0046] Hydroxycarboxylic acids include those with multiple hydroxy substitutes, or in an alternative description, a polyhydroxy substituted carboxylic acid. Such hydroxycarboxylic acids can be polyhydroxy carboxylic acids, for example. substituted di-, tri-, tetra-, penta-, hexahepta- and octa-hydroxycarboxylic acids. The carbon chain of the carboxylic acid can be linear, branched, cyclic or alicyclic. Examples of this are tartaric acid and its isomers, dihydroxy-3-methylpentanoic acid,
3,4-dihydroximandelic acid, gluconic acid, glucuronic acid and the like.
[0047] For example, hydroxycarboxylic acids include glycolic acid, lactic acid (for example, D, L or mixtures of D and L), malic acid, citric acid, tartaric acid, carmine, cyclobutyrol, 3dehydroquinic acid, diethyl tartrate, 2,3-dihydroxy-3-methylpentanoic acid, acid
3,4-dihydroximandelic acid, glycolic acid, homocitric acid, homoisocitric acid, beta-hydroxy beta-methylbutyric acid, 4-hydroxy-4-methylpentanoic acid, hydroxybutyric acid, 2-hydroxybutyric acid, beta-hydroxybutyric acid, gamma-hydroxybutyric acid, alpha acid -hydroxyglutaric acid, 5-hydroxyindoleacetic acid,
3-hydroxyisobutyric, 3-hydroxypentanoic acid, 3-hydroxypropionic acid, hydroxypyruvic acid, gluconic acid, glucuronic acid, alpha, beta, gamma or delta-hydroxyvaleric acids; isocitric acid, isopropylmalic acid, quinurenic acid, mandelic acid, mevalonic acid, monatin, myelin, pamoic acid, pantoic acid, prefenic acid, xiquimic acid, tartronic acid, threonic acid, tropic acid, vanillmandelic acid, xanthurenic acid and mixtures thereof. For the hydroxycarboxylic acids listed, all stereoisomers are included in the list. For example, tartaric acid includes the D, L and meso isomers and mixtures thereof.
PREPARATION OF LACTIC ACID [0048] Organisms can use a variety of pathways
16/118 metabolic processes to convert sugars to lactic acid, and some organisms can selectively only use specific pathways. Some organisms are homofermentative, while others are heterofermentative. For example, some routes are shown in FIG. 2 and are described in Journal of Biotechnology 156 (2011) 286-301. The pathway typically used by organisms fermenting glucose is the glycolytic pathway 2. Five-carbon sugars, such as xylose, can use the heterofermentative phosphoquetolase (PK) pathway. The PK pathway converts two of the 5 carbons of xylose into acetic acid and the remaining 3 into lactic acid (through pyruvate). Another possible route for five-carbon sugars is the pentose-phosphate (PP) / glycolytic route which produces only lactic acid.
[0049] 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 include Rhizopus arrhizus, Rhizopus oryzae, (for example, 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 , CBS 264.28,), Enterococcus faecalis (for example, RKY1), Lactobacillus rhamnosus (for example, ATCC 10863. ATCC 7469, CECT-288, NRRL B445), Lactobacillus helveticus (for example, ATCC 15009, R211),
Lactobacillus bulgaricus (eg NRRL B-548, ATCC 8001, PTCC 1332), Lactobacillus casei (eg NRRL B-441), Lactobacillus plantarum (eg ATCC 21028, TISTR No. 543, NCIMB 8826), Lactobacillus pentosus ( for example, ATCC 8041), Lactobacillus amylophilus (eg GV6), Lactobacillus delbrueckii (for example, NCIMB 8130, TISTR No. 326, Uc-3, NRRL-B445, IFO 3202, ATCC 9649), Lactococcus lactis ssp. lactis (e.g. IFO 12007), Lactobacillus paracasei No. 8, Lactobacillus amylovorus (ATCC 33620), Lactobacillus sp. (for example, RKY2), Lactobacillus coryniformis ssp. torquens (e.g. ATCC 25600, B-4390), Rhizopus sp. (e.g. MK-96-1196), Enterococcus casseliflavus,
11/178
Lactococcus lactis (TISTR No. 1401), Lactobacillus casei (TISTR No. 390), Lactobacillus thermophiles, Bacillus coagulans (eg MXL-9, 36D1, P4-102B), Enterococcus mundtii (eg QU 25), Lactobacillus delbrueckii , Acremonium cellulose, Lactobacillus bifermentans,
Corynebacterium glutamicum, L. acetotolerans, L. acidifarinae, L. acidipiscis, L. acidophilus, L. agilis, L. algidus, L. alimentarius, L. amylolyticus, L. amylophilus, L. amylotrophicus, L. amylovorus, L. animalis , L. antri, L. apodemi, L. aviarius, L. bifermentans, L. brevis (e.g., B-4527), 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).
[0050] Alternatively, the microorganism used to convert
18/118 sugars hydroxycarboxylic acids including lactic acid, Lactobacillus casei, Lactobacillus rhamnosus, Lactobacillus delbrueckii subspecies delbrueckii, Lactobacillus plantarum, Lactobacillus coryniformis subspecies torquens, Lactobacillus pentosus, Lactobacillus brevis, Pediococcus pentosaceus, Rhizopus oryzae, Enterococcus faecalis, Lactobacillus helveticus, Lactobacillus bulgaricus, Lactobacillus casei, lactobacillus amylophilus and mixtures thereof.
[0051] Using the methods, equipment and systems described in this document, both D and L isomers of lactic acid in optical purity of almost 100% (for example, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 99%) can be produced. Optionally, mixtures of isomers can be produced in any ratio, for example, 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 whereas Lactobacillus delbrueckii (IF 3202) produces , reportedly, the D isomer (Wang et al. in Bioresource Technology, June, 2010). As an example to add, 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 mixtures of both.
[0052] 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 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.
19/118 [0053] Co-cultures of organisms, for example, selected from organisms such as those described in this document, 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 (for example, glucose and / or xylose), where the organisms ferment the sugars together, selectively and / or sequentially. Optionally, an organism can be added first and fermentation takes place for a moment, 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 and L-lactic acid by combining a D-fermentable or Lfermentable organism in a suitable ratio to form the desired racemic mixture.
[0054] In certain embodiments, fermentations use Lactobacillus. For example, the fermentation of glucose derived from biomass by Lactobacillus can be very efficient (for example, high, selective and with high conversion) In other modalities the production of lactic acid uses filamentous fungi. For example, the Rhizopus species can ferment glucose aerobically 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 pentose sugars.
[0055] In some embodiments, certain additives (for example, medium components) can be added during fermentation. For example, additives that can be used include yeast extract, rice bran, wheat bran, millhocin, black molasses, chain hydrolyzate, plant extracts, solid corn xerem,
20/118 mutton, peptides, peptone (for example, bacto-peptone, polypeptone), pharmamedia, flour (for example, wheat flour, soy flour, cottonseed flour), malt extract, meat extract, tryptone , K ₂ HPO ₄ , KH ₂ PO ₄ , Na ₂ HPO ₄ , NaH ₂ PO ₄ , (NH ₄ ) ₂ PO ₄ , NH ₄ OH, NH ₄ NO, urea. ammonium citrate, nitrilotriacetic acid, MnSO ₄ 5H ₂ O, MgSO47H ₂ O, CaCl ₂ .2H ₂ O, FeSO4 ^. 7H2O, B-vitamins (e.g., thiamine, riboflavin, niacin, niacinamide, pantothenic acid, pyridoxine, pyridoxal, pyridoxamine, pyridoxine hydrochloride, biotin, folic acid), amino acids, sodium L-glutamate, Na2EDTA, sodium acetate, ZnSO4 ^. 7H2O, ammonium molybdate tetrahydrate, CuCl2, CoCl ₂ and CaCO ₃ . The addition of protease can also be beneficial during fermentation. Optionally, surfactants like TWEEN ™ 80 and antibiotics such as chloramphenicol can also be beneficial. Additional sources of carbon, for example, glucose, xylose and other sugars. Antifoam compounds such as Antifoam 204 can be used.
[0056] In some modalities, fermentation can take from 8 hours to several days. For example, some group fermentations can take from about 1 day to 20 days (for example, about 1-10 days, about 3-6 days, about 8 hours to 48 hours, about 8 hours to 24 hours ).
[0057] In some embodiments, the temperature during fermentation is controlled. For example, the temperature can be controlled between about 20 ° C and 50 ° C (for example between about 25 and 40 ° C, between about 30 and 40 ° C, between about 35 and 40 ° C). In some cases, thermophilic organisms are used that operate effectively above about 50 ° C, for example, between about 50 ° C and 100 ° C (for example, between about 50-90 ° C, between about 50 to 80 ° C, between about 50 to 70 ° C).
[0058] 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 close to neutral (for example, between about 4-8, between about 57, between about 5-6). The acids, for example, can be protic acids such as sulfuric, phosphoric, nitric, hydrochloride and acetic acids. The bases, for
21/118 example, may include metal hydroxides (for example, sodium and potassium hydroxide), ammonium hydroxide and calcium carbonate. Phosphate and other dampers can also be used.
[0059] 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.
[0060] 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 maximum amount for fermentation.
[0061] Options include cell recycling. For example, the use of a hollow fiber membrane to separate cells from medium components and products, once 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 Order with US Serial Number 13 / 293,971, filed on November 10, 2011, and US Patent No. 8,377,668, issued on February 19, 2013 , whose disclosures are incorporated in their entirety in this document by reference.
[0062] 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, about 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 bleaching agent. For example, the broth can be filtered with carbon. The broth is then concentrated, for example, by evaporating the water
22/118 optionally under vacuum and / or mild heating conditions, and can be crystallized or precipitated. Acidification, for example, with sulfuric acid, releases the lactic acid back into the solution that 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.
[0063] 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.
[0064] Other alternative technologies for separating D-lactic acid and L-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.
[0065] The precipitation or crystallization of calcium lactate by the addition of organic solvents is another method for purification. For example, alcohols (for example, ethanol, propanol, butanol, hexanol), ketones (for example, acetone) can be used for this purpose.
[0066] 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 in this document.
USES OF LACTIC ACID [0067] Lactic acid, as described in this document, can be
23/118 used, for example, in the food industry as preservatives, acidulants or flavoring agents. Lactic acid can be used in a wide range of food applications, such as bakery products, beverages, meat products, confectionery, dairy products, salads, sauces, ready meals. Generally, lactic acid acts in food products either as a pH regulator or as a preservative. It can also be used as a flavoring agent, for example, giving a sour taste to food. Lactic acid can be used in meat, poultry and fish, for example, in the form of sodium lactate and potassium lactate to increase shelf life, control pathogenic bacteria (for example, improving food safety), enhance and protect flavor meat, improve water binding capacity and reduce sodium. Lactic acid is also used as an acidic regulator in drinks such as soft drinks and fruit juices. Lactic acid is effective in preserving olives, cucumbers, pearl onions and other vegetables preserved in brine from damage. Lactic acid can also be used as a preservative and / or flavoring additive in salads and sauces. Lactic acid can also be used in the formulation of hard candies, fruit chewing gums and confectionery. Lactic acid is used as an acidifying agent for many dairy products, such as yogurt and cheese. Lactic acid is a natural acid with acidic mass, and therefore can be used for direct acidification in the production of acidic mass. Lactic acid is used to intensify a wide range of tasty flavors, for example, in meat or dairy products.
[0068] Calcium lactate, as produced by the methods described in this document, can also be added to sugar-free foods to prevent dental problems. For example, in combinations with chewing gums containing xylitol, it increases the remineralization of tooth enamel. Calcium lactate is also added to fresh fruits, such as cantaloupe, to prolong its shelf life.
[0069] Lactic acid derived from biomass, as described in this
24/118 document, can be used in pharmaceutical applications, for example, for pH regulation, metal sequestration, as a chiral intermediate and as a natural body component in pharmaceutical products. Calcium lactate is generally used as an antacid and also as a calcium supplement. Other salts of lactic acid, for example, salts containing Mg, Zn and Fe, can also be used as mineral supplements and fortifying agents.
[0070] Lactic acid, as produced by the methods described in this document, can also be used in cleaning products. Lactic acid has descaling properties and is widely applied in household cleaning products. Likewise, lactic acid is used as a natural antibacterial agent in disinfectant products.
[0071] The lactic acid produced by the methods described in this document can be used in a wide variety of industrial processes in which acidity is required and in which its properties offer specific benefits. Some examples are the manufacture of leather and textiles and computer disks, as well as car covers.
[0072] Lactic acid, as produced by the methods described in this document, can also be used as a nutrient in animal feed. Lactic acid has health-promoting properties, thereby enhancing the performance of farm animals. Lactic acid can also be used as an additive in drinking water and / or food for both humans and animals.
PRODUCTS DERIVED FROM LACTIC ACID [0073] Lactic acid can be used as a platform chemical for many industrially relevant chemicals and products. For example, with reference to FIG. 2, lactic acid can be converted to, lactate esters such as ethyl lactate, acrylic acid, 1,2propanediol, 2,3-pentanedione, acetaldehyde, propanoic acid and polylactic acid.
25/118 [0074] 1,2-propanediol (propylene glycol) can be used as a solvent and antifreeze substitute for 1,2-propanediol. Propylene glycol is also used for de-icing solutions (for example, de-icing aircraft). Propylene glycol has been approved for use as a food additive and can be used in the food industry as a humectant, preservative, lubricant (eg for food processing equipment), solvents (eg for pharmaceutical preparations), plasticizers (eg for materials that come into contact with food) [0075] Ethyl lactate has uses in pharmaceutical preparations, food additives, fragrances and as a good chemical for consumption (for example, cosmetics) and industrial solvent.
[0076] Aceltadeide is currently produced on a large scale, mainly from oil sources. It is a synton in a myriad of organic reactions to produce, for example, ethyl acetate (an important solvent), perfumes, polyester resins and basic dyes. It also finds uses as a solvent (for example, in the rubber, tanning and paper industries), as a preservative (for example, fruits and meat), flavoring and denaturing agent for combustible compositions.
[0077] 2.3-pentanedione is useful as a solvent for cellulose acetate, paints, paints and lacquers. It is also a raw material for the synthesis of tinctures, pesticides and drugs. It can also be used as a component in synthetic flavoring agents.
[0078] (Met) acrylic acid and its esters (for example, methyl, butyl, ethyl, hydroxyethyl and 2-ethylhexyl esters) polymerize through their double bond to form polyacrylates (for example, polyacrylic acid). In addition, acrylic acid and its esters can copolymerize with other monomers, (for example, acrylamides, acrylonitriles, styrene, vinyl and butadiene), forming copolymers that are used in the manufacture of plastics, coatings,
26/118 adhesives, elastomers, floor waxes and paints.
[0079] Propanoic acid can be used as a fungicide and bactericide, for the treatment of grains, hay, poultry litter, drinking water for animals, as well as in the treatment of areas used for feed storage. It is also a synton for the production of other chemical substances, for example, herbicides and various esters.
[0080] Polylactic acid is an important biodegradable / recyclable polymer that will be discussed in detail below.
POLYMERIZATION OF LACTIC ACID [0081] Lactic acid, prepared as described in this document, can undergo condensation of esters to form dimers (for example, linear and lactides), trimers, oligomers and polymers. Polylactic acid (PLA) is therefore a condensed lactic acid polyester. PLA can be further processed (for example, grafted, treated or copolymerized to form side chains including ionizable groups). Another name for PLA is polylactide. Both PLA isomers can form polymers and / or can be copolymerized. The properties of polymers depend heavily on the amounts of D-lactic and Llactic acid incorporated into the structure, as will be discussed below.
[0082] FIG. 4 shows methods for the production of PLA, including: direct condensation combined with chain coupling, dehydrating azeotropic coupling; and condensation followed by lactide formation and polymerization by lactide ring opening.
[0083] A low molecular weight PLA can be produced without the aid of catalysts by direct self-condensation of lactic acid. This method produces low molecular weight polymers (for example, about 1000 to 10,000 Mw, more typically about 1000 to 5,000). Condensation produces water that can prevent the production of high molecular weight PLA since the reaction by condensation of esters is reversible. In addition, the lactide can be produced by backbiting from one end of the chain to
27/118 form a lactide ring that reduces the molecular weight of the linear polymer. Consequently, the PLA polycondensation system involves two equilibrium reactions; dehydration / hydrolysis balance for esterification / de-esterification; and the ring / chain balance involving the depolymerization of the PLA to dairy or polymerization of the ring to linear polymer.
[0084] A method for producing high molecular weight PLA is the coupling of low Mw PLA, for example, produced as described above, using chain coupling agents. For example, hydroxy-terminated PLA can be synthesized by condensing lactic acid in the presence of small amounts of multifunctional hydroxy compounds, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclohexanediol, 2-butane-1,4 -diol, glycerol, 1,4-butanediol, 1,6-hexanediol. Alternatively, the carboxyl-terminated PLA can be achieved by condensing lactic acid in the presence of small amounts of multifunctional carboxylic acids such as maleic, succinic, adipic, itaconic and malonic acid. Other chain extending agents may have heterofunctional groups that are coupled either to the PLA carboxylic acid terminal group or to the hydroxy terminal group, for example, 6-hydroxycapric acid, mandelic acid, 4-hydroxybenzoic acid, 4-acetoxybenzoic acid.
[0085] Esterification promoting agents can also be combined with lactic acid to increase the molecular weight of PLA. For example, ester promoting agents include phosgene, diphosgen, triphosgene dicyclohexylcarbodiimide and carbonyldiimidazole. Some potentially undesirable side products can be produced by this method by adding purification steps in the process. After the final purification, the product can be very clean, free of catalyst and low molecular weight impurities.
[0086] The molecular weights of polymers can also be increased through the addition of chain extending agents such as isocyanides,
28/118 acyl chlorides, anhydrides, epoxides, thyrane and oxazoline and orthoester.
[0087] Polymerization by azeotropic condensation is another method for obtaining high molecular weight polymers and does not require chain extenders or coupling agents. A standard procedure for this route is to reflux lactic acid at reduced pressure (between 0.1-300 mm Hg) for 1-10 hours between 110 ^o C-160 ^o C, to remove most of the condensation water. The catalyst and / or solvents are added and heated even more for 1-10 hours between 110 ^o C-180 ^o under 0.1-300 mm Hg. The polymer is then isolated or dissolved (dichloromethane, chloroform) and precipitated by the addition of a solvent (for example, methyl ether, diethyl ether, methane, ethane, isopropanol, ethyl acetate, toluene) for further purification. The solvents used during polymerization, catalyst, reaction time, temperature and level of impurities affect the speed of polymerization and, therefore, the final molecular weight.
[0088] Additives, catalysts and promoting agents that can optionally be used include Lewis and Bronsted acids (protonic) such as H ₃ PO ₄ , H ₂ SO ₄ , methanesulfonic acid, p-toluene sulfonic acid, NAFION® NR 50 H + DuPont formula, Wilmington DE, 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 metal-containing catalysts 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 ) s, Al (y-PrO) s, 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 be added at a time or sequentially, as the polymerization progresses. Catalysts can also be removed, replenished and / or regenerated during the course of polymerization for repeated polymerizations. Optional combinations include protonic acids and one of the
29/118 catalysts containing mental, for example, SnCl ₂ / ptoluenesulfonic acid.
[0089] The azeotropic condensation can be carried out partially or entirely using a solvent. For example, an aprotic solvent with a high boiling point, such as diphenyl ether, p-xylene, o-chlorotoluene, odichlorobenzene and / or isomers thereof. Polymerization can also be done entirely or partially using melt polycondensation. Melting polycondensations are carried out above the boiling point of the polymers / oligomers without the aid of organic solvents. For example, at the beginning of polymerization, when there is a high concentration of low molecular weight species (for example, lactic acid and oligomers) there may be less need for a solvent, whereas, as the molecular weight of polymers increases, the addition of a solvent with a high boiling point can improve reaction rates.
[0090] During polymerization, for example, especially at the beginning of polymerization, when the concentration of lactic acid is high and water is being formed at high speed, the azeotropic lactic acid / water mixture can be condensed and passed through molecular sieves to dehydrate lactic acid, which is then returned to the reaction vessel.
[0091] Copolymers can be produced by adding monomers other than lactic acid during the azeotropic condensation reaction. For example, any of the hydroxy, multifunctional carboxylic 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.
[0092] Optionally, ring opening polymerization of the lactide can provide PLA. The lactide can also be produced by depolymerizing low molecular weight PLA under reduced pressure. Depolymerization to form lactide monomers, for example, the
30/118 forms D, L and meso, depends on the stereochemistry of lactic acid used as raw material and conditions of formation. Methods to form the lactide include condensation of lactic acid, with or without catalysts at 110180 ^o C, and removal of condensation water under vacuum conditions ((1mm Hg- 100 mm Hg) to produce polymers or prepolymers of molecular weight 1000-5000 The prepolymer can then be heated, for example, to temperatures of around 150-250 ^o C and 0.1-100mmHg to form and distill the raw lactic acid. The raw lactic acid can then be recrystallized, for example, of a solution of dry toluene or ethyl acetate.
[0093] Catalysts can be used for the formation of lactides. For example, catalysts that can be used include, tin oxide (SnO), Sn (II) octoate, Li carbonate, dehydrated zinc diacetate, Ti tetraisopropoxide, potassium carbonate, tin powder, combinations and mixtures of these . The catalysts can be used in combination and / or sequentially.
[0094] The lactide monomer can be polymerized by ring opening (ROP) by solution, mass, fusion and suspension polymerization and is catalyzed by cationic, anionic, coordination and radical polymerization. Some catalysts used, for example, include protonic acids, HBr, HCl, triflic acid, Lewis acids, ZnCl ₂ , AlCl ₃ , anions, potassium benzoate, potassium phenoxide, potassium t-butoxide, and zinc stearate, metals , tin, zinc, aluminum, antimony, bismuth, lanthanide and other heavy metals, tin (II) oxide and tin (II) octoate (eg 2-ethyl hexanoate), tetrafenyl tin, tin (II) halides and (IV), tin (II) acetylacetonoate, distanoxanes (for example, hexabutyldistanoxane, R3SnOSnR3 where groups R are alkyl or aryl groups), Al (OiPr) 3, other functionalized aluminum alkoxides (for example, aluminum ethoxide, aluminum), ethyl zinc, lead (II) oxide, antimony octoate, bismuth octoate, rare earth catalysts, yttrium tris (methyl lactate), yttrium (2-NN-dimethylamino ethoxide), samarium
31/118 tris (2-NN-dimethylamino ethoxide), yttrium tris (trimethylsilyl methyl), marsh tris (2,2,6,6tetramethylheptanedionate), yttrium tris (acetylacetonate), marsh tris (acetylacetonate) yttrium, tris (2,2,6,6-tetramethylheptanedionate) of yttrium, combinations thereof (for example, ethyl zinc / aluminum isopropoxide) and mixtures thereof.
[0095] In addition to homopolymer, copolymerization with other cyclic monomers and non-cyclic monomers such as glycolide, caprolactone, valerolactone, dioxipenone, trimethyl carbonate, 1,4-benzodioxepin-2,5- (3H) -dione, lactosalicinate 1,4 - benzodioxepin-2,5- (3H, 3methyl) -dione, dibenzo-1,5 dioxacin-6-12-dione disalicylate, morfoline-2,5-dione, 1,4-dioxane-2,5-dione glycolide, ε-caprolactone oxepane-2-one, trimethylene carbonate 1,3-dioxane-2-one, 2,2-dimethyltrimethylene carbonate, 1,5dioxepane-2-one, p-dioxanone 1,4-dioxane-2-one , gamma-butyrolactone, betabutyrolactone, beta-me-delta-valerolactone, ethylene oxalate 1,4-dioxane-2,3dione, 3- [benzyloxycarbonyl meyl] -1,4-dioxane-2,5-dione, ethylene oxide , propylene oxide, 5.5 '(oxepane-2-one), 2,4,7,9-tetraoxa-spiro [5.5] undecane-3,8dione, spiro-bid-dimethylene carbonate can produce copolymers. Copolymers can also be produced by adding monomers such as hydroxy compounds, multifunctional carboxylics or heterofunctional compounds that can be used as coupling agents for low molecular weight PLA.
[0096] FIG. 5 shows a schematic view of a reactive system for the polymerization of lactic acid. The reactive system (510) includes a stainless steel jacket reaction tank (520), an aerated screw extruder (528), a granulator (530), a heat exchanger (534) and a condensation tank (540) . An outlet (521) of the reaction tank connects to a tube (for example, stainless steel) that connects to an inlet (545) to a heat exchanger. An outlet (546) to a heat exchanger connects to another pipe (for example, stainless steel or other corrosion resistant material) and is connected to an inlet (548) to the tank
32/118 of condensation (540). The tubes and connections of the reaction tank and the condensation tank provide a fluid path (for example, water / air vapor) between two tanks. A vacuum can be applied to a fluid path between the tanks (520) and (540) using a vacuum pump (550) connected to the port (549).
[0097] The reaction tank (520) includes an outlet (524) that can be connected to the tube (for example, stainless steel) that connects to an inlet to a screw extruder (560). An extruder outlet (562) connects to the tube that optionally connects via a valve (560) to the reaction tank (520) through the inlet (527). Optionally, the extruder outlet (562) connects via a valve (560) to a granulator (530) via the inlet (532). Reaction tank and extruder tubes and connections provide a circular fluid path (for example, reagents and products) between the reaction tank and the extruder when the valve (560) is placed in a recirculatory position. The tubes and connections from the reaction tank to the granulator provide a fluid path between the reaction tank and the granulator when the valve (560) is placed in the granulator position.
[0098] When in operation, the tank can be loaded with lactic acid. The lactic acid is heated in the tank using the stainless steel heating jacket (522). In addition, a vacuum is applied to the condensation tank (540) and consequently to the reaction tank (520) through the stainless steel piping and connections using the vacuum pump (550). The heating of lactic acid accelerates condensation reactions (for example, esterification reactions) to form PLA oligomers, while the applied vacuum helps to volatilize the water that is produced. Water vapor travels out of the reagents and out of the reaction tank (520) and into the heat exchanger (534), as indicated by the arrow. The heat exchanger cools the water vapor and the condensed water drips into the condensation tank (540) through the pipes and
33/118 connections described previously. Multiple heat exchangers can be used. Since hydroxycarboxylic acids can be corrosive, reactor equipment and other associated equipment can be covered or coated with corrosion resistant metals, such as tantalum, alloys such as HASTELLOY ™, a trademark alloy from Haynes International, and the like . It can also be coated with high temperature inert polymeric coatings such as TEFLON ™, by DuPont, Wilmington, De. The corrosivity of the hydroxycarboxylic acid system may not be surprising, since the lactic acid pKa is more than 0.8 less than the acid acetic. Also, water undoubtedly hydrates the acid and the acidic end of the polymer. When these hydration waters are removed, the acidity can be much higher, since it is not leveled by the hydration waters.
[0099] In addition, during operation, the extruder (528) can be activated and operated to extract the reagents (eg, lactic acid, oligomers and polymers) out of the tank. When the valve (560) is placed in a recirculatory position, the reagents are circulated back to the reaction tank in the direction shown by the arrows. In addition to the extruder, the flow can be controlled by valve (525), for example, the valve can be adjusted in the closed position to not allow any flow, open for maximum flow, or in an intermediate position for higher or lower flow rates (for example, example, between about 0 and 100% open, about 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or about 100% open).
[00100] The reaction can be continued with reagents following a circular path (for example, with the valve in a recirculatory position) until the desired polymerization is achieved. This circulatory pathway provides mixing and shearing that can assist in polymerization (for example, increasing molecular weight, controlling polydispersity, improving polymerization kinetics, improving temperature distribution and reactive species diffusion). The products (for example, the polymer) can then be
34/118 driven to the granulator by adjusting the valve (560) in the granulator position. The granulator can then produce grains that can be collected. The grains can be of various shapes and sizes. For example, spherical or approximately spherical, in the form of a hollow tube, in the form of a tube filled with, for example, approximate volumes between about 1mm ³ to about 1cm ³ . The granulator can also be replaced by other equipment, for example, extruders, reactors and filament producers.
[00101] The extruder (528) can be an aerated screw extruder, so that water and other volatile compounds can be removed for further processing. The extruder can be a single screw or multiple screw extruder. For example, the extruder can be a twin screw extruder with co-rotating or counter-rotating screws. The screw extruder can also be a hollow flight extruder and can be heated or cooled. The screw extruder can be provided with doors for its interior. The doors can be used, for example, for the addition of additives, the addition of comonomers, the addition of crosslinking agents, the addition of catalysts, irradiation treatments and the addition of solvents. The ports can also be used for testing (for example, testing progress of the reaction or fixing problems). In addition to testing, the torque applied to the extruder can be used to monitor the progress of the polymerization (for example, while increasing viscosity). A line mixer (for example, a static mixer) can also be arranged in the life of the circulating reagents, for example, before or after the screw extruder, providing a tortuous route for the reagents that can enhance the mixture provided to the reagents. The extruder can be of such a size that, for example, the material can be recirculated, for example, about 0.25-10 times per hour (for example, about 1-5 or 1-4 times per hour).
[00102] The position of the return port (527) allows reagents to flow down the sides of the tank, increasing the surface area
35/118 of the reagents, thus facilitating the removal of water. The return port can include multiple (for example, a plurality of ports), arranged in different positions of the tanks. For example, the plurality of return ports can be arranged in circumference around the tank.
[00103] The tank may include a reciprocating scraper (529) that can help push the oligomers / polymers down into the reaction tank, for example, during or after the reaction is complete. Once the reciprocating scraper moves down, the scraper can then be moved back up to a resting position. The scraper can be moved up and down in the tank by engaging with an axle (640) which is attached to the core (650). In another possible embodiment, the center can be adjusted for mechanical coupling to a screw, for example, where the axis is a screw axis that extends to the bottom of the tank. The spindle can then rotate to drive the scraper up and down.
[00104] A top view of an alternative scraper modality is shown in FIG. 6A, while a front view is shown in FIG. 6B. The reciprocating scraper includes pistons (620) attached to a center (650) and to the ends of the scraper (630). The end of the scraper is in the form of a compression ring with an opening (660). The pistons apply pressure against the interior surfaces of the tank (615) through the ends of the scraper (630), while the scraper can be moved up and down in the tank, as shown by the arrow in FIG. 6B. The opening (660) allows the scraper to expand and contract. The scraper can be made of any flexible material, for example, steel such as stainless steel. The opening is preferably the smallest possible (for example, less than about 1 ”, less than about 0.1”, less than about 0.01 ”or even less than about 0.001”).
[00105] Another alternative scraper modality is
36/118 shown in FIG. 6C and in FIG. 6D. In this second embodiment, the ends of the scraper include a retaining ring. The retaining ring can be made of flexible material, for example, rubber. The movement of the retaining ring as the scraper moves up and down acts as a squeegee against the inside of the reaction tank.
[00106] The tank (520) can be 100 gallons in size, although larger and smaller sizes can be used (for example, between about 20 to 10,000 gallons, for example, at least 50 gallons, at least 200 gallons, at least 500 gallons, at least 1000 gallons). The tank, for example, can be configured to have a tapered or rounded bottom.
[00107] In addition to the discussed inlets and outlets, the tank may also include other openings, for example, to allow the addition of reagents or to allow access to the interior of the tank in case repairs are needed.
[00108] During the reaction the temperature in the tank can be controlled between about 100 and 180 ° C. Polymerization can preferably be started at about 100 ° C and the temperature raised to 160 ° C over the course of several hours (for example example, between 1 and 48 hours, 1 and 24 hours, 1 and 16 hours, 1 and 8 hours). A vacuum can be applied between about 0.1 and 2 mmHg). For example, at the beginning of the reaction about 0.1 mmHg and at the end of the reaction about 2 mmHg.
[00109] The water in the condenser tank (540) can be drained through an opening (542), using the control valve (544).
[00110] The heat exchanger can be a fluid cooled heat exchanger. For example, cooled with water, air or oil. Several heat exchangers can be used, for example, as needed to condense as much water as possible. For example, a second heat exchanger can be located between the vacuum pump and the condensation tank (540).
37/118 [00111] The equipment and reactions described in this document (for example, FIG. 5) can also be used for polymerization of other monomers. In addition, the equipment can be used after or during polymerizations for polymer mixing. For example, some of the hydroxyl acids described in this document can be polymerized by the methods, equipment and system described in this document.
[00112] In addition to the chemical method, lactic acid can be polymerized by organism and LA polymerizing enzymes. For example, ROP can be catalyzed by Candida antarctica lipase B, and hydrolases.
PLA STEREOCHEMISTRY [00113] The mechanical and thermal properties of pure PLA are largely determined by the molecular weight and stereochemical composition of the backbone. The stereochemical composition of the backbone can be controlled by the choice and the reason for the monomers; D-Lactic acid, L-Lactic acid or, alternatively, D-Lactide, L-Lactide or meso-Lactide. This stereochemical control allows the formation of block or random stereo copolymers. 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.
[00114] 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 from similarly treated samples. The percentage of crystallinity can be calculated using data from the table and
38/118 applying the equation.
% Z (AH _m -AHj
100 [00115] Where AH _m is the melting enthalpy in J / g, ΔΗ _α 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.
[00116] As can be calculated from the data in the table, crystallinity is directly proportional to the molecular weight of the pure L or D stereo polymer. The stereoisomer DL (for example, atactic polymer) is amorphous.
Table 1: PLA thermal properties
Type of Isomer M _n x 10 ³ M _w / M _n Tg (° C) T _m (° C) ΔΗ (J / g) T _c (° C) AH (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 65.7 170.3 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
[00117] The calculated crystallinities are ordered from top to bottom: 8.2%, 0%, 11.3%, 0%, 15.7%, 13.8%, 14.0% and 25%.
[00118] The heat treatment of the 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.
[00119] 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
39/118 the material is made, for example, tensile forces from 30 to almost 400 MPa, and tensile modulus between 1.7 and about 4.5 GPa.
PLA, HALF AND GRAFT COPOLYMERS [00120] The variation of PLA by the formation of copolymers, as discussed above, also has an enormous influence on properties, for example, by interrupting and decreasing 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.
[00121] In many cases, the improvements are correlated with a decrease in the transition temperature to glass. Some monomers can increase the PLA glass transition temperature. For example, salicylic acid lactones may have homopolymer glass transition temperatures between about 70 and 110 ° C and polymerize with lactide.
[00122] Morpholipediones, which are half alpha hydroxycarboxylic acids and half alpha amino acids co-polymerize with lactide to yield random high molecular weight copolymers with lower glass transition temperatures (for example, according to the Flory-Fox equation), morpholipediones made of glycine and lactic acid (6-methyl-2,5-morpholipedione), when copolymerized with lactide, can produce a polymer with glass transition temperatures of 109 and 71 ° C for a lactic acid of 50 and 75 mol% , respectively, in the polymer. Morfolinediones have been synthesized using glycolic acid and lactic acid and most alphaamino acids (eg, glycine, alanine, aspartic acid, lysine, cysteine, valine and leucine). In addition to reducing the glass transition temperature and improving the 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.
[00123] As an example, glycolide and lactide copolymers can be
40/118 useful as biocompatible surgical sutures due to improved flexibility and hydrophilicity. The higher 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 PLA. 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%. It is reported that beta-methylgamma-valerolactone copolymers 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.
[00124] Some additional useful monomers that can be copolymerized with lactide include 1,4-benzodioxepin2,3 (H) -dione glycolsalicinate; lactosalicinate 1,3-benzodioxepin-2,5- (3H, 3-methyl) -dione; dibenzo-1,5 dioxacin-6-12-dione disalicylate; morfoline-2,5-dione, 1,4-dixane-2,5-dione glycolide; trimethylene oxepane-2-one carbonate; 2,2dimethyltrimethylene carbonate; 1,5-dioxepane-2-one; p-dioxanone 1,4-dioxane-2-one; gamabutirolacton; beta-butyrolactone; beta-methyl-delta-valerolactone; beta-methylgama-valerolactone; ethylene oxalate 1,4-dioxane-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 carbonate 2,4,7,9tetraoxa-spiro [5.5] undecane-3,8-dione.
[00125] PLA polymers and copolymers can be modified through crosslinking. Crosslinking can affect thermal and rheological properties without necessarily deteriorating mechanical properties. For example, crosslinking of 0.2 mol% 5.5'-bis (oxepane-2-one) (bis- ε caprolactone)) and spiro-bis-dimethylene carbonate 0.1-0.2 mol%. Radical hydrogen abstraction reactions and subsequent recombination of polymer radicals is an effective way to induce cross-linking in a
41/118 polymer. Radicals can be generated, for example, by high energy electron beam and other irradiation (for example, between about 0.01 Mrad and 15 Mrad, for example between about 0.01-5 Mrad, between about 0-1-5 Mrad , between about 1-5 Mrad). For example, irradiation methods and equipment are described in detail below.
[00126] Alternatively, or in addition, peroxides such as organic peroxides are effective radical-producing and cross-linking agents. For example, peroxides that can be used include hydrogen peroxide, dicumil peroxide; benzoyl peroxide; 2,5-Dimethyl-2,5-di (tertbutylperoxy) hexane; tert-butylperoxy 2-ethylexyl carbonate; tert-amyl peroxy-2-ethylhexanoate; 1,1-di (tert-amylperoxy) cyclohexane; tert-amyl peroxyenedecanoate; tert-amyl peroxbenzoate; 2-ethylhexyl tert-amylperoxy carbonate; tert-amyl peroxyacetate; 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane; tert-butyl peroxy-2-ethylhexanoate; 1,1-di (tert-butylperoxy) cyclohexane; tert-butyl peroxyenedecanoate; tert-butyl peroxineoheptanoate; tert-butyl peroxyethylacetate; 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane; 3,6,9-triethyl3,6,9-trimethyl-1,4,7-triperoxonan; di (3,5,5-trimethylhexanoyl) peroxide; tertbutyl peroxyisobutyrate; tert-butyl peroxy-3,5,5-trimethylhexanoate; ditert-butyl peroxide; isopropyl tert-butylperoxy carbonate; tert-butyl peroxybenzoate; 2.2di (tert-butylperoxy) butane; di (2-ethylhexyl) peroxydicarbonate; di (2-ethylhexyl) peroxydicarbonate; tert-butyl peroxyacetate; tert-butyl cumyl peroxide; tertamylhydroperoxide; 1,1,3,3-tetramethylbutyl hydroperoxide and mixtures thereof. The effective amounts may vary, for example, depending on the peroxide, crosslinking conditions and the desired properties (for example, crosslinking amount). For example, crosslinking agents can be added between about 0.01 - 10% by weight (for example, about 0.1-10% by weight, about 0.01-5% by weight, about 0.1-1% by weight, about 1-8% by weight, about 4-6% by weight). For example, peroxides such as dicumil peroxide 5.25% by weight and benzoyl peroxide 01% by weight are effective radical and crosslinking agents for PLA and
42/118 derivatives of PLA. Peroxide crosslinking agents can be added to polymers such as solids, liquids and solutions, for example, in water or organic solvents such as mineral alcohols. In addition, radical stabilizers can be used.
[00127] Crosslinking can be carried out effectively by incorporation or unsaturation in the polymer chain either by: initiation with unsaturated alcohols such as hydroxyethyl methacrylate or 2-butene-1,4-diol; o post-reaction with unsaturated anhydrides such as maleic anhydride to transform the hydroxyl chain end; or copolymerization with unsaturated epoxides such as glycidyl methacrylate.
[00128] In addition to crosslinking, grafting functional groups and polymers to a PLA 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 quenching with a functional group containing an unsaturated bond can effectively functionalize the PLA backbone.
MIXING PLA [00129] PLA can be mixed with other polymers as miscible and immiscible compositions. For immiscible mixtures, the composition may be one with the minor component (for example, below 30% by weight) in the form of (for example, micro or submicron) regions in the main component. When a component is between about 30 to 70% by weight, the mixture forms a co-continuous morphology (for example, lamellar hexagonal phases or amorphous continuous phases).
[00130] Mixing can be achieved by melt mixing above the glass transition temperature of the amorphous polymer components. Screw extruders (for example, single screw extruders, corrotating twin screw extruders, counter counter rotating twin screw extruders) can be useful for this purpose. For polymers and
43/118 PLA copolymers, temperatures below about 200 ° C can be used to prevent thermal degradation (for example, less than about 180 ° C). Consequently, polymers that require higher processing temperatures are not, in most cases, good candidates for mixing with PLA.
[00131] Polyethylene oxide (PEO) and polypropylene oxide (PPO) can be mixed with PLA. Glycols with lower molecular weights (300-1000 Mw) are miscible with PLA, 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 PLA. They can also be used as polymeric plasticizers to reduce the modulus and increase the flexibility of the PLA. High molecular weight PEG (20,000) is miscible in PLA up to about 50%, but above that level the PEG crystallizes, reducing the ductility of the mixture.
[00132] Polyvinyl acetate (PVA) is miscible with PLA in all concentrations, where mixtures show only one Tg is observed in all mixing ratios, with a constant decrease up to about 37 ° C in 100% PVA. Low levels of PVA (5-10%) increase tensile strength and% PLA elongation, while reducing the rate of mass loss during biodegradation.
[00133] Mixtures of PLA and polyolefins (polypropylene and polyethylene) result in incompatible systems with poor physical properties due to poor interfacial compatibility and high interfacial energy. However, the interfacial energy can be reduced, for example, by the addition of third component compatibilizers, such as graft polyethylene glycidyl methacrylate. (irradiation would probably work) Polystyrene and high impact polystyrene resins are also non-polar and mixtures with PLA are, in most cases, not very compatible.
[00134] PLA and acetals can be mixed, producing compositions with useful properties. For example, good and high transparency.
44/118 [00135] PLA is miscible with polymethyl methacrylate and many other acrylates and copolymers of (meth) acrylates. Drawn films of PMMA / PLA mixtures are transparent and have high elongation.
[00136] Polycarbonate can be combined with PLA up to about 50% polycarbonate composition weight. The compositions have high heat resistance, flame resistance and hardness and have applications, for example, in consumer electronics products such as laptops. At about 50% by weight of the polycarbonate, the processing temperatures approach the PLA degradation temperature.
[00137] Acrylonitrile butadiene styrene (ABS) can be mixed with PLA, although the polymers are not miscible. This combination is a less brittle material than PLA and provides a way to harden PLA.
[00138] Poly (propylene carbonate) can be mixed with PLA providing a biodegradable composite, since both polymers are biodegradable.
[00139] PLA can also be mixed with poly (butylene succinate). Mixtures can provide thermal stability and impact strength to the PLA.
[00140] PEG, polypropylene glycol, poly (vinyl acetate), anhydrides (eg maleic anhydride) and fatty acid esters have already been added as plasticizers and / or compatibilizers.
[00141] The mixing can also be carried out with the application of irradiation, including irradiation and quenching. For example, irradiation or irradiation and quenching, as described in this document applied to biomass, can be applied to the irradiation of PLA and PLA copolymers for any purpose, for example, before, after and / or during mixing. This treatment can assist in processing, for example, making polymers more compatible and / or making / breaking bonds within the mixed polymer and / or additives (for example, polymer and plasticizer). Per
45/118 example, between about 0.1 Mrad and 150 Mrad, followed by quenching the radicals by adding fluids or gases (eg, oxygen, nitrous oxide, ammonia, liquids), using pressure, heat, and / or adding radical removers. The quenching of the biomass that has been irradiated is described in Pat. US No. 8,083,906 to Medoff, the disclosure of which is hereby incorporated by reference, and the equipment and processes described therein can be applied to PLA and PLA derivatives. Irradiation or extrusion or transport of PLA or PLA copolymers can also be used, for example, as described for the treatment of biomass in Order with Serial Number US 13 / 009,151 filed on May 2, 2011, the disclosure of which is incorporated herein in its entirety by reference.
PLA COMPOSITIONS [00142] Polymers, copolymers and mixtures of PLA can be combined with natural and / or synthetic materials. For example, PLA and any PLA derivative (for example, PLA copolymers, mixtures of PLA, grafted PLA, crosslinking PLA) can be combined with natural and synthetic fibers. For example, protein, starch, cellulose, vegetable fibers (for example, abaca fibers, leaf, skin, stem, 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).
[00143] Nanocompositions can also be produced by dispersing inorganic or organic nanoparticles within a polymer or thermoplastic or thermoset. 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.
[00144] Compositions can be prepared similarly to mixtures
46/118 polymers, for example, using screw extrusion and / or injection molding. Irradiation, as described in this document, can also be applied to compositions, during, after or before their formation. For example, irradiation of the polymer and combination with synthetic and / or natural materials, or irradiation of 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 composite after it has been combined, with or without further processing.
PLA WITH PLASTICIZERS AND ELASTOMERS [00145] In addition to the mixtures previously discussed, PLA and PLA derivatives can be combined with plasticizers.
[00146] For example, as described in J. Appl. Polym. Sci. 66: 15071513, 1997, PLA can be mixed with monomeric and oligomeric plasticizers in order to improve its flexibility and therefore overcome its natural fragility. Monomeric plasticizers, such as tributyl citrate, TbC, and diethyl bishidroximetil malonate, DBM, can dramatically decrease the T _g of PLA. The increase in molecular weight of plasticizers through the synthesis of oligoesters and oligoesteramides can result in mixtures with slightly lower Tg depressions than monomeric plasticizers. Compatibility with PLA may be dependent on the molecular weight of the oligomers and in the presence of polar groups (eg, amide groups, hydroxy groups, ketones, esters) that can interact with PLA chains. Materials can retain high flexibility and morphological stability for long periods of time, for example, when formed into films.
[00147] Ester citrates can also be used as plasticizers with polylactic acid (PLA). 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, about 5 -30
47/118% by weight, about 5-25% by weight, about 5-15% by weight). Plasticizers such as ester citrates can be effective in reducing the transition temperature to glass and improving elongation at break. The plasticizing efficiency may be higher for plasticizers of intermediate molecular weight. The addition of plasticizers can modulate the enzymatic degradation of PLA. For example, citrates of lower molecular weight can increase the rate of enzymatic degradation of PLA and citrates of higher molecular weight can decrease the rate of degradation, compared to non-plasticized PLA.
[00148] The preparation of polylactic acid / elastomeric mixtures can also be prepared by the melt blending technique, for example, as described in the Journal of Elastomersand Plastics, 3 January 2013. PLA and biodegradable elastomer can be mixed in melting and molded on an injection molding machine. The melting temperature may decrease while the amount of elastomer increases. In addition, the presence of elastomer can modulate the crystallinity of the PLA, for example, increasing the crystallinity by between 1 and 30% (for example, about 1 to 20%, between about 5 and 15%) The storage module and complex viscosity of PLA fusion may decrease when elastomer is added. 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.
[00149] It was observed that the temperature of cold crystallization of the mixtures decreased while the weight fraction of the elastomer increased, as well as the temperature of initiation of cold crystallization changed to a lower temperature. For example, as reported in the Journal of Polymer Research, February 2012, 19: 9818. In non-isothermal crystallization experiments, PLA crystallinity increased with a decrease in heating and cooling rates. Fusion crystallization of polylactic acid appeared at low refrigeration rate (1, 5 and 7.5 ° C / min).
48/118
The presence of small amounts of elastomer can also increase the crystallinity of polylactic acid. The DSC thermogram on a 10 ° C / min ramp demonstrated that the maximum crystallinity of polylactic acid is 36.95% with 20% by weight of elastomeric content in mixtures. In isothermal crystallization, the rate 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, which described a one-dimensional crystallization growth with homogeneous nucleation, whereas in the second stage, it varied from 2.09 to 2.71, which described the transitional mechanism for three-dimensional crystallization growth with homogeneous nucleation mechanism. The equilibrium melting point of polylactic acid was also evaluated at 176 ° C.
[00150] 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 in this document, can also be used.
[00151] Some examples of plasticizers that can be combined with PLA include: Triacetin, gicerol triacetate, tributyl citrate, polyethylene glycol, GRINDSTED® SOFT-N-SAFE (acetic acid monoglyceride ester) made from fully hydrogenated castor oil and combinations of these. Mixtures with any other plasticizer, for example, as described in this document, can also be used.
[00152] The main characteristic of elastomeric materials is the high elongation and the flexibility or high elasticity of these materials, against cracking or cracking.
49/118 [00153] Depending on the distribution and the degree of chemical bonds of polymers, elastomeric materials may have properties or characteristics similar to thermoplastics and thermosets, hence, elastomeric materials can be classified into: Thermosetting elastomers (for example, they do not melt when heated) ) and Thermoplastic Elastomers (for example, melt when heated). Some properties of elastomeric materials: They cannot melt, changing to a gaseous state before they melt; swelling in the presence of certain solvents; they are generally insoluble; they are flexible and elastic; less resistance to deformity than thermoplastic materials.
[00154] Examples of applications for elastomeric materials described in this document are: 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 vehicle wheels or 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 in this document can be used as substitutes for polyurethane and silicone adhesives.
FLAVORS, FRAGRANCES AND COLORS [00155] Any of the products and / or intermediates described in this document, for example, hydroxy acids, lactic acid, PLA, PLA derivatives (for example, PLA copolymers, crosslinking PLA, graft PLA, mixtures of PLA or any other PLA containing materials prepared as described in this document) can also be combined with flavors, fragrances, colors and / or mixtures thereof. For example, anyone
50/118 or more of (optionally, together with flavors, fragrances and dyes) sugars, organic acids, fuels, polyols, such as sugar alcohols, biomass, fibers and compositions, hydroxycarboxylic acids, lactic acid, PLA, PLA derivatives they can be combined with (for example, formulated, mixed or reacted) or used in the manufacture of other products. For example, one or more of such products can be used in the manufacture of soaps, detergents, sweets, drinks (for example, cola, wine, beer, alcoholic beverages such as gin or vodka, sports drinks, coffees, teas) , drugs, adhesives, sheets (for example, fabrics, non-fabrics, filters, wipes) and / or compounds (for example, plates). For example, one or more of such 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, chocolate, vanilla, mint, mint, onion, garlic, pepper, saffron, ginger, milk, wine, beer, tea, lean meats, fish, seafood, olive oil, coconut fat, pork fat, butter fat, broth, vegetables, potatoes, marmalade, ham, coffee and cheeses.
[00156] 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% by weight to about 10% by weight, between about 0.1% by weight to about 5% by weight, 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, or more) by any means and in any order or sequence (for example, stirred, mixed, emulsified, gelled, infused, heated) , sonicated, and / or suspended). Fillers, binders, emulsifiers, antioxidants can also be used, for example, protein gels, gums and silicone.
[00157] Flavors, fragrances and colors can be natural materials
51/118 and / or synthetic. 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 in this document). 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 the use of the methods, systems and equipment described here, hot water extraction, supercritical fluid extraction, chemical extraction (for example , solvent or reactive extraction 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, as produced and 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 in this document, for example an ester and a product derived from lignin.
[00158] 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 class of polyphenols are flavonoids, such as anthrocyanins, flavonols, flavan-3-ools, flavones, flavanones and flavanonols. Other phenolic compounds that can be used include phenolic acids and their esters, such as
52/118 chlorogenic acid and polymeric tannins.
[00159] Inorganic compounds, mineral or organic compounds can be used, for example, titanium dioxide, cadmium yellow (for example, CdS), cadmium orange (for example, CD with some SE), alizarin red (for example , synthetic or non-synthetic rose madder), ultramarine blue (for example, synthetic ultramarine blue, natural ultramarine blue, synthetic violet ultramarine), cobalt blue, cobalt yellow, cobalt green, viridian (e.g. hydrated chromium (III) oxide, chalcophilite, conicalcite, cornubite, cornualite and liroconite.
[00160] Some flavors and fragrances that can be used include AZALEIA TBHQ, ACET C-6, ALIL AMIL GLICONATO, ALFA TERPINEOL, AMBRETTOLIDE, AMBRINOL 95, ANDRANE, APHERMATE, APPLELIDE, BACDANOL®, BERGAMAL, ÉPOXIDO DE BETA-IONONA ISOBUTYLIC OF BETA NAFTIL, BICYCLONONALACTONE, BORNAFIX®, CANTOXAL, CASHMERAN®, CASHMERAN® VELUDO, CASSIFFIX®, CEDRAFIX, CEDRAMBER®, CEDRIL ACETATE, CELESTILE, CINNYL CELL, CYLINDERYLIDE, CINNAMELOLOL, CINNAMOLOL, , CITRONELIL ACETATE, PURE CITRONELIL ACETRATE, CITRONELIL FORMIATE, CLARYCET, CLONAL, CONIFERAN, PURE CONIFERAN, ALDEHYDE CORTEZ 50% PEOMOSA, CYCLABUTE, CYCLACET®, CYCLAPROXYCLE, , CYCLACET DIIDRO, MIRCENOL DIIDRO, TERPINEOL DIIDRO, TERPINYL ACIDATE DIIDRO, DIMETHYL CYCLORMOL, DIMETHYL OCTANOL PQ, DIMIRCETOL, DIOLA, DIPENTENE, DULCINYL® RECRISTALIZED, FYRIDALYL, FUELYLIDE, 3-GLYCORATE OZONE, FLORIFFOL, FRAISTONE, FRUCTONA, GALAXOLIDE® 50, GALAXOLIDE® 50 BB, GALAXOLIDE® 50 IPM, GALAXOLIDE® NON-DILUTED, GALBASCONE, GENERALDEHYDE, GERANIOL 5020, GERANIOL TYPE 600, GERANIOL 950, GERANIOLI
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ISOBUTIL QUINOLINA, KHARISMAL® SUPER, LIFFAROME ™, LIMOXAL, (PURE), GERANIOL COEUR CFT, GERANIOL COEUR, GERANIL COEUR ACETATE, GERANIL ACETATE, PURE, GERANIL ACETATE, GRAY, HERBAL, HERBAL, ACRYLIC, HERBAL, ACRYLIC ™, HEXADECANOLIDA, HEXALON, HEXENIL SALICILATO CIS-3, BODY OF JACINTO, NO. BODY OF JACINTO NO. 3, HYDROPROPIC ALDEHYDE, HYDROXYL, INDOLAROME, INTRELEVEN ALDEHYDE, SPECIAL INTRELEVEN ALDEHYDE, ALPHA IONONE, BETA IONONE, ISOCYCLE, CITRAL, ISOCYCLE, GERANIOL, KASMAL, JASMAL, JESMAL, JESMAL, , LINDENOL ™, LYRAL®, LYRAME SUPER,
MANDARINE ALDEHYDE 10% TRI ETH, CITR, MARITIME, CHINESE MCK, MEIJIFF ™, MELAFLEUR, MELOZONE, METHY ANTHRANILATE, METHYL IONONEALFA EXTRA, METHYLONONA GAMA A, METHYLONON GAMA COEUR, METILIONONA GAMAROUU, METHYLONA, MUGUET ALDEHYDE 50, ALMÍSCAR Z4, MYRAC ALDEHYDE, MIRCENYL ACETATE, NECTARATE ™, NEROL 900, NERYLACETATE, OCIMENE, OCTACETAL, ORANGE FLOWER Ether, ORIVONA, ORRINIFF 25%, OXASPUROYLE, OXASPHERO , PICONIA, PRECYCLEMONE B, PRENIL ACETATE, PRISMANTOL, BODY OF RESEDÁ, ROSALVA, PINK ALMÍSCAR, SANJINOL, SANTALIFF ™, SYVERTAL, TERPINEOL, TERPINOLENO 20, TERPINOLENO 90 PQ, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE, TERPINOLETTE. MUGUOL®, MIRCENOL TETRAHIDER, TETRAMERAN, TIMBERSILK ™, TOBACAROL, TRIMOFIX® O TT, TRIPLAL®, TRISAMBER®, VANORIS, VERDOX ™, VERDOX ™ HC, VERTENEX®, VERTENEX® HC, VERTFEX® COFOL, , VIVALDIE, ZENOLIDA, ABS INDIA 75 PCT MIGLYOL, ABS MOROCCO 50 PCT DPG, ABS MOROCCO 50 PCT TEC, ABSOLUTE FRENCH, ABSOLUTE INDIA,
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ABSOLUTE MD 50PCT BB, ABSOLUTE MOROCCO, PG CONCENTRATE, 20 PCT DYE, AMBERGRIS, AMBARETTE ABSOLUTE, AMBERET SEED OIL, ARTEMISIA OIL 70 PCT TUIONA, GRAND VERT, MANJERÃO ABSOLUTE GRAND VERT, VERVEINE BASIL OIL, VIETNAMITE BASIL OIL, DETERPENIZED BAY OIL, NG BEE WAX ABS, BEE WAX ABSOLUTE, BENZOINE SIÃO RESINIDE, BENZOINE SYNTHESE TANK , BENZOINE SIÃO 70.5 PCT TEC RESIN, ABS BLACK CURRANEAN BUTTON 65 PCT PG, ABS BLACK CURRANCY BUTTON MD 37 PCT TEC, MIGLYOL BLACK CURRANT BUTTON ABS, ABSOLUTE BURGUNDY BEAR BUTTON, RUBBER OIL, RUBBER OIL. BRAN, RESINÓIDE BRAN, ABSOLUTE BROOM ITALIANO, CO2EXTRATO OF CARDAMOMO GUATEMALTECO, CARDAMOMO OIL GUATEMALTECO, INDIAN CARDAMOMO OIL, CARROT HEART, ABSOLUTE EGYPTIAN ACACIA, ABSOLUTE EGYPTIAN ACCIDENT: EC, ABS CASTOROUS C 50 PCT MIGLYOL, ABSOLUTE CASTOROUS, CASTOROUS RESINOID, CASTOROUS RESINOID 50 PCT DPG, CEDROL, CEDRENO, REDIST CYLINDER OIL, ROMAN CAMOIL, OIL, CAMOMILE OIL, CAMOILE OIL, CAMOILE OIL, CAMOIL OIL WILD WITH LOW LIMONENE, CEILÃO CINNAMEL BARE OIL, ABSOLUTE CISTE, ABSOLUTE CISTE COLORLESS, CITRONELA OIL. ASIAN WITHOUT IRON, ABS CIVET 75 PCT PG, ABSOLUTE CIVET, CIVET DYE 10 PCT, ABS, FRENCH CLOSE SAVAGE ABSOLUTE FRENCH CLOSE SAVAGE ABSOLUTE, COLORFUL CLARINE SAVAGE 50 PCT PG, FRENCH SLAVE OIL, BALANCE SHEET, FRENCH COURSE COPAÍBA BALM OIL, Cilantro Seed Oil, Cypress Oil,
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ORGANIC CYPRESTE, DAVANA OIL, GALBANOL, ABSOLUTE GOLANAN ABSOLUTE, GALBANE OIL, GALBANE RESINIDIDE, GALBANE RESIDENTIAL 50 PCT DPG, HERCOLINBHT GHETAN RESIDENTIAL, GHETHANEAN RESIDENT, GHETHANEAN AGENT, 20 , EGYPTIAN EGYPTIAN GERANIUM ABS, EGYPTIAN GERANIUM ABSOLUTE, CHINESE GERANIUM OIL, EGYPTIAN GERANIUM OIL, GINGER OIL 624, SOLUBLE RECTIFIED GINGER OIL, ABSOLUTE, WOOLEN WOODEN HEART, ABSOLUTE 50 , ABSOLUTE HAY MD 50 PCTTEC, PALO SANTO, ORGANIC HISSOPO OIL, ABS IMMORTELLE IUGO MD 50 PCT TEC, ABSOLUTE IMMORTELLE SPAIN, ABSOLUTE IMMORTELLE IUGO, ABS JASMIM INDIAN, ABSOLUTE JASMINE, JASMINE ABSOLUTE MOROCCAN JASMINE, ABSOLUTE JASMINE AMBAC, ABS JUNQUILO MD 20 PCT BB, ABSOLUTE JUNGILET FRENCH, ZIMBERRY BERRY OIL FLG, SOLUBLE RECTIFIED ZINBERRY OIL, 50PCS LABD RESIDENTIAL, 50PCS LABID RESIDENTIAL, 50PCS RADIUM LÁDDANO ESINOID MD, LÁDDANO RESINOID MD 50 PCT BB, ABSOLUTE LAVANDINE H, ABSOLUTE LAVANDINE MD, LAVANDINE OIL ABRIAL ORGANIC, LAVANDINE OIL ORGANIC LAUNDRY OIL, LAVANDINE OIL, SUPERIOR OIL LAUNDRY LAVANDA OIL, LAVANDA OIL WITHOUT CUMARINE, LAVANDA OIL WITHOUT ORGANIC CUMARINA, LAVANDA OIL MAILLETTE ORGANIC, LAVANDA OIL MT, ABSOLUTE MACE BB, LOW METHYL OIL, MAGNOLOUS FLOWER, MAGNOLOUS FLOWER OIL, MAGNIUM FLOWER MAGNOLIA FLOWER OIL MD, MAGNOLIA LEAF OIL, MANDARINE OIL MD, MANDARINE OIL MD BHT, ABSOLUTE MATE BB, ABSOLUTE TREE MOSS MD TEX IFRA 43, ABS MOSS OAK MD TEC
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IFRA43, ABSOLUTE OAK MOSS, IFRA 43, ABSOLUTE TREE MOSS, MD IPM IFRA 43, BB MIRRA RESINOID, MD MIRRA RESINOID, TEC MIRRA RESINOID, IRON MIXLET OIL, TUNISISOUS MISSILE TISSUE, OIL, TISSUARY TISSUE, OIL 20PCT BB, FRENCH NARCISSE ABSOLUTE, NEROLI TUNISIANO OIL, DETERPENIZED FLUSHED WALNUT OIL, OEILLET ABSOLUTE, OLYBANE RESINOID, OLÍBANO RESINOID, MD OLÍBANO RESIN, PÍGINO, RESINIDE OLÍBANO MD 50 PCTDPG, OLÍBANO TEC RESINOID, OPOPONAX TEC RESINOID, MD BHT ORANGE OIL OIL MD SCFC ORANGE OLIVE OIL OIL, ABSOLUTE TUNISIAN ORANGE FLOWER, ABSOLUTE LARGE ORANGE FLOWER WATER, ABSOLUTE LONG ORANGE FLOWER WATER , ABSOLUTE ORANGE FLOWER WATER TUNISIAN, ABSOLUTE ORRIS ITALIANA, ORRIS CONCRETA 15PCT IRONA, ORRIS CONCRETA 8 PCT IRONA, NATURAL ORRIS 15 PCT IRONA 4095C, ORRIS NATURAL 8 PCTIRONA 295 OSMANTO, ABSOLUTE OSMANTO MD 50 PCT BB, HEART OF PATCHOULI INDONESIUM, INDONESIAN PATCHOULI OIL WITHOUT IRON, PATCHOULI INDONESIAN MD OIL, PATCHOULI REDIST OIL, HEART OF OIL, POOL ORANGE-AZEDA PETITGRAIN TUNISIANO, PETITGRAIN CITRONNIER OIL, PARAGUAYAN PETITGRAIN OIL DESTERPENIZED, PETITGRAIN OIL DETERPENIZED STAB, PEPPER BERRY OIL, BOTTLE BOTTLE OIL, GOLF OIL MOROCHAN PINK METHYL ABS, LOW TURKISH PINK METHYLENE, ABSOLUTE ROSE, ABSOLUTE BULGARIAN ROSE, ABSOLUTE ROSE DAMASCINE, ABSOLUTE ROSE
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MD, ABSOLUTE ROSE MOROCCAN, ABSOLUTE ROSE TURKISH, BULGARIAN ROSE OIL, LOW METHYLENE OIL DAMASCENE ROSE, TURKISH ROSE OIL, ORGANIC HANDLED OIL, SUNNY OIL, TUNNELIAN OIL, TUNNIAN OIL RECTIFIED INDIAN, SANTALOL, SCHINUS MOLLE OIL, CIPO PAINTING OF SÃO JOÃO 10 PCT, STYRAX RESINOID, TAGETE OIL, TREE HEART, TONKA FAVA ABS 50 PCT SOLVENTS, ABSOLUTE TONKA FAVA, ABSOLUTE , HEART OF VETIVER EXTRA, HAITIAN VETIVER OIL, HAITIAN VETIVER OIL MD, JAVANESE VETIVER OIL, JAVANESE VETIVER OIL MD, ABSOLUTE EGYPTIAN VIOLET SHEET, ABSOLUTE VIOLET VIOLET LEAF ABSOLUTE LEAF VIOLET MD 50 PCT BB, DETERPENIZED ALOSNA OIL, YLANG EXTRA OIL, YLANG III OIL and combinations thereof.
[00161] Dyes may be among those listed in the International Color Index by the Society of Dyers and Colorists. 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, βnaphthols, naphthols, benzimidalozones, diazo-type condensation pigments, pyrazolones, nickel-azo yellow, phthalocyanines, quinacridones, perylenes and perinones, pigments indoline and isoindolinone, triarylcarbonium pigments, diceto-pyrrole-pyrol pigments, thioindigoids, carotenoids include, for example, alpha-carotene, beta-carotene, gamma-carotene, lycopene, lutein extract and astaxanthin, dehydrated beet (dried beet) , canthaxanthin, caramel, Apo-8'-carotenal, mealybug extract, carmine, sodium-copper-chlorophylline, toasted and partially cottonseed flour
58/118 defatted, ferrous gluconate, ferrous lactate, grape-colored extract, grape skin extract (enokyanin), carrot oil, paprika, paprika oleoresin, mica-based pearl pigments, riboflavin, turmeric, titanium dioxide , carbon black, self-dispersing carbon, tomato lycopene extract, tomato lycopene concentrate, turmeric, turmeric oleoresin, FD&C Azul no.1, FD&C Azul no. 2, FD&C Verde no. 3, Orange B, Citrus Red no. 2, FD&C Red no. 3, FD&C Red no. 40, FD&C Yellow no. 5, FD&C Yellow no. 6, alumina (dry aluminum hydroxide), calcium carbonate, potassium-sodium-copper-chlorophyllin (copper-chlorophylline complex), dihydroxyacetone, bismuth oxychloride, ferric ammonium ferrocyanide, ferric ferrocyanide, chromium hydroxide green, greens chromium oxide, guanine, pyrophyllite, talcum powder, aluminum powder, bronze powder, copper powder, zinc oxide, D&C Blue no. 4, D&C Verde no. 5, D&C Verde no. 6, D&C Verde no. 8, D&C Orange no. 4, D&C Orange 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, D&C Red 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33, D&C Red No. 34, D&C Red No. 36 , D&C Red No. 39, D&C Violet No. 2, D&C Yellow No. 7, D&C Yellow No. 7 Ext, D&C Yellow No. 8, D&C Yellow No. 10, D&C Yellow No. 11, D&C Black No. 2, D&C Black No. 3 (3), D&C Brown No. 1, D&C Ext., Chromium-cobalt-aluminum oxide, ferric ammonium citrate, pyrogallol, campeche extract, 1,4-Bis [(2-hydroxy copolymers) -etill) amino] -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], violet carbazole, chlorophyllin-copper complex, chromium-cobalt-aluminum oxide, Vat Vat Vat 1, 2 - [[2,5-Dietoxi- 4 - [(4-methylphenyl) thiol vat) ] 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-D iidro-9,10dioxo- 1,5-anthracenedil) bisbenzamide, 7,16-Dichloro-6,15-dihydro-5,9,14,1859 / 118 anthrazinetetrone, 16,17-Dimethoxydinafto (1,2,3-cd : 3 ', 2', 1'-1m) perylene-5,10dione, poly dye copolymers (hydroxyethyl methacrylate) (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] - 2,4dihydro-5-methyl- 2-phenyl-3H-pyrazol-3-one (Solvent Yellow 18), 6-Ethoxy-2- (6ethoxy-3-oxobenzo [b] thieno-2 (3H) -idene) benzo [b] thiophene-3 (2H ) -one, phthalocyanine green, reactive products based on 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 l-amino -4 - [[4 - [(2bromo-1-oxoalyl) amino] -2-sulfonatophenyl] amino] -9,10-dihydro-9,10dioxoanthracene-2-sulfonate (Reactive Blue 69), D&C Blue No. 9, co bre [hthalocyaninate (2-)] and mixtures thereof.
[00162] For example, a fragrance, for example, natural wood fragrance, can be combined in the resin used to make the composite. In some implementations, the fragrance is combined directly in 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. An example of a twin screw extruder is the WP ZSK 50 MEGACOMPOUNDER ™, manufactured by Coperion, Stuttgart, 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 embodiments, the amount of fragrance in the composite 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
60/118 and brazilwood. 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, marjoram, musk, myrrh, orange, patchouli, rose, rosemary, sage, sandalwood, tea tree, thyme, gualtéria, 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 US Patent No. 8,074,910 issued on December 13, 2011, the disclosure of which is incorporated herein in its entirety by reference.
USES OF PLA AND PLA COPOLYMERS [00163] Some uses of PLA and PLA-containing materials include:
personal hygiene items (for example, handkerchiefs, towels, diapers), ecological packaging, garden (compostable vases), electronic products for personal consumption (for example, laptop covers and cell phones), devices, food packaging, disposable packaging ( eg food containers and drink bottles), garbage bags (eg compostable garbage bags), mulch films, matrices and controlled release containers (eg for fertilizers, pesticides, herbicides, nutrients, drugs , flavoring agents, food), shopping bags, general purpose film, high heat resistant films, heat resistant sealing adhesive, surface coatings, disposable tableware (eg plates, glasses, forks, knives, spoons, sporks, bowls), auto parts (for example, panels, fabrics, under-hood covers), carpet fibers, clothing fibers (for example, fibers, sportswear fibers, footwear fibers), biomedical devices (for example, surgical sutures, implants, scaffolding, drug delivery systems, dialysis equipment and
61/118 engineering [00164] Other industrial uses / sectors that can benefit from the use of PLA and PLA derivatives (for example, elastomers) include information technology and software, electronics, geoscience (for example, oil and gas), engineering, aerospace (for example, armrests, seats, panels), telecommunications (for example, headphones), chemical manufacturing, transportation such as automobiles (for example, dashboards, panels, tires, wheels), materials and steel, consumer packaged goods, wires and cables.
OTHER ADVANTAGES OF PLA AND PLA COPOLYMERS [00165] PLA is biological and can be composted, recycled, used as fuel (incinerated). Some of the degradation reactions include thermal degradation, hydrolytic degradation and biotic degradation.
[00166] PLA can be thermally degraded. For example, at high temperatures (for example, between about 200-300 ° C, about 230260 ° C). The reactions involved in the thermal degradation of PLA can follow different mechanisms such as thermohydrolysis, zipper depolymerization (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.
[00167] PLA can also be subjected to hydrolytic degradation. Hydrolytic degradation includes chain splits that produce smaller polymers, oligomers and eventually monomer lactic acid can be released. Hydrolysis can be associated with thermal and biotic degradation. The process can be carried out by various parameters such as PLA structure, its molecular weight and distribution, its morphology (ie crystallinity), the sample format (for example, isolated thin samples or comminuted samples can degrade more fast), thermal and mechanical history (eg processing) and hydrolysis conditions (eg temperature, agitation, comminution). Hydrolysis of PLA begins with
62/118 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 the PLA are hydrolyzed.
[00168] PLA can also be subjected to 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.
[00169] During composting, the PLA can undergo several stages of degradation. For example, an initial step may occur due to exposure to moisture where degradation is abiotic and PLA is degraded by hydrolysis. This step can be accelerated by the presence of acids and bases and elevated temperatures. The first step can lead to a weakening of the polymer, which can facilitate the diffusion of PLA out of the polymers in bulk. The oligomers can then be attacked by microorganisms. Organisms can degrade oligomers and 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 many orders of magnitude faster than that of typical petroleum-based plastics, such as polyethylene (for example, the order of hundreds of years).
[00170] PLA can also be recycled. For example, PLA can be hydrolyzed to lactide acid, purified and re-polymerized. Unlike other recyclable plastics such as PET and HDPE, PLA does not need to be lowered to make a product of diminished value (for example, from a bottle to cover decks or carpets). The PLA can, in theory, be recycled indefinitely. Optionally, the PLA can be reused and downgraded for several generations and then converted to PLA and re-polymerized.
63/118 [00171] PLA can also be used as a fuel, for example, for the production of energy. PLA can have a high calorific index, for example, up to about 8400 BTU. The incineration of pure PLA releases only carbon dioxide and water. Combinations with other ingredients typically total less than 1ppm of non-PLA waste (eg, gray). Thus, the combustion of PLA is cleaner than that of other renewable fuels, for example, wood.
[00172] PLA can have high gloss, high transparency, high clarity, high rigidity, can be UV-stable, non-allergenic, with high flavor and aroma and barrier properties, easy to mix, easy to mold, easy to format, easy to record, easy to print, lightweight, compostable.
[00173] One can also print on the PLA. For example, by lithographic, inkjet, laser, fixed and cylindrical printing. You can also write about some PLA, for example, using a pen.
[00174] Processing, as described in this document, may include radiation. For example, irradiation with radiation between about 1 and 150 Mrad (for example, any range like those described in this document) can improve the compostability and recyclability of PLA and materials containing PLA.
RADIATION TREATMENT [00175] The raw material (for example, cellulosic, lignocellulosic, PLA, PLA derivatives and combinations thereof) can be treated with electron bombardment to modify its structure, for example, to reduce its resistance or by reticulation of 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 and / or porosity of the raw material. Alternatively, this treatment can produce radicals that can be sites of cross-linking, grafting and / or functionalization.
[00176] In general, electron bombardment through an electron beam is preferable, as it provides a very high performance. The
64/118 accelerators used to accelerate particles can be electrostatic DC, electrodynamic DC, linear RF, continuous wave or linear by magnetic induction. 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 Leitner, CM et al., Status of the Superconducting ECR Ion Source Venus, Proceedings of EPAC 2000, Vienna, Austria.
[00177] 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.
[00178] 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. In
65/118 optional way, 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.
[00179] 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 having a relatively low beam power, avoids excessive temperature rise, thus preventing the combustion of the material, in addition to increasing the uniformity of the dose through the thickness of the material layer.
[00180] It is generally preferred that the raw material bedding has a relatively uniform density. In some embodiments the thickness is less than approximately 1 inch (for example, less than approximately 0.75 inches, less than approximately 0.5 inches, less than approximately 0.25 inches, less than approximately 0.1 inch, between approximately 0.1 inch and approximately 1 inch, between approximately 0.2 and 0.3 inches).
[00181] In some implementations, it is desirable to cool the material during and between dosing the material with electron bombardment. For example, the material can be cooled when transported, for example, by a screw extruder, vibrating conveyor or other transport equipment. For example, refrigeration during transportation is described in International Application No. PCT / US2014 / 021609 filed on March 7, 2014 and International Application No. PCT / US2014 / 021632 filed on March 7, 2014, the full description of which is incorporated herein by reference.
[00182] To reduce the energy required by the resistance reduction process, it is desirable to treat the material as quickly as possible. In general, treatment is carried out at a dose rate greater than approximately 0.25
66/118
Mrad per second, for example: greater than approximately 0.5, 0.75, 1, 1.5, 2, 5, 7, 10, 12, 15 or even approximately 20 Mrad per second, for example: approximately 0.25 to approximately 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 enable higher yield for a target dose (for example, the desired dose). 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 a volume density 0.5 g / cm ³ ).
[00183] 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 embodiments, treatment is carried out until the material receives a dose of approximately 10 Mrad to approximately 50 Mrad, for example: from 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 preferable, ideally applied for a few seconds, for example: at 5 Mrad / pass with each pass being applied for approximately one second. The application of a dose greater than 7 to 8 Mrad / passage can, in some cases, cause the thermal degradation of the raw material. Refrigeration can be applied before, after or during irradiation. For example, refrigeration methods, systems and equipment as
67/118 described in the following applications can be used: International Application No. PCT / US2014 / 021609 filed on March 7, 2014 and International Application No. PCT / US2013 / 064320 filed on October 10, 2013, whose full publication is incorporated herein by reference.
[00184] 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 here, treatment of the material with numerous relatively low doses, instead of a high dose, tends to avoid overheating the material and also increases the uniformity of the dose across the thickness of the material. In some implementations, the material is agitated or mixed in another way during or after each pass and then smoothed to form a uniform layer again before the next pass, further enhancing the uniformity of the treatment.
[00185] In some modalities, electrons are accelerated at a speed, for example, greater than 75% of the speed of light, for example: greater than 85, 90, 95 or 99% of the speed of light.
[00186] In some embodiments, any of the processes described here occur in the raw material material that remains dry when purchased or that has been dried, for example: using heat and / or reduced pressure. For example, in some embodiments, the cellulosic and / or lignocellulosic material has less than 25 pesos% of the water retained, measured at 25 ° C and at fifty percent relative humidity (for example, less than approximately 20 weight%, less than approximately 15 weight%, less than approximately 14 weight%, less than approximately 13 weight%, less than approximately 12 weight%, less than approximately 10 weight%, less than approximately 9 weight%,
68/118 less than approximately 8 weight%, less than approximately 7 weight%, less than approximately 6 weight%, less than approximately 5 weight%, less than approximately 4 weight%, less than approximately 3 weight% less than about 2 weight%, less than about 1 weight%, less than about 0.5 weight%, less than about 15 weight%.
[00187] In some modalities, two or more electron sources are used, as two or more ionizing sources. For example, samples can be treated, in any order, with an electron beam, followed by gamma radiation and UV light that has wavelengths from approximately 100 nm to approximately 280 nm. In some modalities, the samples are treated with three sources of ionizing radiation, such as an electron beam, gamma radiation and UV energy light. The biomass is transported through the treatment zone, where it can be bombarded with electrons.
[00188] It may be advantageous to repeat the treatment to more completely reduce the resistance of the biomass and / or further modify the biomass. In particular, the process parameters can be adjusted after a first (for example: second, third, fourth or more) pass, depending on the strength 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 embodiments, multiple treatment devices (for example, electron beam generators) are used to treat biomass (for example, 2, 3, 4 or more) multiple times. In other modalities, even a single electron beam generator can be a source of multiple beams (for example: 2, 3, 4 or more beams) that can be used for the treatment of biomass.
[00189] The effectiveness in changing the molecular / supermolecular structure and / or in reducing the resistance of the biomass containing carbohydrate depends on the
69/118 energy of the electron used and the dose applied, while the exposure time depends on the power and the dose. In some embodiments, the 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 during the process so that they can be released from biomass intact, for example: as monomeric sugars.
[00190] 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, 540, 10-50, 10-75, 15-50, 20-35 Mrad.
RADIOPACAL MATERIALS [00191] The invention may include processing the material in a cavity and / or a shed that is constructed using radiopaque materials. In some implementations, radiopaque materials are selected to be able to protect components against X-rays with high energy (short wavelength), which can penetrate many materials. An important factor in the design of a radiation protection enclosure is the attenuation of the length of the materials used, which will determine the thickness required for a specific material, a mixture of materials or a layered structure. The attenuation length is the penetration distance over which the radiation is reduced to approximately 1 / e (e = Euler number) times that of the incident radiation. Although virtually all materials are radiation opaque if sufficiently thick, materials that contain a high compositional percentage (eg density) of elements that have a high Z value (atomic number) have a shorter radiation attenuation length, if Those
70/118 materials are used, there is a thinner, lighter protection. Examples of high Z-value materials that are used for radiation protection are tantalum and lead. Another important parameter in radiation protection is to reduce the distance in half, which is the thickness of a specific material that will reduce the intensity of the gamma ray by 50%. As an example for X-ray radiation with an energy of 0.1 MeV, the thickness in half is approximately 15.1 mm for concrete and approximately 0.27 mm for lead, while with an X-ray energy of 1 MeV, the thickness half for concrete is approximately 44.45 mm and for lead it is approximately 7.9 mm. Radiopaque materials can be thick or thin materials, as long as they can reduce the radiation that passes to the other side. Thus, if it is desired that a specific enclosure has a low wall thickness, for example: for light weight or due to size restrictions, the chosen material must have a sufficient Z value and / or an attenuation length so that its length halved is less than or equal to the desired wall thickness for the enclosure.
[00192] In some cases, the radiopaque material may be a layered material, for example, having a layer of a material of higher Z value to provide good protection, and the layer of a material of lower Z value to provide other properties (eg structural integrity, impact resistance, etc.) In some cases, the layered material may be a laminate classified as Z, for example, including a laminate where the layers provide a high Z element gradient through successively lower Z elements. In some cases, radiopaque materials can be radiation blocks can be coupled blocks, for example: lead and / or concrete blocks can be supplied by NELCO Worldwide (Burlington, MA) and reconfigurable cavities can be used as described in the Application International No.
71/118
PCT / US2014 / 021629 filed on March 7, 2014, the complete publication of which is incorporated herein by reference.
[00193] Radiopaque material can reduce radiation by passing through a structure (for example, a wall, a door, a ceiling, a fence, a series or a combination of these structures) formed from the material by approximately 10% (for example, at least approximately 20%, at least approximately 30%, at least approximately 40%, at least approximately 50%, at least approximately 60%, at least approximately 70%, at least approximately 80%, at least at least approximately 90%, at least approximately 95%, at least approximately 96%, at least approximately 97%, at least approximately 98%, at least approximately 99%, at least approximately 99.9%, at least approximately 99.99%, at least approximately 99.999%) compared to incident radiation. Consequently, a enclosure made of radiopaque material can reduce the exposure of equipment / systems / components by an identical amount. Radiopaque materials can include stainless steel, metals with Z values above 25 (for example: lead, iron), concrete, dirt, sand and combinations of these. Radiopaque materials may include a barrier in the direction of incident radiation of at least approximately 1 mm (for example: 5 mm, 10 mm, 5 cm, 10 cm, 100 cm, 1 m, 10 m).
ELECTRON SOURCES [00194] Electrons interact through Coulomb collision and the bremsstrahlung radiation produced by changes in electron speed. Electrons can be produced by radioactive nuclei that undergo beta decay, such as isotopes of iodine, cesium, technetium and iridium. Alternatively, an electron injector can be used as an electron source through thermionic emission and accelerated through an acceleration potential. An electron injector generates electrons, speeds them up
72/118 through great potential (for example: greater than approximately 500 thousand, 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 approximately 10 million volts) and then does a magnetic scan on them in the xy plane, where electrons are initially accelerated in the z direction through the tube and extracted in a leaf window . The scanning of the electron beam is useful for increasing the irradiation surface when irradiating materials, for example: a biomass, which is transported through the beam where the scanning was carried out. Scanning the electron beam also distributes the thermal charge evenly across the window and helps reduce breakage of the leaf window due to heating by the electron beam. The rupture of the leaf window is the cause of a significant interruption due to the necessary subsequent repairs and the reclosing of the electron injector.
[00195] 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, recirculation accelerators or static, dynamic linear accelerators, van de Graff accelerators and folded tandem accelerators. Such devices are disclosed, for example, in United States Patent No. 7,931,784 to Medoff, the complete publication of which is incorporated herein by reference.
[00196] An electron beam can be used as a source of radiation. An electron beam has high dose rates (for example: 1, 5 or even 10 Mrad per second), high performance, less containment and less confinement equipment. Electron beams can also have high electrical efficiency (for example, 80%),
73/118 allowing a reduced use of energy compared to other radiation methods, which can result in a lower operating cost and a reduced emission of greenhouse gases corresponding to the lesser 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.
[00197] Electrons may also be more efficient in causing changes in the molecular structure of materials containing carbohydrates, for example, by a chain splitting mechanism. In addition, electrons having energies of 0.5-10 MeV can penetrate low density materials, such as the biomass materials described here, for example: materials that have a volume density of less than 0.5 g / cm ³ and a depth of 0.3 -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 approximately 0.7 MeV to approximately 1.25 MeV. methods of irradiation materials are discussed in the United States patent App. Pub. 2012/0100577 A1, filed on October 18, 2011, the publication of which is incorporated herein by reference.
[00198] Electron beam irradiation devices can be obtained commercially from Ion Beam Applications, Louvain-la-Neuve, Belgium or from Titan Corporation, San Diego, CA Typical electron energies can be 0.5 MeV, 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV or 10 MeV. The power
74/118 typical of the electron beam irradiation device 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.
[00199] The disadvantages when considering the power specifications of the electron beam irradiation device include capital cost, depreciation and device footprint. The disadvantages when considering the exposure dose levels 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.
[00200] The electron beam irradiation device can produce a fixed beam or a scanning 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. Below, sweep widths of 0.5 m, 1 m, 2 m or more are available. The scanning beam is preferable in most of the modes described here because of the wider scanning width and the reduced possibility of local heating and window failure.
ELECTRON INJECTORS - WINDOWS [00201] The extraction system for an electron accelerator can include two shutters. The window leaves are described in the International App. No. PCT / US2013 / 064332 deposited on October 10, 2013, the complete publication of which is incorporated herein by reference. The cooling gas in the two window window extraction systems can be a pure 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
75/118 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).
[00202] When using a siege, the enclosed conveyor can also be removed with an inert gas in order to maintain an atmosphere at a reduced oxygen level. Keeping oxygen levels low prevents the formation of ozone, which in some cases is undesirable due to its reactive and toxic nature. For example, oxygen may be less than approximately 20% (for example, less than approximately 10%, less than approximately 1%, less than approximately 0.1%, less than approximately 0.01%, or even less than approximately 0.001% oxygen). Removal can be done with an inert gas including, but not limited to, nitrogen, argon, helium or carbon dioxide. This can be provided, for example, from the evaporation of a liquid source (for example, liquid nitrogen or helium), generated or separated from the air in situ or supplied from tanks. The inert gas can be recirculated and all residual oxygen can be removed using a catalyst, such as a copper catalyst bed. Alternatively, combinations of removal, recirculation and oxygen removal can be done to keep oxygen levels low.
[00203] The enclosure can also be removed with a reactive gas that can react with biomass. This can be done before, during or after the irradiation process. Reactive gas can be, but is not limited to, nitrous oxide, ammonia, oxygen, ozone, hydrocarbons, aromatics, starches, peroxides, azides, halides, oxyhalides, phosphides, phosphines, arsines,
76/118 sulfides, thios, boranes and / or hydrides. The reactive gas can be activated in the enclosure, for example, by irradiation (for example, electron beam, UV irradiation, microwave irradiation, heat, IR radiation), so that it reacts with the biomass. Biomass itself can be activated, for example, by irradiation. Preferably the biomass is activated by the electron layer, to produce radicals which then react with the reactive gas activated or deactivated, for example, by coupling or by extinction of the radical.
[00204] The removal gases supplied to a surrounded conveyor can also be cooled, for example, below approximately 25 ° C, below approximately 0 ° C, below approximately -40 ° C, below approximately -80 ° C, below approximately -120 ° C. For example, the gas can be evaporated from a compressed gas like liquid nitrogen or sublimated from a solid carbon dioxide. As an alternative example, the gas can be cooled by a refrigerator or part or the entire conveyor can be cooled.
HEATING AND PERFORMANCE DURING RADIATION TREATMENT [00205] Several processes can occur in biomass when the electrons in an electron beam interact with matter in inelastic collisions. For example, ionization of the material, polymer chain fission in the material, crosslinking 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. Heat the
77/118 irradiation sample can help to reduce resistance, but overheating can destroy the material, as explained below.
[00206] 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 ⁰ C and AT is the change in temperature at ⁰ C. A typical dry biomass material will have a heat capacity close to 2. Wet biomass will have a higher heat capacity depending on the amount of water, as the heat capacity of the water is very high (4.19 J / g ⁰ C). Metals have much lower heat capacities, for example: 304 stainless steel has a heat capacity of 0.5 J / g ⁰ C. The temperature change due to the instantaneous absorption of radiation in a biomass and from stainless steel to various radiation doses are shown in table 1.
Table 1: Calculated temperature rise for biomass and stainless steel.
Dose (Mrad) Estimated biomass ΔΤ (° C) Steel ΔT (° C) 10 50 200 50 250, Decomposition 1000 100 500, Decomposition 2000 150 750, Decomposition 3000 200 1000, Decomposition 4000
[00207] Elevated temperatures can destroy and / or modify the biopolymers in the biomass, so that the polymers (for example, cellulose) are inappropriate for further processing. A biomass subjected to high temperatures can become dark, sticky and release odors that indicate decomposition. Viscosity can even make the material hard to transport. Odors can be unpleasant and pose a safety problem. In fact, it has been found that keeping biomass below approximately 200 ° C is beneficial in the process described here (for
78/118 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 and 160 ° C, between approximately 60 ° C and 150 ° C, between approximately 60 ° C and 140 ° C, between approximately 60 ° C and 130 ° C, between approximately 60 ° C and 120 ° C, between approximately 80 ° C and 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).
[00208] 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 yield is also desired so that irradiation does not become a strangler in the processing of biomass. The treatment is governed 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 absorbed (without unit), P is the power emitted (KW = Voltage in MeV * current in mA), time is the treatment time (sec) and D is the absorbed dose (KGy). In an exemplary process where the fraction of the absorbed power is fixed, the Power emitted 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 ^-1 K ^-1 ), heat dissipation is slow, unlike, for example, metals (greater than approximately 10 Wm ^-1 K ^-1 ) which can dissipate energy quickly as long as there is a heat sink
79/118 heat to which to transfer energy.
ELECTRON INJECTORS - BEAM SWITCHES [00209] In some embodiments, systems and methods include a beam switch (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 switch can be used to energize the electron beam, for example, the beam switch can interrupt the electron beam until a beam current of a desired level is obtained. The beam switch can be placed between a primary leaf window and a secondary leaf window. For example, the beam switch can be mounted so that it is movable, that is, so that it can be moved in and out of the beam path. Even 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 switch is fixed in relation to the scan alarm, so that the beam can be effectively controlled by the beam switch. The beam switch can incorporate a hinge, a rail, wheels, grooves and other means that allow 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.
[00210] 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 with these metals (for example, metallized ceramic, metallized polymer, metallized composite, metallic materials with
80/118 multilayer).
[00211] The beam switch can be cooled, for example, with a coolant 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 switch can take any shape, including flat, curved, round, oval, square, rectangular, beveled and wedge shapes.
[00212] The beam switch can have perforations in a way that allows some electrons to pass through, thereby controlling (for example, reducing) radiation levels across 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.
BIOMASS MATERIALS [00213] 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 (for example, wild grass, miscantum, tusk grass, ice grass, Coastal Bermuda grass), grain residues, (for example, bark rice, oat husks, wheat chaff, barley husks), agricultural residues (for example, silage, canola straw, wheat straw, barley straw, oat straw, straw
81/118 rice, jute, hemp, flax, bamboo, sisal, abaca, corn on the cob, soy stubble, corn fiber, alfalfa, hay, coconut fiber, nut shells, palm leaves and coconut oil by-products ), cotton, cottonseed fibers, flax, sugar processing residues (eg bagasse, beet pulp, agave bagasse), algae, seaweed, seaweed, manure (for example, solid livestock manure, pig waste), debris, carrot processing waste, molasses washing used, bivalve alfalfa and mixtures of these materials.
[00214] In some cases, the lignocellulosic material includes ear of corn. Ground or ground corn cobs can be spread in a layer of relatively uniform thickness for irradiation, and after irradiation they 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 the corn stalk, corn seeds, and in some cases even the plant's root system.
[00215] Advantageously, no additional nutrients (with the exception of 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.
[00216] 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 and lignocellulosic materials, such as hay and grass.
[00217] Cellulosic materials include, for example, paper, paper products, paper waste, paper pulp, pigmented papers, loaded papers, coated papers, filled papers, magazines, printed matter (for example: books, catalogs, manuals , labels, calendars, cards, brochures, prospectuses, newspapers), printer paper, coated paper, cardboard, materials with a high content of α-cellulose, such as cotton and mix of any of these materials. For example, paper products
82/118 as described in Application U. S. No. 13 / 396,365 (“Magazine Feedstocks” by Medoff et al., Filed on February 14, 2012), the complete publication of which is incorporated herein by reference.
[00218] Cellulosic materials may also include lignocellulosic materials that have been partially delignified.
[00219] 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 starch material can be carrot, buckwheat, banana, barley, cassava, kudzu, ogres, sago, sorghum, conventional homemade potatoes, sweet potatoes, taro, yams or one or more grains, such as broad beans, lentils or peas. Mixtures of two or more starchy materials are also starchy materials. Mixtures of starchy, cellulosic or lignocellulosic materials can also be used. For example, a biomass can be an entire plant, a part of a plant or different parts of a plant, for example, a wheat plant, cotton plant, corn plant, rice plant or a tree. Starch materials can be treated by any of the methods described here.
[00220] Microbial materials include, but are not limited to, any microorganisms present in nature or genetically modified or organisms that contain or are capable of offering a source of carbohydrates (for example, cellulose), for example, protists, for example: protist animals (for example, protozoa such as flagellates, ameboids, ciliates and sporozoans), plant protists (for example, algae like alveolates, chloroachnophytes, cryptomonas, euglenides, glaucophytes, haptophytes, red algae, alveolate stramenopils, chlorarachnoids and cryptocurrencies, , glaucophytes, haptophytes, red algae,
83/118 stramphenophylls and viridiplantae). Other examples include seaweed, plankton (for example, macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton and phentoplankton), phytoplankton, bacteria (for example, gram-positive and extremophilic bacteria), gram - positive bacteria, grass - negative bacteria, and extremophiles), yeast and / or mixtures thereof. In some cases, microbial biomass can be obtained from natural resources, for example: the ocean, lakes, bodies of water, for example: salt water or fresh water or on land. Alternatively or in addition to the previous cases, microbial biomass can be obtained from culture systems, for example: large-scale dry culture and fermentation systems.
[00221] In other modalities, biomass materials, such as cellulosic, starchy and lignocellulosic materials, can be obtained from transgenic microorganisms and plants that have been modified in relation to a wild variety. Such modifications can occur, for example, through iterative stages of selection and production to obtain the desired characteristics in a plant. In addition, the plants may have had the genetic material removed, modified, silenced and / or added in relation to the wild variety. For example, genetically modified plants can be produced by recombinant DNA methods, where genetic modifications include the introduction or modification of specific genes of parental varieties or, for example, by the use of transgenic productions in which a specific gene or more genes are introduced into a plant of 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, radiation
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UV) and thermal shocks or other external pressures and subsequent selection techniques. 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 into the seed or plant include, for example, the use of a bacterial, biological carrier, calcium phosphate precipitation, electroporation, genetic junction, gene silencing, lipofection, microinjection and viral transporters. Additional genetically modified materials have been described in U.S. Application, Serial No. 13 / 396,369 filed February 14, 2012, the complete publication of which is incorporated herein by reference.
Some of the methods described here can be practiced with mixtures of all the biomass materials described here.
PREPARATION OF THE BIOMASS MATERIAL - MECHANICAL TREATMENTS [00222] The biomass can be in dry form, for example, with moisture content below approximately 35% (for example, less than approximately 20%, less than approximately 15%, less than about 10%, less than about 5%, less than about 4%, less than about 3%, less than about 2% or even less than about 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 pesos% solids (for example, at least approximately 20 pesos%, at least approximately 30 pesos%, at least approximately 40 pesos%, at least approximately 50 pesos%, at least approximately 60 pesos%, at least approximately 70 pesos%).
[00223] The processes disclosed here may use low volumetric density materials, for example: cellulosic raw materials or
85/118 lignocelluloses 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 . The volumetric density is determined using ASTM D1895B. Briefly, the method involves filling a known volume measuring cylinder with a sample and obtaining a sample weight. Volumetric density is calculated by dividing the sample weight in grams by the known volume in cubic centimeters. If desired, low volumetric density materials can be densified, for example, less methods described in US Patent No. 7,971,809 to Medoff, the complete publication of which is incorporated herein by reference.
[00224] In some cases, the 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). configuration, the desired biomass falls through the perforations or the screen and thus the bi larger mass than the perforations or the screen is not
86/118 irradiated. These larger materials can be reprocessed, for example, by commuting, or they can simply be removed from processing. In another configuration, the material larger than the perforations is irradiated and the smaller 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 drilled 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.
[00225] 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. Screening can also be by magnetic screening, in which a magnet is placed close to the transported material and the magnetic material is removed magnetically.
[00226] An optional pretreatment may include heating the material. For example, a portion of the carrier can be shipped through a heated region. The heated region 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 only a portion of the material or for the whole material. For example, a portion of the transport channel can be heated by using a heating liner. Heating may, for example, serve the purpose of drying the material. In the case of drying the material, this can be facilitated, with or without heating, by the movement of a gas (for example, air, oxygen, nitrogen, He, CO ₂ , argon) over and / or through the biomass while it is being transported.
[00227] Optionally, the pre-treatment process can include cooling the material. The cooling material is described in the patent of the
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United States No. 7,900,857 to Medoff, the complete publication of which is incorporated herein by reference. For example, refrigeration can take place by supplying a cooling 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.
[00228] Another optional pretreatment processing method may include adding a material to the biomass. The additional material can be added, for example, by watering, spraying and / or pouring the material into the biomass as it is transported. Materials that can be added include, for example, metals, ceramics and / or ions as described in US Patent Application Publication 2010/0105119 A1 (filed October 26, 2009) and US Patent Application Publication 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 (eg, peroxides, chlorates), polymerizable monomers (eg, 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 made to evaporate, for example, by heating and / or insufflation of the gas as previously described. The added material can form a uniform coating on 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 by increasing the efficiency of the irradiation, moistening the irradiation or changing the effect of the irradiation (for example, from electron beams to X-rays or heat).
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Method may not have an impact on irradiation, but may be useful for further downstream processing. The added material can help transport the material, for example, by decreasing dust levels.
[00229] The biomass can be distributed to the conveyor (for example, the vibrating conveyors used in the cavities described here) 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, dumped and / or positioned on the conveyor by any of these methods. In some embodiments, the material is distributed to the conveyor using an enclosed material distribution system to help maintain an atmosphere with low oxygenation and / or control dust and fine particles. Dust and fine particles of biomass accumulated or suspended in the air are undesirable because they can produce a risk of explosion or damage the windows of an electron injector (if this device is used to treat the material).
[00230] The material can be leveled to form a uniform thickness between approximately 0.0312 and 5 inches (for example, between approximately 0.0625 and 2000 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.
[00231] Generally, it is preferred to transport the material as quickly
89/118 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 ¹ Λ inch and 100 mA, the conveyor can move at approximately 20 feet / min to provide a useful irradiation dose, at 50 mA the conveyor can move at approximately 10 feet / min to provide approximately the same irradiation dosage.
[00232] After the biomass material has been transported through the radiation region, an optional post-treatment process can be performed. The optional post-treatment process can, for example, be a process described in relation to the pre-irradiation process. For example, biomass can be screened, heated, cooled and / or combined with additives. Exceptionally for post-irradiation, radical extinction may occur, for example, radical extinction by the addition of fluids or gases (eg, oxygen, nitrous oxide, ammonia, liquids), using pressure, heat and / or addition of radical removers. 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, the biomass is exposed during irradiation to the reactive fluid or gas. The extinction of the biomass that has been irradiated is described in U.S. Patent No. 8,083,906 to Medoff, the complete publication of which is incorporated herein by reference.
[00233] If desired, one or more mechanical treatments can be used in addition to irradiation to further reduce the resistance of the material containing carbohydrate. These processes can be applied before, during and / or after irradiation.
[00234] In some cases, mechanical treatment may include a
90/118 initial preparation of the raw material as received, for example, reduction of the size of the materials, as by comminution, for example, by cutting, grinding, shearing, spraying or flap. 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.
[00235] Alternatively, or additionally, the raw material material may undergo another treatment, for example: chemical treatments, such as with acid (HCl, H ₂ SO ₄ , H ₃ PO ₄ ), a base (eg KOH and NaOH), a chemical oxidant (eg, peroxides, chlorates, ozone), irradiation, vapor explosion, pyrolysis, sonication, oxidation, chemical treatment. Treatments can be in any order and in any sequence and combination. For example, the raw material material may 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 these treatments, for example, irradiation or pyrolysis, tend to be more fragile and, therefore, it may be easier to make additional changes in the material structure 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 pre-hydrolyzed material. The methods can also be used with
91/118 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 in material non-hydrolyzed, with about 60% or more in material non-hydrolyzed, with about 70% or more in material non-hydrolyzed, with
approximately 80% or more of non-hydrolyzed material or even with 90% or more of non-hydrolyzed material.
[00236] In addition to the size reduction, which can be performed initially and / or later during the process, mechanical treatment can also be advantageous to open, press, break or fragment the materials containing carbohydrates, making the cellulose of the materials more susceptible chain fission and / or disruption of the crystalline structure during physical treatment.
[00237] Methods for mechanically treating carbohydrate-containing material include, for example, grinding or crushing. Grinding can be carried out using, for example, a hammer mill, a ball mill, a cone or conical mill, a disc mill, an edge mill, a Wiley mill, a corn mill or another mill. The crushing can be carried out using, for example, an impact / cutting grinder. Some exemplary grinders include stone grinders, pin grinders, coffee grinders and burr 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 mechanical treatment methods include mechanical tearing or tearing, other methods that apply pressure to the fibers and air friction grinding. 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.
[00238] Mechanical feed preparation systems can be configured to produce flows with specific characteristics, such as,
92/118 for example, specific maximum size, width by specific 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.
[00239] The volumetric density of raw materials can be controlled (for example, increased). In some situations, it may be desirable to prepare a material with low volumetric density, for example, by densifying the material (for example, densification can facilitate and make it less laborious to transport to another location) and then revert the material to a state of lower volumetric 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 US Patent No. 7,932,065 to Medoff and International Publication No. WO 2008/073186 (which was filed on October 26, 2007, published in English and designated the United States) , whose complete publications are hereby incorporated by reference. Densified materials can be processed by any of the methods described here, or any material processed by any of the methods described here can be subsequently densified.
[00240] In some embodiments, the material to be processed is in the form of a fibrous material that includes fibers produced by the shearing of
93/118 a fiber source. For example, shearing can be performed with a rotary knife cutter.
[00241] 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.
[00242] In some incorporations, the cutting of the fiber source and the passage of the first resulting fibrous material through a first fabric are performed simultaneously. Shearing and passing can also be carried out in one process and passing can also be carried out in a batch-type process.
[00243] For example, a rotary knife cutter can be used to simultaneously shear the fiber source and screen the first fibrous material. A rotary knife cutter includes a funnel that can be loaded with a defibrated fiber source prepared by shredding a fiber source.
[00244] In some implementations, the raw material receives the
94/118 physical treatment before saccharification and / or fermentation. Physical treatment processes can include one or more of any of those described here, such as mechanical treatment, chemical treatment, irradiation, 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 a molecular structure of a biomass raw material can be used, alone or in combination with the processes disclosed here.
[00245] The mechanical treatments that can be used, and the characteristics of mechanically treated materials containing carbohydrates, are described in more detail in US Patent Application Publication 2012/0100577 A1, filed on October 18, 2011, whose publication is incorporated here by reference.
[00246] The mechanical treatments described here can also be applied to process PLA and PLA-based materials.
SONICATION, PYROLYSIS, OXIDATION, VAPOR EXPLOSION [00247] If desired, one or more sonication, pyrolysis, oxidative or vapor explosion processes can be used instead of or in addition to irradiation to further reduce or reduce the resistance of the carbohydrate-containing material or processing PLA and / or PLA-based materials. For example, these processes can be applied before, during and / or after irradiation. These processes are described in detail in U.S. relative No. 7,932,065 to Medoff, the complete publication of which is incorporated herein by reference.
BIOMASS HEAT TREATMENT [00248] 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,
95/118 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.
[00249] The 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 weight% in the water. In case the biomass is the irradiated biomass, water is added and the heating treatment is carried out.
[00250] The heat treatment is carried out in an aqueous suspension or mixture of biomass. The amount of biomass is 10 to 90 weight% of the total mixture, alternatively 20 to 70 weight% or optionally 25 to 50 weight%. The irradiated biomass can have a minimum water content so water must be added before the heat treatment.
[00251] 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 [00252] Using the methods described here, an initial biomass material (for example, plant biomass, animal biomass, paper and waste biomass from a municipality) can be used as raw material for produce useful intermediates and products such as organic acids, salts of organic acids, hydroxycarboxylic acids, PLA, anhydride acid, esters of
96/118 organic acids and fuels, for example, fuels for internal combustion engines or raw materials for fuel cells. The systems and processes described here can use cellulosic and / or lignocellulosic materials that are readily available as raw material, but can often be processed with difficulty, for example: municipal waste streams and paper waste streams, such as the streams that include newspaper, kraft paper or mixtures thereof.
[00253] To convert the raw material into a form that can be immediately processed, the glucan- or cellulose containing 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 an acid, a process referred to as saccharification. Low molecular weight carbohydrates can then be used, for example, in an existing manufacturing facility, such as a single-cell protein facility, an enzyme manufacturing facility or a fuel plant, for example, an ethanol manufacturing plant.
[00254] The raw material can be hydrolyzed using an enzyme, for example, by combining the materials and the enzyme in a solvent, for example, in an aqueous solution.
[00255] 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 metabolites of biomass degradation with small molecules. These enzymes can be a complex of enzymes that act synergistically to degrade crystalline cellulose or the lignin portions of the biomass. Examples of cellulosic enzymes include: endoglucanases, cellobiohydrolases and cellobiases (beta-glycosidases).
[00256] During saccharification, a cellulosic substrate can be initially hydrolyzed by endoglycolases at random locations producing oligomeric intermediates. These intermediaries are then carcasses for
97/118 exo-cracking glucanases such as cellobiohydrolase to produce cellobiose from the ends of the cellulose polymer. Cellobiosis is a 1,4-bonded, water-soluble glucose dimer. Finally, celobiase is divided into cellobiosis to generate glucose. The efficiency (for example, hydrolyzation time and / or completion of hydrolysis) of this process depends on the strength of the cellulosic material.
INTERMEDIARIES AND PRODUCTS [00257] Using the processes described here, the biomass material can be converted into one or more products, such as energy, fuels, food and materials. Specific examples of products include, but are not limited to, hydrogen, sugars (eg, glucose, xylose, arabinose, mannose, galactose, fructose, disaccharides, oligosaccharides and polysaccharides), alcohols (eg, monohydric alcohols or dihydric alcohols, such as ethanol, n-propanol, isobutanol, seg-butanol, tert-butanol or n-butanol), hydrated or hydrous alcohols (eg containing more than 10%, 20%, 30% or even 40% water ), biodiesel, organic acids, hydrocarbons (for example, methane, ethane, propane, isobutene, pentane, n-hexane, biodiesel, biogasoline and mixtures thereof), co-products (eg proteins, such as cellulolytic proteins (enzymes) or single-cell proteins ) and mixtures thereof in any combination or relative concentration, or optionally in combination with any additives (for example, fuel additives). Other examples include carboxylic acids, salts of a carboxylic acid, a mixture of carboxylic acids and salts of carboxylic acids and esters of carboxylic acids (for example, methyl, ethyl and n-propyl esters), ketones (for example, acetone) , aldehydes (for example, acetaldehyde), alpha and beta unsaturated acids (for example, acrylic acid) and olefins (for example, ethylene). Other alcohols and alcohol derivatives include propanol, propylene glycol, 1.4-butanediol, 1.3-propanediol, sugar alcohols (eg, erythritol, glycol, glycerin, sorbitol treitol, arabitol, ribitol, mannitol, dulcitol, fucitol, iditol, isomalt , maltitol, lactitol, xylitol and other polyols) and esters
98/118 of methyl or ethyl of any of these alcohols. Other products include methyl acrylate, methyl methacrylate, lactic acid, PLA, citric acid, formic acid, acetic acid, propionic acid, butyric acid, succinic acid, valeric acid, caproic acid, 3-hydroxypropionic acid, palmitic acid, stearic acid, oxalic acid, glutaric acid, oleic acid, linoleic acid, glycolic acid, hydroxybutyric acid-gamma and mixtures of these, salts of any of these acids, mixtures of any of these acids and their respective salts.
[00258] Any combinations of the above products with each other, and / or the above products with other products, in which these other products can be made by the processes described here or otherwise, can be packaged together and sold as products. Products can be combined, for example, mixed, smoothed or codissolved, or they can simply be packaged or sold together.
[00259] Any of the products or product combinations described here can be sanitized or sterilized before the products are sold, for example, after purification or isolation or even after packaging, to neutralize one or more potential undesirable contaminants that could be present in the product (s). This cleaning can be done with electron bombardment, for example, being in a dosage less than approximately 20 Mrad, for example, approximately 0.1 to 15 Mrad, approximately 0.5 to 7 Mrad or approximately 1 to 3 Mrad.
[00260] The processes described here can produce numerous variants of by-products useful for generating steam and electricity to be used in other parts of the plant (cogeneration) or sold on the open market. For example, the steam generated from the burnt product variants can be used in the distillation process. As another example, the electricity generated from the by-product variants being burned can be used to charge electron beam generators used in the pre-99/118 treatment.
[00261] The by-products used to generate steam and electricity are derived from a number of sources throughout the process. For example, anaerobic digestion of wastewater can produce biogas high in methane and a small amount of residual biomass (sludge). As another example, post-saccharification and / or post-distillation solids (eg, unconverted lignin, cellulose and hemicellulose remaining from pretreatment and primary processes) can be used, for example, burnt, as a fuel.
[00262] Other intermediates and products, including food and pharmaceutical products, are described in Patent Application Publication U.
S. 2010/0124583 A1, published on May 20, 2010, Medoff, whose full publication is incorporated here by reference.
LIGNIN DERIVED PRODUCTS [00263] The spent biomass (eg spent lignocellulosic material) from the lignocellulosic process by the methods described is expected to have a high lignin content and, in addition to being useful for the production of energy by combustion in a plant cogeneration, can have uses like other valuable products. For example, lignin can be used as captured as a plastic, or it can be synthetically elevated to other plastics. In some examples, it can also be converted to lignosulfonates, which can be used as binders, dispersants, emulsifiers or sequestrants.
[00264] 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, for the production of a slab of particle or plywood, to bind animal food, as a fiberglass binder, as a linoleum paste binder and as a soil stabilizer.
[00265] As a dispersant, lignin or lignosulfonates can
100/118 be used, for example, as mixtures of concrete, clay and ceramics, coloring peppers, leather tanning and plasterboard.
[00266] As an emulsifier, lignin or lignosulfonates can be used, for example, in asphalt, in pigments and dyes, pesticides and in wax emulsions.
[00267] 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.
[00268] For the production of energy, lignin generally has a higher energy index than holocellulose (cellulose and hemicellulose), since it contains more carbon than holocellulose. For example, dry lignin can have an energy rating of between approximately 11,000 and 12,500 BTUs per pound, compared to 7,000 and 8,000 BTUs per pound of holocellulose. As such, lignin can be densified and converted to briquettes and pellets for incineration. For example, lignin can be converted to pellets by any method described here. For a slower incineration pellet or briquette, lignin can be cross-linked, as by applying a radiation dose between approximately 0.5 Mrad and 5 Mrad. Crosslinking can produce a slower incineration form factor. The form factor, such as a pellet or a briquette, can be converted to synthetic coal or charcoal by pyrolysis in the absence of air, for example, between 400 and 950 ° C. Before pyrolysis, it may be desirable to cross-link lignin to maintain its structural integrity.
[00269] Cogeneration using spent biomass is described in International Application No. PCT / US2014 / 021634 deposited on March 7, 2014, the complete publication of which is incorporated here by reference.
[00270] Products derived from lignin can also be combined with PLA and products derived from PLA (for example, PLA that was produced as described here). For example, lignin and derived products
101/118 lignin can be beaten, grafted or otherwise combined and / or mixed with PLA. Lignin can, for example, be useful to reinforce, plasticize or modify PLA in other ways.
SACARIFICATION [00271] The treated biomass materials can be saccharified generally by combining the material and the cellulase enzyme in a medium fluid, for example, an aqueous solution. In some cases, the material is boiled, soaked or cooked in hot water before saccharification, as described in US Patent Application Publication 2012/0100577 A1 by Medoff and Masterman, published on April 26, 2012, the complete indices of which are incorporated here.
[00272] Saccharification can be done by inoculating a mixture of raw sugar produced by saccharification of a reduced resistant lignocellulosic material to produce a hydrocarboxylic 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.
[00273] The saccharification process can be partially or completely performed in a tank (for example, a tank that has a volume of at least 4000, 40,000 or 500,000 L) in a manufacturing plant, and / or can be partially or completely executed in transit, for example: in a wagon, in a tanker truck or in a supertanker or in the 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 at a manufacturing plant under controlled conditions, cellulose will be converted substantially completely into sugar, for example: glucose, in approximately 12-96 hours. If saccharification is performed
102/118 partially or completely in transit, saccharification may take longer.
[00274] 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 complete publication of which is incorporated herein by reference.
[00275] The addition of surfactants can enhance 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.
[00276] 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. The water can be removed, for example: by evaporation, to increase the concentration of the sugar solution. This reduces the volume to be sent and also inhibits microbial growth in the solution.
[00277] Alternatively, sugar solutions of lower concentrations 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: from 50 to 150 ppm . Other suitable antibiotics include amphotericin B, ampicillin, chloramphenicol, ciprofloxacin, gentamicin, hygromycin B, kanamycin, neomycin, penicillin, puromycin, streptomycin. Antibiotics will inhibit the growth of microorganisms during transport and storage, and can be used in appropriate 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 additives with
103/118 antimicrobial preservative properties can be used. Preferably, the antimicrobial additive (s) is / are food grade.
[00278] A solution of relatively high concentration can be obtained by limiting the amount of water added to the material containing carbohydrate with the enzyme. The concentration can be controlled, for example, by controlling the amount of saccharification present. For example, the concentration can be increased by adding more carbohydrate-containing material to the solution. 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.
SACARIFYING AGENTS [00279] Suitable cellulite enzymes include cellulases of Bacillus, Coprinus, Myceliophthora, Cephalosporium, Scytalidium, Penicillium, Aspergillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acrylic, Variety, Chryssosporium species and Chrysosporium Aspergillus species (see, for example, EP Pub. 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. dichromosporum, A. obclavatum, A. pinkertoniae, A. roseogriseum, A. incoloratum and A. furatum). Preferred variants 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. CBS 535.71, Acremonium brachypenium CBS 866.73,
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Acremonium dichromosporum CBS 683.73, Acremonium obclavatum CBS 311.74, Acremonium pinkertoniae CBS 157.70, Acremonium roseogriseum CBS 134.56, Acremonium incoloratum CBS 146.62 and Acremonium furatum CBS 299.70H. Cellulosic enzymes can also be obtained from Chrysosporium, preferably a variant of Chrysosporium lucknowense. Additional variants 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 EP Pub. No. 0 458 162) and Streptomyces (see, for example, EP Pub. No. 0 458 162).
[00280] 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, H ₂ SO ₄ , H ₃ PO ₄ ) and strong bases (for example, NaOH, KOH).
SUGARS [00281] In the processes described here, for example, after saccharification, sugars (eg, 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 and any other isolation method known in the art and combining these.
HYDROGENATION AND OTHER CHEMICAL TRANSFORMATIONS [00282] The processes described here may include hydrogenation. For example, glucose and xylose can be hydrogenated to sorbitol and xylitol, respectively. Esters, for example, produced as described herein, can also be hydrogenated. Hydrogenation can be achieved by using a catalyst (for example, Pt / gamma-Al2O3, Ru / C, Raney Nickel, copper chromite and other catalysts known in the art) in
105/118 combination with H ₂ under high pressure (for example, 10 to 12000 psi). Other types of chemical transformation of the products of the processes described here can be used, for example: production of products derived from organic sugar (for example, furfural and products derived from furfural). The chemical transformations of sugar products are described in International Application No. PCT / US201 / 049562, deposited on July 3, 2013, the publication of which is incorporated herein by reference in its entirety.
FERMENTATION [00283] Yeast and bacteria Zymomonas, for example, can be used for the fermentation or conversion of sugar (s) to alcohol (s). Other microorganisms are discussed below. The optimum pH for fermentation is approximately 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. Typical fermentation times are approximately 24 to 168 hours (for example, 24 to 96 hours) with temperatures in the range of 20 ° C to 40 ° C (for example, 26 ° C to 40 ° C), but thermophilic microorganisms prefer higher temperatures.
[00284] In some embodiments, for example, when anaerobic organisms are used, at least a portion 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 of these. In addition, the mixture may have a constant removal of an inert gas that flows 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.
[00285] In some embodiments, all or a portion of the fermentation process can be stopped before the low molecular weight sugar is completely converted to a product (for example, ethanol). Intermediate fermentation products include sugar and carbohydrates in high concentrations. Sugars and carbohydrates
106/118 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. In addition 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.
[00286] Nutrients for microorganisms can be added during saccharification and / or fermentation, for example, the food-based nutrient packages described in US Patent Application Publication 2012/0052536, filed on July 15, 2011, whose full publication is hereby incorporated by reference.
[00287] "Fermentation" includes the methods and products that are disclosed in International Application No. PCT / US2012 / 071093 filed on December 20, 2012 and in International Application No. PCT / US2012 / 071097 filed on December 12, 2012 , the contents of both being incorporated here by reference in their entirety.
[00288] 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 patent issued No. 8,318,453, the contents of which are incorporated herein in their entirety. Similarly, the saccharification equipment can be mobile. In addition, saccharification and / or fermentation can be performed in part or entirely during transit.
FERMENTATION AGENTS [00289] The microorganism (s) used in the fermentation can be microorganism (s) found in nature and / or projected microorganism (s). For example, the microorganism can be a bacterium
107/118 (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.
[00290] The appropriate fermenting microorganisms have the ability to convert carbohydrates, such as glucose, fructore, xylose, arabinose, mannose, galactore, oligosaccharides or polysaccharides into fermentation products. Fermentation microorganisms include variants 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, GP, 1996, Cellulose bioconversion technology, in Handbook on Bioethanol: Production and Utilization, Wyman, CE, ed., Taylor & Francis, Washington, DC, 179-212. Other suitable microorganisms include, for example, Zymomonas, 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), Monil iella 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,
108/118 and fungi of the dematioid genus Torula (for example, T. corallina).
[00291] Many of these microbial variants are available to the public commercially or through depositaries such as the ATCC (American Type Culture Collection, Manassas, Virginia, USA), the NRRL (Agricultural Research Service Culture Collection, Peoria, Illinois, USA) or DSMZDeutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Braunschweig, Germany), to name a few.
[00292] Commercially available yeasts include, for example, Red Star® / Lesaffre Ethanol Red (available from Red Star / Lesaffre, USA), FALI® (available from Fleischmann's Yeast, a division of Burns Philip Food Inc., USA), SUPERSTART® (available from Alltech, now Lallemand), GERT STRAND ^® (available from Gert Strand AB, Sweden) and Fermol ^® (available from DSM Specialties).
DISTILLATION [00293] After fermentation, the resulting fluids can be distilled using, for example, a beer column to separate ethanol and other alcohols from most water and residual solids. The steam coming out of the beer column can be, for example, 35% by weight of ethanol and can be fed into a grinding column. A mixture of practically azeotropic ethanol (92.5%) and water from a rectification column can be purified to pure ethanol (99.5%) using molecular sieves in a vapor phase. The bottoms 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 a second and third evaporator effect. Most of the condensate from the evaporator can be returned to the process as a reasonably clean condensate with a small
109/118 separate portion for the treatment of waste water to prevent the development of low boiling compounds.
HYDROCARBON CONTAINING MATERIALS [00294] In other embodiments using the methods and systems described here, materials containing hydrocarbons can be processed. The entire process described here can be used to treat any hydrocarbon-containing material described here. “Hydrocarbon-containing materials as used here refers to the inclusion of petroleum sands, shale oil, asphalt sands, coal slurry, bitumen, various types of coal and other materials present in nature or synthetics that include hydrocarbon components and solid matter. The solid matter may include stone, sand, clay, stone, mud, drilling mud and other solid organic and / or inorganic materials. The term may also include waste products such as drilling waste and by-products, refining waste and by-products and other waste products containing hydrocarbon components, such as asphalt waste and coating, asphalt pavement, etc.
TRANSPORT SYSTEMS [00295] 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 complete publication of which is incorporated herein by reference.
OTHER MODALITIES
110/118 [00296] Any material, process or processed materials described here can be used to make products and / or intermediates such as compositions, fillers, binders, plastic additives, absorbents and controlled release agents. Methods can include densification, for example, by applying pressure and heat to materials. For example, compositions can be made by combining fibrous materials with a 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. Such materials can be useful, for example, as building materials, protective foils, 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. Absorbents can be used, for example, as a bed for pets, packaging material or in pollution control systems. The controlled release dies also also take the form of, for example, pellets, chips, fibers and / or blades. Controlled release matrices can be used, for example, to release drugs, biocides, fragrances. For example, compositions, absorbents and release control agents and their uses are described in International Application No. PCT / US2006 / 010648, filed on March 23, 2006 and in patent No. 8,074,910, filed on November 22 2011, whose full disclosures are hereby incorporated by reference.
[00297] In some cases, the biomass material is treated at 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 can
111/118 include the application of 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 be 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 into the solution, can be separated from the solids and optionally the solids can be bathed with a solvent / solution (for example, with water and / or acidified water). Optionally, solids can be dried, for example, in air and / or under vacuum, optionally with heating (for example, below approximately 150 ° C, below approximately 120 ° C) to a water content below approximately 25 pesos% (below approximately 20 pesos%, below approximately 15 pesos% (below approximately 10 pesos%, below approximately 5 pesos%). 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 approximately 5 Mrad, less than approximately 1 Mrad or simply null) and then treated with an enzyme (eg, cellulase) to release glucose. The glucose (eg, glucose in solution) can be separated from the remaining solids.
112/118 receive additional processing, for example, being used to make energy or other products (for example, products derived from lignin).
EXAMPLES
L- Production of lactic acid from saccharified corncob in Lactobacillus species.
Materials and methods
Variants of producer lactic acid tested:
The variants of producer lactic acid that were tested are listed in table 2
Table 2: Variants of lactic acid tested:
NRRL B-441 Lactobacillus casei NRRL B-445 Lactobacillus rhamnosus NRRL B-763 Lactobacillus delbrueckii subspeciesdelbrueckii ATCC 8014 Lactobacillus plantarum ATCC 9649 Lactobacillus delbrueckii subspeciesdelbrueckii B-4525 Lactobacillus delbrueckii subspecies lactis B-4390 Lactobacillus coryniformis subspecies torquens B-227 Lactobacillus pentosus B-4527 Lactobacillus brevis ATCC 25745 Pediococcus pentosaceus NRRL 395 Rhizopus oryzae CBS 112.07 Rhizopus oryzae CBS 127.08 Rhizopus oryzae CBS 396.95 Rhizopus oryzae
Cultivation of Seed [00298] Cells from a bank of frozen cement (-80 ° C) were grown in a propagation medium (BD DIFCO ™ Lactobacilli MRS Broth) 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.
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Main Cultivation Media [00299] All media included saccharified corncob 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.
[00300] Experiments were conducted with several components of additional media using lactobacillus casei NRRL B-44 as the lactic acid producing organism. A 1.2L bioreactor with 0.7 L of culture volume was used. 1% of a seed with 20 hours of cultivation 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.
[00301] The experiences are summarized in table 3. The components of the means; the initial glucose concentration, nitrogen sources, yeast extract concentration, calcium carbonate, metals and inoculum size, were tested for a lactic acid yeast or for the lactic acid production rate. 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 scales for the production of some lactic acids and the scales are shown in table 3.
Table 3 - Production of L-lactic acid in a bioreactor with B-441
Media components Test Parameters Tested scale Scale ^to Optional Range ^b Initial glucose concentration Lactic acid concentration 33-85 g / l 33-75 g / L 33 - 52 g / L Tested Nitrogen Sources Lactic acid concentration Yeast extract, malt extract, Yeast extract, tryptone, peptone Yeast extract
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millet,tryptone,peptone Yeast Extract ^c Lactic acid concentration 0-10 g / L 2.5-10 g / L 2.5 g / L Calcium carbonate Lactic acid concentration 0-7 weight% / vol.% 3 - 7% weight% / vol.% 5 pesos% / vol.% Metal Solutions Lactic acid concentration With or without metals With or without metals Without metals Minor components: sodium acetate Lactic acid concentration With or without componentsminors With or withoutcomponentsminors Withoutcomponentsminors Polysorbate ™ 80 ^d , Dipotassium hydrogen phosphate, Triamonium citrate Inoculum Size Production rate of lactic acid 0.1-5 vol. % 1 - 5 vol. % 1 vol. % Conditionphysics Test Parameter Tested scale Scale- Scale Temperature Lactic acid concentration 27-47 ° C 27-42 ° C 33-37 ° C Agitation (in the 1.2L reactor) Lactic acid concentration 50-400 rpm 50-400 rpm 100-300 rpm Autoclave Time Lactic acid concentration 25min-145min 25min-145min 25 min Heating(withoutautoclave) Lactic acid concentration 50-70 ° C 50-70 ° C 50 - 70 ° C
^a 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 approximately 90% and 100%, between approximately 95% and 100%) ^c A yeast extract from the brand Fluka was used.
115/118 ^d Polysorbate ™ 80 is a nonionic surfactant from ICI Americas, Inc.
Results with Optional Media and Optional Physical Conditions [00302] 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 20L bioreactor was loaded with 10 L of media. 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 cultivation of 20 hours. The 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% (weight% / vol.%) Throughout the fermentation. The temperature was maintained at approximately 37 ° C. Antifoam 204 was also added (0.1vol.%) At the beginning of the fermentation. Several varieties of Lactobacillus casei were tested (NRRL B-441, NRRL B-445, NRRL B-763 and ATCC 8014).
[00303] A portion of sugar consumption and lactic acid production for the NRRL B-441 variety is displayed in 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 (total 42 g / L) were almost equivalent to the lactic acid produced.
Similar data on fermentation results using the NRRL B-441 variant in the 20L 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.
[00305] The analysis of the enantiomer is summarized for all
116/118 variants 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 the D-lactic acid. L. plantarum (ATCC 8014) showed an approximate equal mixture of each enantiomer.
Table 4: Relationship of L and D-lactic acid to Various Organisms
Fermenters
Variant 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
Polymerization of lactic acid [00306] A 250ml 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 pesos. % of the Lactic acid was dehydrated at 150 ^o 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 liquid of oligo (L-lactic acid) was formed quantitatively.
[00307] 400mg (0.4 weight%) of tin (II) chloride dihydrate and para-toluene sulfonic acid were added to the mixture and subsequently heated to 180 ^o C for 5 hours at 8mmHg. 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 another 19 hours.
[00308] 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 portion of the GPC data for samples A, B and C.
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Sample: Time toreaction (hours) Molecular weight Time toRetention THE 2 8000 18.3 B 5 12000 19.3 Ç 24 35000 20.3
[00309] In addition to the examples present here, or unless the contrary is expressly specified, all numerical scales, quantities, values and percentages, such as the quantities of the 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 may be read as if 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 light of the number of significant digits reported and by the application of conventional rounded techniques.
[00310] Although the numerical scales 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 numerical scales are determined here, these scales include the final indicator of the enumerated scale (that is, final indicators can be used). When the
118/118 percentages by weight are used here, the reported numerical values are relative to the total weight.
[00311] Furthermore, it should be understood that it is intended that the entire numerical scale reported here includes 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 .
[00312] Any patent, publication or other publication material, in whole or in part, is referred to as incorporated here by reference only so that the incorporated material does not conflict with existing definitions and claims or other publication 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 referred to as incorporated herein by reference, but that conflicts with existing definitions and statements or with other publication material made available here will be incorporated only to the extent that there is no conflict between the incorporated material and the existing publication material.
[00313] When this invention is shown specifically and described with reference to the preferred modalities thereof, it will be understood by those skilled in the art that various changes can be made in form and details without departing from the scope of the present invention covered by the appended claims.
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权利要求:
Claims (13)
[1]
1. Method for processing biomass, characterized by the fact that it comprises:
treating a cellulosic or lignocellulosic material with an electron beam to provide a reduced recalcitrance lignocellulosic or cellulosic material;
treating a reduced recalcitrance lignocellulosic or cellulosic material with one or more enzymes to obtain a sugar solution comprising xylose and glucose;
the fermentation of the sugar solution with a thermophilic organism that selectively ferments glucose to lactic acid, while xylose is not significantly consumed; and converting lactic acid to a product, where the product is an ester or polymer.
[2]
2. Method according to claim 1, characterized in that the conversion comprises the conversion of a lactic acid to esters, in which, optionally, the conversion comprises the chemical conversion of lactic acid to esters when treating with an alcohol and an acid catalyst.
[3]
Method according to claim 1, characterized in that the conversion comprises the polymerization of lactic acid to a polymer.
[4]
4. Method according to claim 3, characterized by the fact that the polymerization of lactic acid to a polymer comprises a polymerization method selected from the group consisting of direct condensation of lactic acid, azeotropic dehydration condensation of lactic acid, and dimerization of lactic acid to lactide followed by a ring-opening polymerization of the lactide, where, optionally, the polymerization method is direct condensation and includes the use of coupling agents and / or chain extenders to increase the molecular weight of the
Petition 870180063283, of 07/23/2018, p. 12/19
2/6 polymer, and in which, optionally, coupling agents and / or chain extenders are selected from a group consisting of triphosgene, carbonyl diimidazole, dicyclohexylcarbodiimide, diisocyanate, acid chlorides, acid anhydrides, epoxides, thyrane, oxazoline, and orthoester, or mixtures thereof.
[5]
5. Method according to claim 4, characterized by the fact that the polymerization method is azeotropic condensation.
[6]
6. Method according to either of claims 3 or 4, characterized in that it further comprises the use of catalysts and / or promoters, which are selected from the group consisting of Lewis acids, Bronsted acids, H3PO4 , H2SO4, methanesulfonic acid, p-toluenesulfonic acid, polymerically supported sulfonic acids, metals, Mg, Al, Ti, Zn, Sn, metal oxides, TiO2, ZnO, GeO2, ZrO2, SnO, SnO2, Sb2O3, metal halides, ZnCl2, SnCl2, SnCl4, Mn (AcO) 2, Fe2 (LA) 3, Co (AcO) 2, Ni (AcO) 2, Cu (OA) 2, Zn (LA) 2, Y (OA) 3, Al (i- PrO) 3, Ti (BuO) 4, TiO (acac) 2, (Bu) 2SnO, Sn (octoate) 2, and solvates of any of these, or mixtures thereof.
[7]
Method according to either of claims 5 or 6, characterized in that it additionally comprises conducting at least a part of the polymerization at a temperature between 100 and 200 ° C, such as between 110 ° C and 170 ° C or between 120 and 160 ° C, and / or where at least part of the polymerization is carried out in a vacuum (for example, between 0.1 mmHg to 300 mmHg).
[8]
8. Method according to claim 4, characterized by the fact that the polymerization method includes the lactic acid dimerization to lactide followed by a lactide ring polymerization, where, optionally, the dimerization includes heating the lactic acid between 100 and 200 ° C in a vacuum of 0.1 to 100 mmHg, and / or where the dimerization includes a catalyst selected from the group consisting of Sn octoate, Li carbonate, Zn dehydrate diacetate, tetraisopropoxide You,
Petition 870180063283, of 07/23/2018, p. 13/19
3/6 potassium carbonate, tin powder and mixtures thereof, and / or in which a ring opening polymerization catalyst is used, which is selected from the group of Bronsted acids, HBr, HCl, triflic acid, Lewis, ZnCl2, AlCh, anions, potassium benzoate, potassium phenoxide, potassium t-butoxide and zinc stearate, metals, tin, zinc, aluminum, antimony, bismuth, lanthanide and other heavy metals, tin (II) oxide and tin (II) octoate, tetrafenyl tin, tin (II) and (IV) halides, tin (II) acetylacetonoate, distanoxanes, Al (OiPr) 3, other functionalized aluminum alkoxides, ethyl zinc, lead oxide ( II), antimony octoate, bismuth octoate, rare earth catalysts, yttrium tris (methyl-lactate), yttrium tris (2-NN-dimethylamino ethoxide), tris (2-NN-dimethylamino ethoxide), yttrium tris (trimethylsilylmethyl), lanthanum tris (2,2,6,6-tetramethyl-heptanedionate), tris (acetylacetone to) lanthanum, yttrium octoate, yttrium tris (acetylacetonate), and yttrium tris (2,2,6,6-tetramethylheptanedionate), or mixtures thereof.
[9]
Method according to any one of claims 3 to 8, characterized in that the conversion additionally includes mixing the polymer with a second polymer in which, optionally, the second polymer is selected from the group consisting of polyglycols , polyvinyl acetate, polyolefins, styrenic resins, polyacetals, poly (meth) acrylates, polycarbonate, polybutylene succinate, elastomers, polyurethanes, natural rubber, polybutadiene, neoprene, silicone and combinations thereof; and / or in which a comonomer is copolymerized with lactic acid, in which, optionally, the comonomer is selected from the group consisting of elastomeric units, lactones, glycolic acid, carbonates, morpholiniones, epoxides, 1,4-benzodioxepine glycosalicilide- 2,5- (3H) dione, 1,4-benzodioxepine-2,5- (3H, 3-methyl) -dione lactosalicilide, dibenzo-1,5dioxacin-6-12-dione disalicilide, morpholine-2,5 -dione, 1,4-dioxane-2,5-dione glycolide, oxepane-2-one ε-caprolactone, 1,3-dioxane-2-one trimethylene carconate, 2,2Petition carbonate 870180063283, 23 / 07/2018, p. 14/19
4/6 dimethyltrimethylene, 1,5-dioxepano-2-one, 1,4-dioxane-2-one p-dioxanone, gamma-butyrolactone, beta-butyrolactone, beta-me-delta-valerolactone, ethylene oxalate 1, 4-dioxane-2,3-dione, 3- [benzyloxycarbonyl methyl] -1,4-dioxane-2,5dione, ethylene oxide, propylene oxide, 5.5 '(oxepane-2-one), Spiro carbonate -bid-dimethylene, and 2,4,7,9-tetraoxa-spiro [5.5] undecane-3,8-dione, or mixtures thereof; and / or additionally comprises the combination of polymer with fillers, where, optionally, the fill is selected from the group consisting of organically modified silicates, layered silicates, polymers and layered silicates, synthetic mica, carbon, carbon fibers, glass fibers, boric acid, talc, montmorillonite, clay, starch, corn starch, wheat starch, cellulose fibers, paper, regenerated cellulose fibers, non-woven fibers, wood flour, potassium titanate yarn, yarn aluminum borate, 4,4'-thiodiphenol, glycerol and mixtures thereof, and / or wherein the combination additionally includes extrusion and / or compression molding; and / or additionally comprises the branching or crosslinking of the polymer, where, optionally, a crosslinking agent is used to crosslink the polymer and the crosslinking agent is selected from the group consisting of 5,5'-bis (oxepano-2- ona) (bis-and-caprolactone), spiro-bis-dimethylene carbonate, peroxides, dicumyl peroxide, benzoyl peroxide, unsaturated alcohols, hydroxyethyl methacrylate, 2butene-1,4-diol, unsaturated anhydrides, maleic anhydride, epoxides saturated, and glycidyl methacrylate, or combinations thereof; and / or further comprises processing the polymer by a method selected from injection molding, blow molding and thermoforming; and / or further comprises combining the polymer with a dye or pigment; and / or where the conversion additionally includes mixing the polymer with a plasticizer, where, optionally, the plasticizer is selected from the
Petition 870180063283, of 07/23/2018, p. 15/19
5/6 group consisting of triacetin, tributyl citrate, polyethylene glycol, acetic acid ester of a monoglyceride, and bishhydroxymethyl diethyl malonate, or mixtures thereof; and / or additionally comprises grafting a molecule to the polymer, where, optionally, the molecule is selected from a monomer or polymer, and / or additionally includes treating the polymer with a peroxide, heating above 120 ° C, and irradiation, or combinations thereof; and / or additionally comprises the modeling, molding, carving, extrusion and / or assembly of the polymer in the product; and / or in which the product is selected from the group consisting of toiletries, handkerchiefs, towels, diapers, ecological packaging, compostable pots, consumer electronics, laptop cases, cell phone cases, appliances, food packaging, disposable packaging, food containers, beverage bottles, garbage bags, compostable waste bags, plant cover films, controlled release matrices, controlled release containers, fertilizer containers, pesticide containers, herbicide containers, nutrient containers , containers for pharmaceutical products, containers for flavoring agents, food containers, shopping bags, general purpose films, high heat film, heat sealing layer, surface coatings, disposable tableware, plates, cup, forks, knives, spoons, plastic cutlery, bowls, car parts, panels, fabrics, covers for the hood, carpet fibers, clothing fibers, clothing fibers, sports clothing fibers, shoe fibers, surgical sutures, implants, frames and drug delivery systems.
[10]
10. Method, according to claim 1, characterized by the fact that, after irradiation, prior to saccharification, the reduced recalcitrance lignocellulosic material is heat treated at a temperature of 95 to
160 ° C; or
Petition 870180063283, of 07/23/2018, p. 16/19
6/6 where, optionally, the electron beam has a total beam power of 100 to 1500 kW and where, optionally, after irradiation and before saccharification, the reduced-strength lignocellulosic material is treated with heat at a temperature of 95 ° C to 160 ° C.
[11]
11. Method according to claim 10, characterized by the fact that lactic acid is selected from the group of D-lactic acid and L-lactic acid.
[12]
12. Method, according to claim 1, characterized by the fact that the fermentation step occurs at a temperature above 50 ° C.
[13]
13. Method according to claim 1, characterized in that it additionally comprises isolating lactic acid from xylose.
Petition 870180063283, of 07/23/2018, p. 17/19
1/10

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法律状态:
2017-09-19| B27A| Filing of a green patent (patente verde)|

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2017-10-03| B27B| Request for a green patent granted|

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2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-04-24| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2018-08-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2018-11-13| 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. |

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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US61/816,664|2013-04-26|

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PCT/US2014/035467|WO2014176508A2|2013-04-26|2014-04-25|Processing biomass to obtain hydroxylcarboxylic acids|

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