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    • 专利摘要:
    process to produce pulp from biomass. greenbox+ technology is suitable for extracting sugars from hemicellulose before the production of biomass pulp into pulp products. the revenue obtainable from the sugar stream can significantly improve the economics of a pulp and paper mill. an initial extraction and recovery of sugars is followed by the production of a pulp product with better or similar properties. other co-products such as acetates and furfural are also possible. some variations provide a process for co-producing hemicellulose pulp and sugars from biomass which comprises: digesting the biomass in the presence of water vapor and/or hot water to extract hemicellulose in a liquid phase; washing the extracted solids, thereby generating a liquid washing filtrate and washed solids; separating the liquid wash filtrate from the washed solids; refine the washed solids to a refining ph of about 4 or more, thereby generating pulp; and hydrolyzing hemicellulose to generate fermentable hemicellulose sugars.
    公开号:BR112015007539B1
    申请号:R112015007539-8
    申请日:2013-10-03
    公开日:2021-07-20
    发明作者:Theodora Retsina；Vesa Pylkkanen；Steven Rutherford
    申请人:GranBio Intellectual Property Holdings, LLC；
    IPC主号:
    专利说明:

    PRIORITY DATA
    [001] This international patent application claims priority to each of the following patent applications: U.S. Patent Application No. 14/044,784, filed October 2, 2013; U.S. Patent Application 14/044,790, filed October 2, 2013; U.S. Provisional Patent Application 61/709,960, filed October 4, 2012; U.S. Provisional Patent Application 61/781,635, filed March 14, 2013; and U.S. Provisional Patent Application 61/842,356, filed July 2, 2013. Each such patent application is incorporated herein by reference herein. FIELD
    [002] The present invention relates, in general, to improved processes to produce cellulose pulp by recovering fermentable sugars from lignocellulosic biomass. BACKGROUND
    [003] In recent years, GreenPower+ technology has been developed by American Process, Inc. (API). GREEN POWER+ is a registered trademark of API, US Registration No. 4062241. GreenPower+ technology is a patent technology for the production of low-cost sugars from hemicelluloses from any type of biomass, including broadleaf trees, softwood trees and waste agricultural. The Green Power+ process produces low-cost C5 and C6 sugars from hemicelluloses from biomass feedstocks. These sugars are co-produced together with the power of biomass, pellets or pulp. Essentially, sugars are extracted from solids which are then used for existing applications, in synergy with pulp mills, pellet mills, renewable biomass-based power plants and many other existing sites. Value is added by minimizing capital costs for commercial deployment, which can be upgrades, capacity additions, or green sites. When applied to a pulp production operation, GreenPower+ technology is also known as GreenBox+™ Technology. GREENBOX+ is a mark of API, serial number U.S. 86000173.
    [004] It would be desirable to retrofit the existing pulp mill with a GreenBox+ process. The revenue obtainable from the sugar chain can significantly improve the economy of a pulp and paper mill. Ideally, an initial extraction and recovery of sugars is followed by a pulping process that produces a pulp product with equivalent or similar properties, or potentially even better properties for certain downstream products. In addition to sugars, other co-products become possible, in particular acetates since hemicellulose has a high concentration of acetyl groups which are released as acetic acid during sugar extraction.
    [005] In addition to the potential for more revenue, there is also the potential for reduced costs. For example, if the GreenBox+ process can replace a chemical pulp production method, the chemical recovery cycle can be eliminated. There can also be environmental compliance benefits and reduced compliance costs.
    [006] To date, there has been limited commercial success in extracting hemicellulose prior to pulp production. Further improvements are needed to establish an economic process. SUMMARY
    [007] Some variations provide a process to co-produce hemicellulose pulp and sugars from biomass, the process comprising: (a) providing lignocellulosic biomass comprising cellulose, hemicellulose and lignin; (b) digest the biomass in the presence of water vapor and/or hot water to extract at least a portion of the hemicellulose in a liquid phase, thereby generating extracted solids; (c) optionally separating at least some of the liquid phase from the extracted solids; (d) washing the extracted solids with water at a wash pH of about 7 or less, thereby generating a liquid wash filtrate and washed solids; (e) separating at least some of the liquid wash filtrate from the washed solids; (f) refining the washed solids to a refining pH of about 4 or more, thereby generating pulp; and (g) hydrolyzing the hemicellulose contained in the liquid phase and/or the liquid wash filtrate, in the presence of a hydrolysis catalyst, to generate hemicellulose sugars.
    [008] In some embodiments, step (b) is conducted at a digester temperature selected from about 140 °C to about 220 °C, such as from about 170 °C to about 190 °C. In some embodiments, step (b) is conducted at a digester residence time selected from about 1 minute to about 60 minutes, such as from about 2 minutes to about 10 minutes.
    [009] In some embodiments, step (b) is conducted at a digester pH of from about 2 to about 6, such as from about 3 to about 5. In various embodiments, the refining pH is selected at from about 5 to about 9, such as about 6 to about 8, or about 6.5 to about 7.5. The refining pH will generally be higher than the digester pH, following pH adjustment with a suitable base. It is possible, however, that the digester pH is higher than the refining pH, or that the digester pH and refining pH are similar.
    [010] In certain embodiments, step (b) comprises introducing a sulfur-containing compound selected from the group consisting of sulfur dioxide, sulfuric acid, sulfuric acid, lignosulfonic acid and combinations or derivatives thereof.
    [011] The pulp yield in biomass can range from about 75% to about 95% (or more) by weight. In some embodiments, the pulp yield in biomass is at least 85% or at least 90% by weight. In certain embodiments that achieve only mild extraction of hemicelluloses, the pulp yield in biomass is greater than 95%, such as about 96%, 97%, 98%, or 99% by weight.
    [012] In some modalities, the washing in step (d) uses fresh water. In these or other embodiments, the washing in step (d) can use recycled water, which is preferably alkali-free recycled water to reduce or prevent alkaline degradation of sugars.
    [013] In some embodiments, steps (b) and (d) are performed in a single unit. For example, a continuous countercurrent unit can be configured for both digestion and washing of solids.
    [014] When step (c) is carried out, the liquid phase and the liquid washing filtrate can be separately processed. Alternatively, the liquid phase and liquid wash filtrate can be combined for hydrolysis in step (g). When step (c) is not performed, the liquid phase (from digestion) forms part of the liquid wash filtrate, which also includes washing water.
    [015] In some embodiments, the hydrolysis catalyst comprises one or more compounds selected from the group consisting of sulfur dioxide, sulfuric acid, sulfuric acid, lignosulfonic acid and combinations or derivatives thereof. In other embodiments, the hydrolysis catalyst comprises hemicellulase enzymes.
    [016] Some variations of the invention provide a process to co-produce hemicellulose pulp and sugars from biomass, the process comprising: (a) providing lignocellulosic biomass comprising cellulose, hemicellulose and lignin; (b) digest the biomass in the presence of water vapor and/or hot water to extract at least a portion of the hemicellulose in a liquid phase, thereby generating extracted solids; (c) optionally separating at least some part of the liquid phase from the extracted solids; (d) washing the extracted solids with water at a wash pH selected from about 7 or less, thereby generating a liquid wash filtrate and washed solids; (e) separating at least some of the liquid wash filtrate from the washed solids; (f) further digesting extracted solids and/or washed solids using a chemical pulp production method, thereby generating digested solids; (g) refining the digested solids to a refining pH selected from about 4 or more, thereby generating pulp; and (h) hydrolyzing the hemicellulose contained in the liquid phase and/or the liquid wash filtrate, in the presence of a hydrolysis catalyst, to generate hemicellulose sugars.
    [017] In some modalities, the chemical method of pulp production is selected from the group consisting of Kraft pulp production, sulfite pulp production, soda pulp production and organ-solvent pulp production. In certain embodiments, soda pulp production is employed to further digest extracted solids, washed solids, or both.
    [018] Some variations of the invention provide a process to co-produce hemicellulose pulp and sugars from biomass, the process comprising: (a) providing lignocellulosic biomass comprising cellulose, hemicellulose and lignin; (b) digest the biomass in the presence of water vapor and/or hot water to extract at least a portion of the hemicellulose in a liquid phase, thereby generating extracted solids; (c) optionally separating at least some part of the liquid phase from the extracted solids; (d) washing the extracted solids with water at a wash pH selected from about 7 or less, thereby generating a liquid wash filtrate and washed solids; (e) separating at least some of the liquid wash filtrate from the washed solids; (f) refining the washed solids to a refining pH selected from about 4 or more, thereby generating pulp; (g) further digesting the pulp using a chemical pulp production method; and (h) hydrolyzing the hemicellulose contained in the liquid phase and/or the liquid wash filtrate, in the presence of a hydrolysis catalyst, to generate hemicellulose sugars.
    [019] In some modalities, the chemical method of pulp production is selected from the group consisting of Kraft pulp production, sulfite pulp production, soda pulp production and organ-solvent pulp production. In certain embodiments, soda pulp production is employed to further digest the pulp.
    [020] In some variations, a process for producing pulp from biomass comprises: (a) providing lignocellulosic biomass comprising cellulose, hemicellulose and lignin; (b) digest the biomass in the presence of water vapor and/or hot water to extract at least a portion of the hemicellulose in a liquid phase, thereby generating extracted solids; (c) optionally separating at least some part of the liquid phase from the extracted solids; (d) washing the extracted solids with water at a wash pH of about 7 or less, thereby generating a liquid wash filtrate and washed solids; (e) separating at least some of the liquid wash filtrate from the washed solids; (f) refining the washed solids to a refining pH of about 4 or more, thereby generating pulp; and (g) recovering or further processing the pulp.
    [021] Pulp from any of the disclosed processes can be combined with a second source of cellulose fiber prior to downstream processing of the pulp. The second source of cellulose fiber can be selected from, but not limited to, OCC pulp, Kraft pulp, sulfite pulp, soda pulp, NSSC pulp and organ-solvent pulp.
    [022] Pulp from any of the disclosed processes can be characterized by a Concora test of about 25 lbf or more, such as about 32 lbf or more. The pulp from any of the disclosed processes can be characterized by a ring crush strength of about 111 N/0.15 m (25 lbf/6 in) or more, such as about 177 N/0.15 m ( 40 lbf/6 in) or more. The pulp from any of the disclosed processes can be characterized by a rupture length of about 2.0 km or more, such as about 3.6 km or more.
    [023] Optionally, at least a portion of the pulp can be hydrolyzed to generate glucose.
    [024] In some embodiments, the process further comprises recovering an acetate co-product (with the use of, for example, reverse osmosis), such as potassium acetate or sodium acetate.
    [025] Some variations provide a process to produce hemicellulose sugars from biomass, the process comprising: (a) providing lignocellulosic biomass comprising cellulose, hemicellulose and lignin; (b) digest the biomass in the presence of water vapor and/or hot water to extract at least a portion of the hemicellulose in a liquid phase, thereby generating extracted solids; (c) optionally separating at least some part of the liquid phase from the extracted solids; (d) washing the extracted solids with water at a wash pH of about 7 or less, thereby generating a liquid wash filtrate and washed solids; and (e) hydrolyzing the hemicellulose contained in the liquid phase and/or the liquid wash filtrate, in the presence of a hydrolysis catalyst, to generate hemicellulose sugars.
    [026] Preferably, the process (in any modality) includes mass and/or energy process integration that involves at least two steps of said process. In some embodiments, the process includes mass and/or energy process integration that involves at least three steps of said process. Several examples of process integration are revealed in the detailed description below.
    [027] For example, process integration may include recycling evaporator condensates that can be recycled for use in step (b); recycle evaporator condensate that can be recycled for use in one or more wash steps; integration with downstream operations involving the pulp, during or after step (g); concentrating fermentable sugars, recovering a stream of condensate therefrom, and introducing the stream of condensate elsewhere with a water requirement; sterilizing a fermenter or fermenter feed stream with a stripping of steam from the one or more evaporators; and/or concentrating a fermentation product in a non-externally heated effect of a multi-effect evaporation unit.
    [028] The invention provides pulp intermediates or products produced by processes as described. The invention also provides consumer products (e.g. paper or corrugated medium) produced from the intermediate or pulp product. Intermediates or hemicellulose sugar products produced by the disclosed processes are also provided. Fermentation products can be produced from hemicellulose sugar intermediates or products. BRIEF DESCRIPTION OF THE FIGURES
    [029] Figure 1 is a flowchart of high-level blocks according to some embodiments of the invention.
    [030] Figure 2 is a simplified process flowchart for the production of pulp, hemicelluloses and acetates, in some modalities.
    [031] Figure 3 is a simplified process flowchart for the production of pulp, sugars and acetates, in some modalities.
    [032] Figure 4 is a simplified process flowchart for the production of pulp, acetates and furfural, in some modalities. DETAILED DESCRIPTION OF SOME MODALITIES
    [033] This description will allow a person skilled in the art to create and use the invention and it describes various modalities, adaptations, variations, alternatives and uses of the invention. These and other embodiments, features and advantages of the present invention will become more apparent to those skilled in the art when taken with reference to the following detailed description of the invention in conjunction with any accompanying drawings.
    [034] As used in this specification and the accompanying claims, the singular forms "a", "an", "the" and "a" include plural referents unless the context clearly indicates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All composition numerals and percentage-based ranges are percentages by weight, unless otherwise indicated. All ranges of numbers or conditions are intended to encompass any specific value contained within the range, rounded to any suitable decimal point.
    [035] Unless otherwise indicated, all numbers expressing reaction conditions, stoichiometries, concentrations of components and so on used in the specification and claims are to be understood to be modified in all cases by the term "about ". Consequently, unless otherwise indicated, the numerical parameters presented in the following descriptive report and attached claims are approximations that may vary depending on at least one specific analytical technique.
    [036] The term "comprise", which is synonymous with "include", "contain" or "characterized by", is inclusive or open-ended and does not exclude additional, unquoted elements or method steps. "Understanding" is an art term used in claim language which means that the so-called claim elements are essential, but other claim elements can be added and still form a construct within the scope of the claim.
    [037] As used herein, the term “consists of” excludes any element, step, or ingredient not specified in the claim. When the expression “consists of” (or variations thereof) appears in a clause of the body of a claim, instead of immediately following the preamble, it limits only the element presented in that clause; other elements are not excluded from the claim as a whole. As used herein, the term "consist essentially of" limits the scope of a claim to specified method elements or steps, plus those that do not materially affect the basis and the innovative feature(s) of the claimed matter.
    [038] With respect to the terms "comprise" "consist of" and "consist essentially of" where one of these three terms is used herein, the subject matter presently disclosed and claimed may include use of both the other two terms. Thus, in some modalities not otherwise explicitly cited, any case of "understanding" can be replaced by "consisting of" or, alternatively, by "consisting essentially of".
    [039] Some variations of the present invention are premised on the surprising finding that the extraction of water vapor or hot water from biomass is an effective pulp production step to produce a pulp product, such as a chemical pulp material or semichemical, by also producing a stream of hemicellulose sugar. Through experimentation, the inventors determined suitable conditions for hot water extraction as well as suitable downstream conditions and general process configurations to co-produce pulp and sugars.
    [040] The biomass feedstock can be selected from broadleaved trees, resinous trees, forest residues, industrial residues, consumer residues, or combinations thereof. Exemplary biomass feedstocks include maple, birch and aspen. Some modalities use agricultural residues, which include lignocellulosic biomass associated with food crops, annual grasses, energy crops, or other annually renewable raw materials. Exemplary agricultural wastes include, but are not limited to, corn husk, corn fiber, wheat straw, sugarcane bagasse, rice straw, oat straw, barley straw, miscanthus, energy cane, or combinations thereof .
    [041] Some variations provide a process to co-produce hemicellulosic pulp and sugars from biomass, the process comprising: (a) providing lignocellulosic biomass comprising cellulose, hemicellulose and lignin; (b) digest the biomass in the presence of water vapor and/or hot water to extract at least a portion of the hemicellulose in a liquid phase, thereby generating extracted solids; (c) optionally separating at least some part of the liquid phase from the extracted solids; (d) washing the extracted solids with water at a wash pH of about 7 or less, thereby generating a liquid wash filtrate and washed solids; (e) separating at least some of the liquid wash filtrate from the washed solids; (f) refining the washed solids to a refining pH of about 4 or more, thereby generating pulp; and (g) hydrolyzing the hemicellulose contained in the liquid phase and/or the liquid wash filtrate, in the presence of a hydrolysis catalyst, to generate hemicellulose sugars.
    [042] In some embodiments, step (b) is conducted at a digester temperature selected from about 140 °C to about 220 °C, such as from about 170 °C to about 190 °C. In some embodiments, step (b) is conducted at a digester residence time selected from about 1 minute to about 60 minutes, such as from about 2 minutes to about 10 minutes.
    [043] In some embodiments, step (b) is conducted at a digester pH of from about 2 to about 6, such as from about 3 to about 5. In various embodiments, the refining pH is selected at from about 5 to about 9, such as about 6 to about 8, or about 6.5 to about 7.5. The refining pH will generally be higher than the digester pH, following pH adjustment with a suitable base. It is possible, however, that the digester pH is higher than the refining pH, or that the digester pH and refining pH are similar.
    [044] In certain embodiments, step (b) comprises introducing a sulfur-containing compound selected from the group consisting of sulfur dioxide, sulfuric acid, sulfuric acid, lignosulfonic acid and combinations or derivatives thereof. In these embodiments, the digester pH can be less than 2, such as about 1.5, 1, 0.5, 0 or less.
    [045] The pulp yield in biomass can range from about 75% to about 95% (or more) by weight. Yield is the fraction of initial solids that remain after pulping and washing, on a dry basis. In some embodiments, the pulp yield in biomass is at least 85% or at least 90% by weight. In certain embodiments that aim at mild extraction of hemicelluloses, the pulp yield in biomass is greater than 95%, such as about 96%, 97%, 98% or 99% by weight. When the biomass yield is high, hemicelluloses in relatively low amounts are extracted. However, it may be advantageous to extract a small amount of hemicelluloses under mild conditions.
    [046] In some modalities, the washing in step (d) uses fresh water. In these or other embodiments, the washing in step (d) can use recycled water, which is preferably alkali-free recycled water to reduce or prevent alkaline degradation of sugars. "Alkali-free recycled water" means that no alkali metal, or a base, salt, or derivative thereof (eg, sodium hydroxide or potassium chloride) is introduced into the recycled water prior to use for washing. If desired, the pH of the wash water can be adjusted or maintained in the range of about 4 to 9, such as about 4.5, 5, 5.5, 6, 6.5, 6.6, 6, 7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 8, or 8.5. For example, a fresh water source at a pH of about 8 can be adjusted with an acid to a pH of about 6 for washing. Or a stream of recycled water at a pH of about 4 can be adjusted to a pH of about 7 for washing.
    [047] In some embodiments, steps (b) and (d) are performed in a single unit. For example, a continuous countercurrent unit can be configured for both digestion and washing of solids. Multiple units can be employed in parallel, where each unit is configured for both digestion and washing. Or, a first unit can be configured for digestion only, with a downstream unit configured for either digestion or washing. Or, a first unit can be configured for either digestion or washing, followed by a downstream wash-only unit. Many variations are possible.
    [048] When step (c) is performed, the liquid phase and the liquid washing filtrate can be separately processed. Alternatively, the liquid phase and liquid wash filtrate can be combined for hydrolysis in step (g). When step (c) is not carried out, the liquid phase (from digestion) forms part of the liquid wash filtrate. That is, the digester liquor is fed forward, without solid-liquid separation, for washing. Additional wash water is added depending on the desired wash amount and wash unit wash efficiency. The digester liquor therefore becomes combined (and diluted) with the added wash liquid.
    [049] Step (g) is desirable to increase the yield of fermentable sugars, hydrolyzing (with water) the soluble oligomers into monomers. In some embodiments, the hydrolysis catalyst comprises one or more compounds selected from the group consisting of sulfur dioxide, sulfuric acid, sulfuric acid, lignosulfonic acid, and combinations or derivatives thereof. In other embodiments, the hydrolysis catalyst comprises hemicellulase enzymes or other enzymes capable of catalyzing the hydrolysis of hemicellulose. In certain embodiments, step (g) is not performed and the hemicellulose oligomers (with some monomers typically present) recovered for sale or further processing.
    [050] Some variations of the invention provide a process to co-produce hemicellulose pulp and sugars from biomass, the process comprising: (a) providing lignocellulosic biomass comprising cellulose, hemicellulose and lignin; (b) digest the biomass in the presence of water vapor and/or hot water to extract at least a portion of the hemicellulose in a liquid phase, thereby generating extracted solids; (c) optionally separating at least some part of the liquid phase from the extracted solids; (d) washing the extracted solids with water at a wash pH selected from about 7 or less, thereby generating a liquid wash filtrate and washed solids; (e) separating at least some of the liquid wash filtrate from the washed solids; (f) further digesting extracted solids and/or washed solids using a chemical pulp production method, thereby generating digested solids; (g) refining the digested solids to a refining pH selected from about 4 or more, thereby generating pulp; and (h) hydrolyzing the hemicellulose contained in the liquid phase and/or the liquid wash filtrate, in the presence of a hydrolysis catalyst, to generate hemicellulose sugars. Some variations of the invention provide a
    [051] Some variations of the invention provide a process to co-produce hemicellulose pulp and sugars from biomass, the process comprising: (a) providing lignocellulosic biomass comprising cellulose, hemicellulose and lignin; (b) digest the biomass in the presence of water vapor and/or hot water to extract at least a portion of the hemicellulose in a liquid phase, thereby generating extracted solids; (c) optionally separating at least some part of the liquid phase from the extracted solids; (d) washing the extracted solids with water at a wash pH selected from about 7 or less, thereby generating a liquid wash filtrate and washed solids; (e) separating at least some of the liquid wash filtrate from the washed solids; (f) refining the washed solids to a refining pH selected from about 4 or more, thereby generating pulp; (g) further digesting the pulp using a chemical pulp production method; and (h) hydrolyzing the hemicellulose contained in the liquid phase and/or the liquid wash filtrate, in the presence of a hydrolysis catalyst, to generate hemicellulose sugars.
    [052] In some modalities, the chemical method of pulp production is selected from the group consisting of Kraft pulp production, sulfite pulp production, soda (sodium carbonate, Na2CO3) pulp production and pulp production with organsolvent. In certain embodiments, soda pulp production is employed to further digest extracted solids, washed solids, or both.
    [053] Pulp from any of the disclosed processes can be combined with a second source of cellulose fiber prior to downstream processing of the pulp. The second source of cellulose fiber can be selected, but without limitation, from OCC pulp, Kraft pulp, sulfite pulp, soda pulp, NSSC pulp, or organ-solvent pulp.
    [054] Pulp from any of the disclosed processes can be characterized by a Concora test of about 111 N (25 lbf) or more, such as about 115 N (26 lbf), 120 N (27 lbf), 124N (28lbf), 128 (29lbf), 133N (30lbf), 137N (31lbf), 142N (32lbf), 146N (33lbf), 151N (34lbf), 155N (35 lbf), 160 N (36 lbf), 164 N (37 lbf) or more. Pulp from any of the disclosed processes can be characterized by a ring crush strength of about 111 N/0.15 m (25 lbf/6 in) or more, such as about 177 N/0.15 m (40 lbf/6 in) or more. Pulp from any of the disclosed processes can be characterized by a break length of about 2.0 km or more, such as about 2.1, 2.2, 2.3, 2.4, 2, 5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6 km or more.
    [055] The invention provides pulp intermediates or products produced by processes as described. Using known techniques, consumer products (eg, paper or corrugated medium) can be produced from the pulp or product intermediate. See, for example, Twede and Selke, "Cartons, crates and corrugated board: a handbook of paper and wood packaging technology", DEStech Publications, pages 41-56, 2005; and Foster, "Boxes, Corrugated" in the Wiley Encyclopedia of Packaging Technology, 1997, eds. Brody A and Marsh K, 2nd edition.
    [056] Optionally, at least a portion of the pulp can be hydrolyzed to generate glucose. For example, pulp that has inferior properties (such as fiber length or strength) can be hydrolyzed to glucose using cellulase enzymes or an acid catalyst (eg, sulfuric acid). In some embodiments, the entire pulp product is hydrolyzed to glucose to maximize sugar production, either as a transient operation or as a steady state operation.
    [057] Hemicellulose sugars can be recovered in purified form, such as an aqueous sugar slurry or dry sugar solids, for example. Any known technique can be employed to recover an aqueous sugar slurry or to dry the solution to produce dry sugar solids. Thus, the invention provides hemicellulose sugar intermediates or products produced by the disclosed processes. In certain embodiments, the extracted hemicellulose stream is combusted for energy, or discarded.
    [058] Fermentation products can be produced from hemicellulose sugar intermediates or products. In some embodiments, hemicellulose sugars are fermented to ethanol, 1-butanol, isobutanol, acetic acid, lactic acid, succinic acid, or any other fermentation product. A purified product can be produced by distillation, which will also generate a distillation bottom stream that contains residual solids. A bottom evaporation stage can be used to produce residual solids. Residual solids (such as distillation bottoms) can be recovered, or burned to produce energy for the process.
    [059] In some embodiments, the process further comprises recovering an acetate co-product, such as potassium acetate or sodium acetate. The process can include hydrolyzate evaporation to remove some or most of the volatile acids. The evaporation step is preferably carried out below acetic acid dissociation pH 4.8, such as about 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, or 4.5. In certain embodiments, the process further comprises combining, at a pH of about 4.8 to 10 or more, a portion of the vaporized acetic acid with an alkali oxide, alkali hydroxide, alkali carbonate, and/or alkali bicarbonate, to that the alkali is selected from the group consisting of potassium, sodium, magnesium, calcium and combinations thereof, to convert the vaporized acetic acid portion to an alkaline acetate. Alkaline acetate can be recovered by reverse osmosis or other membrane separation or filtration (See, for example, U.S. Patent Document 8,211,680 which is incorporated by reference). If desired, purified acetic acid can be generated from alkaline acetate. Acetic acid and acetate salts have several known commercial uses.
    [060] Some modalities also recover a furfural co-product. When furfural is desired, the conditions of the initial extraction and/or hydrolysis of hemicellulose can be more stringent (compared to sugar production) so that C5 sugars are converted to furfural. Under hot and acidic conditions, xylose and other five-carbon sugars dehydrate, losing three water molecules to become furfural (C5H4O2). Hydrogenation of furfural provides furfuryl alcohol, which is a useful chemical intermediate and which can be further hydrogenated to furfuryl tetrahydroalcohol. Furfural is used to produce other furan chemicals, such as furoic acid, through oxidation and furan through decarbonylation.
    [061] In some embodiments, additional evaporation steps may be employed. These additional evaporation steps can be carried out under different conditions (eg temperature, pressure and pH) than the first evaporation step.
    [062] Some embodiments employ reaction conditions and operating sequences described in U.S. Patent Document 8,211,680, issued on July 3, 2012; and/or U.S. Patent Applications 13/471,662; 13/026,273; 13/026280; 13/500,917; 61/536,477; 61/612,451; 61/612,453; 61/624,880; 61/638,730; 61/641,435; 61/679,793; 61/696,360; 61/709,960. Each of these commonly owned patents and patent applications is hereby incorporated by reference into this document in its entirety. In some embodiments, the process is a variation of the GreenPower+ technology or GreenBox+ process that is commonly owned by the assignee of this patent application.
    [063] Effective "hot water extraction" (or "HWE") conditions may include contacting lignocellulosic biomass with water vapor (at various pressures in saturated, superheated or supersaturated form) and/or hot water. In some embodiments, the HWE step is performed using hot liquid water at a temperature of about 140 to 220 °C, such as about 150 °C, 160 °C, 170 °C, 175 °C, 180 ° C, 185 °C, 190 °C, 200 °C, or 210 °C. In some embodiments, the HWE step is performed using hot liquid water with a residence time of about 1 minute to about 60 minutes, such as about 2, 2.5, 3, 3.5, 4 , 5, 7.5, 10, 12.5, 15, 20, 25, 30, 35, 40, 45, 50 or 55 minutes.
    [064] Figure 1 is a flowchart of high-level blocks according to some modalities. Wood is fed to one or more digesters, which can be existing digesters in an upgrade of an existing pulp mill, for example. Existing washer(s) and evaporator(s) can also be used. In the modalities depicted in Figure 1, pulp is the primary product and acetate and furfural are co-products.
    [065] Figure 2 is a simplified process flowchart for the production of pulp, hemicelluloses and acetates, in some modalities. Figure 3 shows a simplified process flowchart for the production of pulp, sugars and acetates, in some modalities. Figure 4 shows a simplified process flowchart for the production of pulp, acetates and furfural, in some modalities. These Figures in no way limit the invention and are intended to be exemplary only. Additional unit operations can be included. For example, additional digesters for the production of HWE pulp can be employed anywhere in the processes pictured.
    [066] In some modalities, washing of HWE pulp is carried out using fresh water. In some embodiments, washing of HWE pulp is carried out using recycled water that does not contain significant amounts of alkali. The absence of significant amounts of alkaline components reduces or prevents caustic degradation of sugars.
    [067] The production of HWE pulp will typically produce liquid digested solids with a pH of about 3 to 5, such as about 3.5 to 4.5. In some embodiments, following the production of HWE pulp, the pH of the pulp is adjusted prior to refining the solids. In certain embodiments, the pH is adjusted to neutral or near neutral pH, such as a pH selected from about 5 to about 9, preferably about 6.5 to 7.5, more preferably about 6.8 to 7 ,two. The pH adjustment can be completed by any known means, such as (but not limited to) treatment with sodium hydroxide or ammonia.
    [068] In some embodiments, following the production of HWE pulp, an additional pulp production step is employed, such as soda pulp production (sodium carbonate). In some embodiments, the hydrolyzate (which contains hemicelluloses) from the HWE pulp production is separated from the solids before introducing soda to the solids. TABLE 1A

    TABLE 1B

    [069] Tables 1A and 1B summarize physical pulp properties measured from laboratory scale tests for a range of HWE pulp production conditions (hot water extraction). In these tables, LHW is "liquid hot water". Soda cooks were performed for comparison. The results in Table 1A were used to adjust and optimize conditions for the experiments in Table 1B. Note that in Table 1B, the refining pH is about 7 to 7.3, compared to a refining pH range of about 3.8 to 4.2 in the HWE experiments. TABLE 2

    [070] Table 2 summarizes the data collected in relation to the stream of hemicellulose extracted during the production of HWE pulp (hot water extraction).
    [071] The HWE pulp obtained can be combined with another source of biomass before downstream processing. For example, HWE pulp can be combined with recycled fiber (eg OCC or old corrugated container pulp) and then fed to a paper machine in some embodiments. Or, the HWE pulp can be combined with an NSSC pulp, soda pulp, sulfite pulp, Kraft pulp, or other pulp for further processing.
    [072] In some embodiments, the process further comprises removing a stream of vapor comprising water and vaporized acetic acid from the extract liquor in at least one evaporation stage at a pH of 4.8 or less, to produce an extract liquor concentrate comprising fermentable hemicellulose sugars. At least one evaporation stage is preferably operated at a pH of 3.0 or less.
    [073] The process may additionally comprise a step of fermentation of the fermentable hemicellulose sugars to a fermentation product. The fermentation product can be ethanol, 1-butanol, isobutanol, or any other product (fuel or chemical). An amount of the fermentation product can be cultured from a microorganism or enzymes, which can be recovered if desired.
    [074] In some embodiments, fermentable hemicellulose sugars are recovered from the solution, in purified form. In some embodiments, fermentable hemicellulose sugars are fermented to produce biochemical or biofuel agents such as (but not limited to) ethanol, 1-butanol, isobutanol, acetic acid, lactic acid, or any other fermentation products. A purified fermentation product can be produced by distilling the fermentation product, which will also generate a distillation bottoms stream that contains residual solids. A bottom evaporation stage can be used to produce residual solids.
    [075] Pentose sugars can react to produce furfural. Under hot and acidic conditions, xylose and other five-carbon sugars dehydrate, losing three water molecules to become furfural (C5H4O2). Furfural is an important non-petroleum based renewable chemical feedstock. Hydrogenation of furfural provides furfuryl alcohol, which is a useful chemical intermediate and which can be further hydrogenated to furfuryl tetrahydroalcohol. Furfural is used to produce other furan chemicals, such as furoic acid, through oxidation and furan through decarbonylation. Generally speaking, process conditions that can be adjusted to promote furfural include, in one or more reaction steps, temperature, pH or acid concentration, reaction time, catalysts or other additives (eg, FeSO4), flow patterns reactor and control of encounter between liquid and vapor phases.
    [076] In some embodiments, the process further comprises recovering lignin as a co-product, either in combination with a salt such as gypsum, or in substantially pure form.
    [077] Process integration can be performed for any of the disclosed processes or configurations. In some embodiments, process integration includes pinch analysis and energy optimization that involves one or more steps (including all steps) in the process.
    [078] For example, evaporator condensates can be recycled for use in one or more washing steps, and/or as part of the digester cooking liquor. In some embodiments, evaporator condensates can be recycled to a reverse osmosis unit configured to recover alkaline acetates. Process integration can also be conducted with downstream papermaking operations.
    [079] In some embodiments, process integration includes concentrating fermentable sugars, recovering a stream of condensate from them, and introducing the stream of condensate to another location with a water requirement, such as washing, filter regeneration, or fermentation . The other location can be upstream or downstream of the condensate stream or it can still be at a colocalized site.
    [080] In some embodiments, process integration includes sterilizing a fermenter or fermentor feed stream with a removal of steam from one or more evaporators used to concentrate the fermentable sugars and/or one or more evaporators used to concentrate the product from fermentation. In some embodiments, process integration includes pre-cooling a fermenter feed stream with a product stream that comprises the fermentation product.
    [081] In some embodiments, process integration includes concentrating the fermentation product in a non-externally heated effect of a multiple-effect evaporation unit, such as the last effect of the multiple-effect evaporation unit. In some embodiments, process integration includes the use of steam recompression and vacuum pumping to concentrate the fermentation product to minimize cooling water requirements.
    [082] In some embodiments, process integration includes concentrating one or more organic waste streams and combusting the one or more organic waste streams with lignin or other biomass-derived material.
    [083] In some embodiments, process integration includes using a rectifier reflux condenser to pre-evaporate stillage from a fermentation product distillation column. Process integration can also include preheating demineralized water or preheating turbine condenser condensate, for example.
    [084] When lignosulfonic acid is used, both to aid the initial extraction as for hydrolysis of hemicellulose oligomers to monomers, the lignosulfonic acid can be provided by another biorefining process. For example, the AVAP® process employs sulfur dioxide and a solvent for lignin to fractionate biomass, which produces lignosulphonic acids during digestion.
    [085] The present invention, in various embodiments, offers several benefits including, but not limited to, (i) increased pulp yield, (ii) recovery of hemicelluloses that can be converted into value-added products, (iii) removal of chemicals from process pulp production, (iv) elimination of chemically reclaimed plant operations, (v) reduction in the number of evaporation stages required, and (vi) reduced environmental footprint.
    [086] The present invention also provides systems configured to carry out the disclosed processes and compositions or products produced therefrom. Biorefineries can be configured to carry out the disclosed processes using known equipment. Biorefineries can be improvements to existing mills, or new sites.
    [087] Any stream generated by the disclosed processes can be partially or completely recovered, purified or further treated and/or marketed or sold.
    [088] In this detailed description, reference has been made to multiple embodiments of the invention and non-limiting examples relating to how the invention may be understood and practiced. Other modalities that do not provide all the features and advantages presented in this document can be used, without departing from the spirit and scope of the present invention. This invention incorporates routine experimentation and optimization of the methods and systems described herein. Such modifications and variations are considered to be within the scope of the invention defined by the claims.
    [089] All publications, patents, and patent applications cited in this specification are hereby incorporated by reference in their entirety as if each publication, patent, or patent application has been specifically and individually shown in this document.
    [090] Where the methods and steps described above indicate certain events that occur in a certain order, those of common skill in the art will recognize that the ordering of certain steps can be modified and that such modifications are in accordance with variations of the invention. Additionally, certain steps can be performed concurrently in a parallel process when possible, as well as performed sequentially.
    [091] Therefore, to the extent that there are variations of the invention that are within the spirit of the disclosure or equivalent to the inventions set forth in the appended claims, it is intended that this patent application will also cover those variations.
    权利要求:
    Claims (12)
    [0001]
    1. PROCESS FOR PRODUCING PULP FROM BIOMASS, characterized in that it comprises: (a) providing lignocellulosic biomass comprising cellulose, hemicellulose and lignin; (b) digesting said biomass in the presence of water vapor and/or hot water to extract at least a portion of said hemicellulose in a liquid phase, thereby generating extracted solids, where step (b) does not include a chemical pulping method; (c) separating at least some part of said liquid phase from said extracted solids; (d) washing said extracted solids with water at a wash pH of about 7 or less, thereby generating a liquid wash filtrate and washed solids; (e) separating at least some part of said liquid wash filtrate from said washed solids; (f) refining said washed solids to a refining pH of about 4 to 6.5, thereby generating pulp; and (g) recovering or further processing said pulp, wherein step (c) is carried out before step (d), where said liquid phase separated in step (c) and said liquid washing filtrate are separately processed and no longer combined later.
    [0002]
    2. Process according to claim 1, characterized in that step (b) is conducted at a digester temperature selected from 140°C to 220°C.
    [0003]
    3. Process according to claim 1, characterized in that step (b) is conducted in a residence time of the digester selected from 1 minute to 60 minutes.
    [0004]
    4. PROCESS according to claim 1, characterized in that step (b) is conducted at a digester pH of 2 to 6.
    [0005]
    Process according to claim 1, characterized in that the pulp yield in the biomass is from 75% to 95% by weight.
    [0006]
    Process according to claim 1, characterized in that said washing in step (d) uses fresh water.
    [0007]
    Process according to claim 1, characterized in that said washing in step (d) uses recycled water free of alkali.
    [0008]
    8. PROCESS according to claim 1, characterized in that steps (b) and (d) are performed in a single unit.
    [0009]
    Process according to claim 1, characterized in that said pulp has a Concora test of 111 N (25 lbf) or more.
    [0010]
    Process according to claim 1, characterized in that said pulp has a ring crush strength of about 111 N/0.15 m (25 lbf/6 in) or more.
    [0011]
    Process according to claim 1, characterized in that said pulp has a rupture length of about 2.0 km or more.
    [0012]
    Process according to claim 1, characterized in that, during step (g), at least a portion of said pulp is hydrolyzed to generate glucose.
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    EP2904144A4|2016-05-25|
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    US20160222586A1|2016-08-04|
    CA2887149C|2016-01-05|
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    US20140096923A1|2014-04-10|
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    US20140096922A1|2014-04-10|
    WO2014055726A1|2014-04-10|
    US20170204563A1|2017-07-20|
    EP2904144B1|2020-08-05|
    EP2904144A1|2015-08-12|
    BR112015007539A2|2017-07-04|
    HRP20201723T1|2021-03-05|
    CA2887149A1|2014-04-10|
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    法律状态:
    2018-07-31| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|
    2018-11-13| B08G| Application fees: restoration [chapter 8.7 patent gazette]|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2019-12-03| B25D| Requested change of name of applicant approved|Owner name: GRANBIO INTELLECTUAL PROPERTY HOLDINGS, LLC (US) |
    2019-12-24| B25G| Requested change of headquarter approved|Owner name: GRANBIO INTELLECTUAL PROPERTY HOLDINGS, LLC (US) |
    2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-20| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/10/2013, OBSERVADAS AS CONDICOES LEGAIS. |
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