WO2009155673A1 - Procédé de fermentation pour biomasse végétale lignocellulosique - Google Patents

Procédé de fermentation pour biomasse végétale lignocellulosique Download PDF

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Publication number
WO2009155673A1
WO2009155673A1 PCT/BR2009/000177 BR2009000177W WO2009155673A1 WO 2009155673 A1 WO2009155673 A1 WO 2009155673A1 BR 2009000177 W BR2009000177 W BR 2009000177W WO 2009155673 A1 WO2009155673 A1 WO 2009155673A1
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accordance
fermentative process
biomass
fermentative
hemicellulases
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Inventor
Henrique Macedo Baudel
Celia Maria Araujo GALVÃO
Jaime Finguerut
José Augusto TRAVASSOS RIOS TOMÉ
Dionísio MORELLI FILHO
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CTC Centro de Tecnologia Canavieira SA
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CTC Centro de Tecnologia Canavieira SA
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention refers to a fermentative process comprising pre- treatment steps of a lignocellulosic plant biomass, in which steam is used in the presence or absence of chemical and/or biochemical catalysts, an enzymatic hydrolysis of the aforesaid biomass and a fermentation of the hydrolyzed juice obtained by this enzymatic process.
  • the plant biomass is sugar cane bagasse and/or straw and the product is ethanol.
  • Cellulose is a linear polymer of D-glucose composed of ⁇ -1 ,4, glycosidic bonds with repeated units of cellobiose, forming a highly crystalline material that is insoluble in water.
  • the degree of polymerization is located in the range of 7500-15000 molecules of glucose present in the cellulosic chain.
  • Cellulose is organized in fibers with a diameter of 2.0-4.0 nm. These fibers are associated with hydrogen bridges and van der Waals bonds, forming a rigid molecular structure (microfibrils), with diameters from 10 to 30 nm.
  • the crystalline fraction is constituted from 50 to 90% of cellulose. In this fraction, the capillaries are small, which makes it exceedingly difficult for the penetration of the matrix by the enzymes (average size of 5 nm). Therefore, processes of enzymatic hydrolysis require a prior treatment (pre-treatment) of lignocellulosic biomass, seeking to "open" the cellulosic matrix to the action of the enzymes.
  • the regions of low crystallinity (amorphous) existing in the microfibrils are susceptible to enzymatic action, dispensing with the pre-treatment of the biomass.
  • hemicelluloses are heterogeneous polymers subdivided from different carbohydrates and linked by different chemical bonds.
  • substitutes e.g., acetyl groups and uronic acids are associated with the principal chain or with its respective subdivisions, in structures with a degree of polymerization varying from 20 to 300.
  • Hemicelluloses do not present either the degree of crystallinity or the microfibril structure found in cellulose and they do not exercise effective influence over the structural properties of the plant tissue. In this manner, they present a greater susceptibility to acid and enzymatic hydrolysis, as well as higher solubility in aqueous-alkaline solutions.
  • holocellulose is used to refer to the total saccharide fraction (cellulose and hemicelluloses) of the plant tissue free of extractives.
  • Hemicelluloses are associated with phenolic fraction (lignin) through covalent bonds and with cellulose via the hydrogen bond. Its composition varies according to the lignocellulosic material. Softwoods, such as Pinus radiata, contain a higher content of glucomannans, while hardwoods, such as birch, present a higher content of glucoxylans.
  • the hemicelluloses of sugar cane bagasse are predominantly constituted of xylans, although they also present lower quantities of glucoxylans and arabinoxylans.
  • lignin is one of the most abundant organic polymers in the plant kingdom. Usually, lignin is seen as a "cement” or “incrusting substance” of the plant tissue, contributing significantly to the mechanical resistance of the tissue. On the other hand, while a relatively large quantity of microorganisms is capable of decomposing and converting cellulose and the hemicelluloses, only a significantly reduced number has the capability to decompose lignin effectively, which justifies the high resistance of the plants to deterioration.
  • Lignin is a complex tridimensional amorphous polymer, with a high molecular weight, generally associated with cellulose and hemicelluloses through ether and carbon-carbon bonds. Its chemical structure, in its natural state, is highly aromatic, phenolic in character, and composed of units of phenyl-propane associated with the methoxyl and phenolic and aliphatic hydroxyl groups.
  • pre- treatment of the lignocellulosic biomass, seeking to remove non-cellulosic components, predominantly the hemicelluloses, in order to improve the accessibility of the enzymes to the cellulose.
  • Acid hydrolysis is a common method for the conversion of cellulose into glucose, which is a fermentable sugar. It generally involves the use of concentrated or diluted acids. This process produces moderate amounts of glucose, with problems of cost associated with the need to recuperate the acid and the use of special construction materials for the equipment and its corrosion.
  • the present invention differs fundamentally from the abovementioned documents because it includes the pre-treatment of the lignocellulosic biomass with steam until the final step of fermentation of the sugars available in the enzymatic hydrolysis step, particularly the glucose from the cellulose. Additionally, the present invention also embodies the use of a "pool" of enzymes (hemicellulases and cellulases) in the process of availability of the sugars, particularly glucose, in SHF (Separated Hydrolysis and Fermentation) and SSF (Simultaneous Saccharification and Fermentation) systems. The present invention specifically includes p re-treatments using non-catalytic and auto- catalyzed conditions, as well as catalytic systems using acids, metal salts (e.g.
  • Lewis acids e.g. calcium salts
  • neutral or weak acids e.g. carbonates
  • It also includes the enzymatic treatment of the residual hemicelluloses present in the pre-treated biomass by the physical-chemical processes of pre-treatment with steam. Such a sequence configures a pre-treatment in two steps, the first physical-chemical and the second enzymatic.
  • Patent US 6,423,145 describes a production process of cellulose that comprises a step of hydrolysis of a lignocellulosic material in a steam explosion reactor (continuous or discontinuous) in the presence of a mixture of catalysts.
  • the catalysts are diluted inorganic acids (e.g. H 2 SO 4 , SO 2 , HCI and HNO3) and metal salts of acidic character, selected from ferrous sulfate, ferric sulfate, ferric chloride, aluminum sulfate, aluminum chloride and magnesium sulfate.
  • the pre-treatment step employs not only inorganic acids and acid metal salts as chemical catalysts, but also organic acids (e.g.
  • the present invention also employs hemicellulases as biochemical (enzymatic) catalysts. Another aspect that differentiates the present process from the abovementioned process is its global character. Accordingly, beyond the pre- treatment, it also embodies the steps of the enzymatic hydrolysis of the pre- treated biomass using cellulases and the fermentation of the sugars produced in the two prior steps, both in the SHF systems and the SSF systems.
  • Document US 7,189,306 describes a process to treat lignocellulosic material comprising steps of crushing, pre-treatment with steam in an alkaline (pH>8) in two steps, in the presence or absence of an oxidizing agent (e.g. 02 and/or H 2 O 2 ), followed by a fractionation step of the cellulose and subsequent fermentation of the carbohydrates by the SSCF (Separated Saccharification and Co-Fermentation) process.
  • the present invention differs from this document because the pre- treatment can be performed in acid (organic and inorganic), neutral and alkaline products, using metal catalysts (acid and alkaline salts) with the possibility of using an enzymatic step (hemicellulases) for the removal of the residual hemicelluloses.
  • it includes steps of enzymatic hydrolysis of the cellulose and fermentation of the generated hydrolyzed juice, using yeast of the type Saccharomices cerevisae, for example, for the production of the cellulosic ethanol, in the SHF and SSF processes.
  • the present invention differs from the abovementioned document because it does not include any step relative to the pyrolisis process of the pre- treated biomass, among the other grounds already presented and discussed throughout the present text. Therefore, based on what is available until now, it can be seen that the state of the art does not anticipate or suggest the embodiments of the present invention. Thus, there is a need of a process for the pre-treatment of lignocellulosic material for the production of sugars and also ethanol that provides a high yield.
  • the object of the present invention is a fermentative process comprising the steps of: a) Pre-treatment of the lignocellulosic plant biomass in one (steam explosion) or two (steam explosion followed by treatment with hemicellulases) steps; b) Enzymatic hydrolysis of the pre-treated biomass using mixtures containing cellulases and/or ⁇ -glycosidases and/or hemicellulases c) Fermentation of the carbohydrates produced during the step of the enzymatic hydrolysis of the pre-treated biomass.
  • the sugar cane bagasse that constitutes the process proposed in this invention is derived from a diffuser, when possible.
  • the bagasse can also be derived from a crusher or a mixture from a diffuser and a crusher.
  • chemical catalysts and oxidizing agents can be used in the pre-treatment of the biomass with steam.
  • the pre-treatment process comprises a step of enzymatic hydrolysis of the hemicelluloses present in the pre-treated biomass with steam using a mixture of hemicellulases.
  • the processes of the enzymatic hydrolysis of the hemicelluloses and of the cellulose occur simultaneously with the fermentation of the carbohydrates.
  • An additional object of the present invention is a fermented product obtained by the abovementioned fermentative process.
  • the fermented product is ethanol.
  • Figure 1 displays a process for the production of ethanol from a lignocellulosic biomass, in which the pre-treatment can be performed by physical-chemical means and enzymatically (hemicellulases). The subsequent steps of the enzymatic hydrolysis of the cellulose (cellulases) and the fermentation (Saccharomyces cerevisiae) occur separately (SHF process).
  • Figure 2 displays a process for the production of ethanol, in which the pre-treatment of the lignocellulosic biomass can be performed in three steps: physical-chemical treatment, enzymatic hydrolysis (hemicellulases) for the removal of the residual hemicellulose and washing of the final pre-treated bagasse. Subsequently, the pre-treated bagasse is submitted to the simultaneous process of the enzymatic hydrolysis of the cellulose (cellulases) and the fermentation ⁇ Saccharomyces cerevisiae) - (SSF process).
  • Figure 3 displays a process for the production of ethanol from the lignocellulosic biomass, in which the pre-treatment step is performed in two steps: physical-chemical treatment and washing of the final pre-treated bagasse.
  • the pre-treated bagasse is submitted to the simultaneous process of the enzymatic hydrolysis of the cellulose (cellulases) and of the residual hemicellulose (hemicellulases) and the fermentation (Saccharomyces cerevisiae) - (SSF process).
  • Figure 4 displays the chromatogram with respect to the liquid fraction after the pre-treatment of the biomass with steam.
  • the presence of xylose is evidence of the partial removal of the hemicelluloses from the biomass after the process.
  • Glucose is produced from the sucrose that is derived from the crushing of the cane and from the cellulose of the bagasse.
  • Figure 5 displays the chromatogram with respect to the compositional analysis of the pre-treated biomass (PTB) with steam.
  • the presence of xylans (characterized in the form of xylose) in the biomass is evident, indicating the non-total removal of the hemicelluloses.
  • Figure 6 displays the chromatogram with respect to the SHF experiment.
  • a lower production of glucose can be observed in relation to the condition presented in Figure 4, due to the recalcitrance exercised by the residual hemicelluloses present in the biomass.
  • Figure 7 displays the chromatogram with respect to the SHF experiment.
  • a higher production of glucose can be observed in relation to the condition presented in Figure 3, due to the action of the hemicellulases, which is evidence of the synergy between the different enzymes.
  • the presence of sorbitol in the hydrolyzed enzymatic product characterizes a potential activation of the glucose in the presence of the hemicellulases, which remove the hemicelluloses from the biomass.
  • Figure 8 displays the chromatogram with respect to the fermented juice from the SSF experiments, using only hemicellulases (without cellulases) and washed pre-treated biomass (PTB).
  • the significant production of xylose can be observed and the selective removal of the residual hemicelluloses present in the PTB (Cxyiose: C g ⁇ UC ose > 100).
  • No production or consumption of glucose can be observed during the process, which is evidenced by the almost zero production of ethanol by the yeasts present in the reaction.
  • the efficiency of the enzymatic pre-treatment (using hemicellulases) of the biomass is represented here, supplementing the pre-treatment process with steam, in the selective removal of the residual hemicelluloses, with minimal cellulosic loss.
  • Figure 9 displays the chromatogram with respect to the fermented juice from the SSF experiments, using only cellulases (without hemicellulases) and washed pre-treated biomass (PTB).
  • a minimal concentration of glucose can be observed but with a high production and simultaneous consumption of the same, evidenced by the production of ethanol by the yeasts present in the reaction (C etha n o ⁇ O.5 %m/m).
  • Figure 10 displays the chromatogram with respect to the fermented juice from the SSF experiments, of the PTB washed and treated with hemicellulases.
  • a minimal concentration of glucose can be observed but with a high production and simultaneous consumption of the same, evidenced by the production of ethanol (0.5 %m/m) by the yeasts present in the reaction.
  • the presence of xylose can be observed in the juice in a concentration of the order of 0.49 g/kg, but with a high production and consumption of the same. This is evidenced by the production of products distinct from ethanol, characterizing potential synergy from the hemicellulases and the yeasts.
  • FIG. 11 displays the chromatogram with respect to the fermented juice from the SSF experiments of the washed PTB, with cellulases complemented with a saccharidic solution (sugar cane juice).
  • A Time 0 (zero)
  • B Time 24 hours. The practically complete consumption of the glucose can be observed, evidencing that the addition of a solution rich in fermentable sugars (booster) does not inhibit the fermentative activity of the yeasts.
  • Figure 12 displays the chromatogram with respect to the a:
  • CEI concentration of ethanol from experiment i.
  • lignocellulosic plant biomass comprises any type of plant, namely: herbaceous biomass; cultivated plants such as C4 plants - belonging to the genera Lolium, Spartina, Panicum, Miscanthus, and combinations thereof; sugar cane bagasse (from crusher and/or diffuser, the bagasse from the diffuser being preferred); straws of cereals such as wheat, rice, rye, barley, oatmeal, corn and similar products (e.g. switchgrass); wood; trunks and stalks of the banana tree; cacti and combinations thereof.
  • lignocellulosic materials can also comprise cardboard, sawdust, newspaper and agro-industrial residuals or similar products.
  • Vegetable biomasses from different origins can present specific differences although they may have a relatively similar global chemical composition. Some variations in the composition from different species and even from the same species are due to environmental and genetic variables, as well as the location of the tissue in different parts of the plant. Typically, approximately 35-50% is constituted of cellulose, 20-35% of hemicelluloses and approximately 20-30% of lignin. The remainder consists of smaller quantities of ashes, soluble phenolic compounds and fatty acids, as well as other constituents, denominated extractives.
  • Cellulose and the hemicelluloses of the plant tissue are constituted of structural carbohydrates (e.g. glucans, xylans and mannans), generally denominated from the saccharidic fraction.
  • Lignin is constituted in the phenolic fraction of the plant biomass.
  • the present invention comprises a fermentative process that has technical-operational advantages when compared to the processes disclosed in the state of the art and involves the following steps: a) Pre-treatment of the lignocellulosic plant biomass with a steam explosion step; optionally followed by a second step of pre-treatment of the biomass using hemicellulases (enzymes); b) Enzymatic hydrolysis of the pre-treated biomass using mixtures containing cellulases and/or ⁇ -glycosidases and/or hemicellulases; c) Fermentation of the carbohydrates produced from the enzymatic hydrolysis of the pre-treated biomass.
  • hemicellulases hemicellulases
  • Pre-treatment step The removal of the hemicelluloses from the lignocellulosic biomasses such as the bagasse and the straw of the cane and the corn allow the increased accessibility of the cellulose to the chemical agents (e.g. acids or alkalis) or biochemicals (e.g. enzymes) that convert it into fermentable sugars, particularly glucose.
  • chemical agents e.g. acids or alkalis
  • biochemicals e.g. enzymes
  • the combination of the chemical processes (e.g. treatment with steam) and biochemical processes (e.g. hydrolysis with hemicellulases) allows the fragmentation and subsequent removal of the hemicelluloses present in the biomass with high selectivity, embodying a particularly efficient alternative in terms of pre-treatment.
  • the pre-treatment is conceived as a group of operational steps that follow the preparation of the biomass and the feeding of the reactor and precede the enzymatic hydrolysis of the cellulose.
  • the pre-treatment of the lignocellulosic biomass with saturated steam or water under pressure at different levels of temperature and processing time promotes the partial removal of the hemicelluloses, increasing the accessibility of the cellulosic matrix to the cellulolytic enzymes (cellulases).
  • the steam used can be generated in its own chamber or can be introduced into the chamber.
  • the pre-treatment processes can be performed by the configuration of a steam explosion - STEX or a wet explosion - WEX, in which a rapid decompression occurs in the discharge of the material.
  • a cooking configuration can also be used, in which a rapid decompression is not used after the process time.
  • the steam explosion processes tend to produce a larger fragmentation of the hemicelluloses, making the cellulose more accessible to the chemical and enzymatic agents.
  • catalysts and adjuvants such as oxidants (e.g. O 2 and H 2 O 2 ) in acid, alkaline or neutral systems allows the removal of large quantities of hemicelluloses under less severe process conditions. Furthermore, there is evidence of a high selectivity in terms of extraction predominantly of hemicelluloses, preserving the cellulosic content of the pre-treated biomass.
  • oxidants e.g. O 2 and H 2 O 2
  • the deacetylation of the hemicelluloses can be intensified in order to produce acetic acid, which acts, in this context, as an hemicelluloses "autochthonous catalyst", characterizing an autocatalytic process.
  • the pre-treatment presented in the present invention can comprise of one or more catalysts, including, although not limited to, inorganic acids such as
  • H 2 SO 4 HCI, HNO 3 , H 3 PO 4 or combinations of these, organic acids such as acetic, formic and carbonic acid (H 2 COs), oxides (SO 2 , MnO 2 , CO 2 ), sulfates
  • Compounds that are generated during the pre-treatment can also act as catalysts and are denominated auto-catalysts.
  • examples of these compounds include organic acids, such as acetic acid and acids arising from the degradation of carbohydrates, as well as phenolic species derived from lignin.
  • the catalysts can be present in a concentration that varies from 0.10% to 8% in relation to the dry mass of the biomass, but should preferentially be situated in the range from 0.25% to 6%.
  • a selective enzymatic treatment of the pre-treated biomass using a physical-chemical process e.g. STEX, WEX
  • a physical-chemical process e.g. STEX, WEX
  • moderate conditions of temperature allows the production of a material with a high cellulosic content as well as the greater accessibility of cellulose to the enzymes, for example, mixtures of cellulases and ⁇ -glycosidases.
  • the present invention presents the complementary enzymatic pre-treatment of the lignocellulosic biomass (pre- treated by physical-chemical processes) based on the use of hemicellulases (enzymes that fragment the hemicelluloses) under temperature conditions varying from 35 0 C to 6O 0 C, preferentially from 45 0 C to 55 0 C, with reaction times varying from 6 hours to 48 hours, preferentially from 12 hours and 24 hours.
  • hemicellulases enzymes that fragment the hemicelluloses
  • the hemicellulases are in the proportions varying from 5.5% to 30%, preferentially from 12% to 22%, in relation to the quantity of the pre-treated biomass (dry base).
  • Base Sugar cane bagasse pre-treated with steam.
  • the fermentation step can be performed after the enzymatic hydrolysis, by a process known as SHF (Separated Hydrolysis and Fermentation), or concomitantly with the hydrolysis, in a process known as SSF (Simultaneous Saccharification and Fermentation).
  • SHF Separatated Hydrolysis and Fermentation
  • SSF Simultaneous Saccharification and Fermentation
  • a concentrated saccharidic solution can be optionally added to the reaction, varying from 80 g/L to 820 g/L, preferentially from 120 g/L to 200 g/L (e.g. cane molasses or juice).
  • the present invention also allows the possibility of simultaneously performing the enzymatic pre-treatment of the hemicelluloses, the enzymatic hydrolysis of the cellulose and the fermentation, characterizing a Consolidated BioProcess (CBP) using the pre-treated biomass with steam or other agents as a base.
  • Figures 1 , 2 and 3 display flowcharts concerning the different configurations contemplated in the present invention.
  • Figure 1 displays a typical SHF process, consisting of three distinct steps (pre-treatment, enzymatic hydrolysis and fermentation) performed separately.
  • the cellulosic biomass is submitted to a physical-chemical pre-treatment (e.g. STEX, WEX, etc.), in the presence or absence of catalysts, oxidants and other inputs.
  • a physical-chemical pre-treatment e.g. STEX, WEX, etc.
  • the catalysts are present in a concentration that varies from 0.10% to 8% in relation to the dry mass of the biomass, preferentially from 0.25% to 6%.
  • the charge of the solids varies from 5% to 60%, preferentially from 15% to 50%, in relation to the total mass.
  • the biomass remains in the reactor during a reaction time from 30 seconds to 60 minutes, preferentially from 5 minutes to 15 minutes, at a process temperature that can vary from 11O 0 C to 24O 0 C, preferentially from 18O 0 C to 21O 0 C.
  • the reactor is preferentially unloaded by sudden decompression and optionally without sudden decompression.
  • the pre-treated biomass can be submitted to a complementary pre-treatment using specific enzymes (hemicellulases).
  • the hemicellulases are in proportions varying from 5.5% to 30%, preferentially from 12% to 22%, in relation to the mass of the pre-treated biomass (dry base).
  • the biomass remains in the reactor for a reaction time from 6 hours to 48 hours, preferentially from 12 hours to 24 hours, at a process temperature varying from 35 0 C to 6O 0 C, preferentially from 45 0 C to 55 0 C.
  • the amount of solids varies from 2% to 20%, preferentially from 7.5% to 15%, in relation to the total mass.
  • the biomass can optionally be submitted to washing with water or acidic or alkaline solutions at an ambient temperature.
  • the pre-treated biomass is next submitted to an enzymatic hydrolysis, where it is sent to a reactor, which is preferentially discontinuous and optionally continuous, together with specific enzymes (cellulases and ⁇ -glycosidases).
  • the cellulases are in proportions that vary from 5.5% to 30%, preferentially from 12% to 22%, in relation to the mass of the pre-treated biomass (dry base).
  • the ⁇ -glycosidases are in proportions varying from 2.5% to 15%, preferentially from 5.5% to 7.5%, in relation to the mass of the pre-treated biomass (dry base).
  • the charge of the solids varies from 2% to 20%, preferentially from 7.5% to 15%, in relation to the total mass.
  • the biomass remains in the reactor for a reaction time that varies from 12 hours to 72 hours, preferentially from 24 hours to 48 hours, at a process temperature varying from 35 0 C to 6O 0 C, preferentially from 45 0 C to 55 0 C.
  • reaction time elapses, the reactor is unloaded and the material is submitted to a separation process, preferentially filtration and optionally centrifugation or ultra-filtration, producing a liquid fraction (hydrolyzed enzymatic product) and a solid fraction (lignocellulosic residue or cellulignin).
  • the hydrolyzed enzymatic product is then submitted to an ethanolic fermentation preferentially using yeasts of the type Saccharomices cerevisae and optionally using bacteria of the type Zymomonas mobilis.
  • the hydrolyzed enzymatic product is preferentially mixed with cane molasses or juice and optionally fermented individually, without any type of mixture with molasses or juice.
  • Figure 2 presents a typical SSF process, in which the steps of enzymatic hydrolysis and fermentation are performed simultaneously.
  • the cellulosic biomass is submitted to a physical-chemical pre-treatment (e.g. STEX, WEX, etc.), in the presence or absence of catalysts, oxidants and other inputs.
  • a physical-chemical pre-treatment e.g. STEX, WEX, etc.
  • catalysts these are present in concentrations that vary from 0.10% to 8% in relation to the dry mass of the biomass, preferentially from 0.25% to 6%.
  • the amount of the solids varies from 5% to 60%, preferentially from 15% to 50%, in relation to the total mass.
  • the biomass remains in the reactor during a reaction time from 30 seconds to 60 minutes, preferentially from 5 minutes to 15 minutes, at a process temperature varying from 11O 0 C to 24O 0 C, preferentially from 18O 0 C to 21O 0 C.
  • the reactor is preferentially unloaded by sudden decompression and optionally without sudden decompression.
  • the pre-treated biomass can be submitted to a complementary pre-treatment using specific enzymes (hemicellulases).
  • the hemicellulases are in proportions varying from 5.5% to 30%, preferentially from 12% to 22%, in relation to the mass of the pre-treated biomass (dry base).
  • the biomass remains in the reactor for a reaction time varying from 6 hours to 48 hours, preferentially from 12 hours to 24 hours, at a process temperature varying from 35 0 C to 6O 0 C, preferentially from 45 0 C to 55 0 C.
  • the amount of the solids varies from 2% to 20%, preferentially from 7.5% to 15%, in relation to the total mass.
  • the biomass can optionally be submitted to washing with water or acidic or alkaline solutions at an ambient temperature.
  • the pre-treated biomass is submitted to an enzymatic hydrolysis, where it is sent to a fermentation reactor, which is preferentially discontinuous and optionally continuous, together with specific enzymes (cellulases and ⁇ - glycosidases).
  • the cellulases are in proportions varying from 5.5% to 30%, preferentially from 12% to 22%, in relation to the mass of the pre-treated biomass (dry base).
  • the ⁇ -glycosidases are in proportions varying from 2.5% to 15%, preferentially from 5.5% to 7.5%, in relation to the mass of the pre-treated biomass (dry base).
  • the charge of the solids varies from 2% to 20%, preferentially from 7.5% to 15%, in relation to the total mass.
  • a concentrated saccharidic solution (“booster”) is added, preferentially cane molasses and, optionally, cane juice, to the fermentation at the start or during the enzymatic hydrolysis process although it can operate without the addition of the saccharidic solution.
  • the saccharidic solution (“booster”) presents a concentration of sugars varying from 80 g/L to 820 g/L, preferentially from 120 g/L to 200 g/L.
  • the biomass remains in the reactor during a reaction time varying from 80 g/L to 820 g/L, preferentially from 120 g/L to 200 g/L.
  • the reactor When the reaction time elapses, the reactor is unloaded and the material is submitted to a separation process, preferentially filtration and optionally centrifugation, producing a liquid fraction (must) and a solid fraction (lignocellulosic residue or cellulignin).
  • Figure 3 presents an advanced SSF process, in which the enzymatic pre- treatment steps with hemicellulases, enzymatic hydrolysis with cellulases and fermentation are performed simultaneously.
  • the cellulosic biomass is submitted to a physical-chemical pre-treatment (e.g. STEX, WEX, etc.), in the presence or absence of catalysts, oxidants and other inputs.
  • the catalysts are present in a concentration that varies from 0.10% to 8% in relation to the dry mass of the biomass, preferentially from 0.25% to 6%.
  • the amount of the solids varies from 5% to 60%, preferentially from 15% to 50%, in relation to the total mass.
  • the biomass remains in the reactor during a reaction time from 30 seconds to 60 minutes, preferentially from 5 minutes to 15 minutes, at a process temperature that varying from 11O 0 C to 24O 0 C, preferentially from 18O 0 C to 21O 0 C.
  • the reactor is preferentially unloaded by sudden decompression and optionally without sudden decompression.
  • the pre-treated biomass is submitted to an additional pre-treatment using specific enzymes (hemicellulases).
  • specific enzymes hemicellulases.
  • the pre-treated biomass by physical- chemical processes is sent to a fermentation reactor, which is preferentially discontinuous and optionally continuous, together with specific enzymes
  • hemicellulases The hemicellulases are in proportions varying from 5.5% to
  • the biomass remains in the reactor for a reaction time varying from 6 hours to 48 hours, preferentially from 12 hours to 24 hours, at a process temperature varying from 35 0 C to 6O 0 C, preferentially from 45 0 C to 55 0 C.
  • the amount of the solids varies from 2% to 20%, preferentially from 7.5% to 15%, in relation to the total mass.
  • the fermentation step begins with the enzymatic hydrolysis of the cellulose and the fermentation, characterizing an SSF process
  • the cellulases are in proportions varying from 5.5% to 30%, preferentially from 12% to 22%, in relation to the mass of the pre-treated biomass (dry base).
  • the ⁇ -glycosidases are in proportions varying from 2.5% to 15%, preferentially from 5.5% to 7.5%, in relation to the mass of the pre-treated biomass (dry base).
  • the amount of the solids varies from 2% to 20%, preferentially from 7.5% to 15%, in relation to the total mass.
  • a concentrated saccharidic solution (“booster”) is added, preferentially cane molasses and, optionally, cane juice, to the fermentation at the start or during the enzymatic hydrolysis process although it can operate without the addition of the saccharidic solution.
  • the saccharidic solution (“booster”) presents a concentration of sugars varying from 80 g/L to 820 g/L, preferentially from 120 g/L to 200 g/L.
  • the biomass remains in the reactor during a reaction time varying from 12 hours to 72 hours, preferentially from 24 hours to 48 hours, at a process temperature varying from 3O 0 C to 5O 0 C, preferentially from 37 0 C to 4O 0 C, with the pH of the reaction varying from 4.2 to 5.5, preferentially from 4.8 to 5.0.
  • the reactor When the reaction time elapses, the reactor is unloaded and the material is submitted to a separation process, preferentially filtration and optionally centrifugation, producing a liquid fraction (must) and a solid fraction (lignocellulosic residue or cellulignin).
  • a separation process preferentially filtration and optionally centrifugation, producing a liquid fraction (must) and a solid fraction (lignocellulosic residue or cellulignin).

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Abstract

La présente invention concerne un procédé de fermentation comprenant une étape de prétraitement et une hydrolyse enzymatique d’une biomasse végétale lignocellulosique. Ledit prétraitement inclut l’utilisation de vapeur, éventuellement en présence de catalyseurs. L’invention porte également sur un prétraitement enzymatique et sur un produit fermenté issu de ce procédé. Plus spécifiquement, la biomasse végétale est de la bagasse de canne à sucre et le produit est de l’éthanol.
PCT/BR2009/000177 2008-06-23 2009-06-23 Procédé de fermentation pour biomasse végétale lignocellulosique Ceased WO2009155673A1 (fr)

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BRPI0802153A BRPI0802153B1 (pt) 2008-06-23 2008-06-23 processo fermentativo copreendendo etapa de pré-tratamento, hidrólise enzimática e produto fermentado utilizando biomassa vegetal lignocelulósica

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US20110154721A1 (en) * 2009-12-31 2011-06-30 Chheda Juben Nemchand Biofuels via hydrogenolysis-condensation
CN102586897A (zh) * 2011-12-21 2012-07-18 中国热带农业科学院海口实验站 利用汽爆技术制备香蕉纤维素纳米纤维的方法
WO2012129622A1 (fr) * 2011-03-30 2012-10-04 Ctc - Centro De Tecnologia Canavieira S.A Utilisation de vinasse dans le procédé de saccharification de biomasses lignocellulosiques
US20140135470A1 (en) * 2011-06-17 2014-05-15 Chemtex Italia, S.p.A. Lignin conversion process
CN104321435A (zh) * 2012-03-30 2015-01-28 Ctc-蔗糖技术中心不记名股份公司 用于第一代和第二代乙醇的整合生产的系统和方法以及用于所述生产的整合点的使用
CN107868802A (zh) * 2017-12-21 2018-04-03 叶芳 一种以农林废弃物为原料制备生物乙醇的方法
CN113234772A (zh) * 2021-06-04 2021-08-10 华南农业大学 一种杨木酶解生产葡萄糖的方法
WO2021155452A1 (fr) * 2020-02-03 2021-08-12 Petróleo Brasileiro S.A. - Petrobras Procédé optimisé pour la production de sucres de deuxième génération et produits de fermentation
CN114774147A (zh) * 2022-04-28 2022-07-22 华南农业大学 一种促进木质纤维素定向转化为中间化学品的方法及应用

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WO2007136843A2 (fr) * 2006-05-18 2007-11-29 North Carolina State University Traitement de matière cellulosique au moyen de plasma à la pression atmosphérique
US20080044877A1 (en) * 2004-06-04 2008-02-21 Merja Penttila Process for Producing Ethanol

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US20080044877A1 (en) * 2004-06-04 2008-02-21 Merja Penttila Process for Producing Ethanol
WO2007136843A2 (fr) * 2006-05-18 2007-11-29 North Carolina State University Traitement de matière cellulosique au moyen de plasma à la pression atmosphérique

Cited By (16)

* Cited by examiner, † Cited by third party
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US9493719B2 (en) * 2009-12-31 2016-11-15 Shell Oil Company Biofuels via hydrogenolysis-condensation
US20140173975A1 (en) * 2009-12-31 2014-06-26 Shell Oil Company Biofuels via hydrogenolysis-condensation
US9447347B2 (en) * 2009-12-31 2016-09-20 Shell Oil Company Biofuels via hydrogenolysis-condensation
US20110154721A1 (en) * 2009-12-31 2011-06-30 Chheda Juben Nemchand Biofuels via hydrogenolysis-condensation
US9611492B2 (en) 2011-03-30 2017-04-04 Ctc-Centro De Tecnologia Canavieira S.A. Use of vinasse in the process of saccharification of lignocellulosic biomass
WO2012129622A1 (fr) * 2011-03-30 2012-10-04 Ctc - Centro De Tecnologia Canavieira S.A Utilisation de vinasse dans le procédé de saccharification de biomasses lignocellulosiques
US9187390B2 (en) * 2011-06-17 2015-11-17 Biochemtex S.P.A. Lignin conversion process
US20140135470A1 (en) * 2011-06-17 2014-05-15 Chemtex Italia, S.p.A. Lignin conversion process
CN102586897A (zh) * 2011-12-21 2012-07-18 中国热带农业科学院海口实验站 利用汽爆技术制备香蕉纤维素纳米纤维的方法
CN104321435A (zh) * 2012-03-30 2015-01-28 Ctc-蔗糖技术中心不记名股份公司 用于第一代和第二代乙醇的整合生产的系统和方法以及用于所述生产的整合点的使用
CN107868802A (zh) * 2017-12-21 2018-04-03 叶芳 一种以农林废弃物为原料制备生物乙醇的方法
WO2021155452A1 (fr) * 2020-02-03 2021-08-12 Petróleo Brasileiro S.A. - Petrobras Procédé optimisé pour la production de sucres de deuxième génération et produits de fermentation
US12565669B2 (en) 2020-02-03 2026-03-03 Petróleo Brasileiro S.A.—Petrobras Optimized process for producing second-generation sugars and fermentation products
CN113234772A (zh) * 2021-06-04 2021-08-10 华南农业大学 一种杨木酶解生产葡萄糖的方法
CN114774147A (zh) * 2022-04-28 2022-07-22 华南农业大学 一种促进木质纤维素定向转化为中间化学品的方法及应用
CN114774147B (zh) * 2022-04-28 2023-06-20 华南农业大学 一种促进木质纤维素定向转化为中间化学品的方法及应用

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