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WO2013103111A1 - Procédé et dispositif pour produire de l'éthanol - Google Patents

Procédé et dispositif pour produire de l'éthanol Download PDF

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Publication number
WO2013103111A1
WO2013103111A1 PCT/JP2012/083561 JP2012083561W WO2013103111A1 WO 2013103111 A1 WO2013103111 A1 WO 2013103111A1 JP 2012083561 W JP2012083561 W JP 2012083561W WO 2013103111 A1 WO2013103111 A1 WO 2013103111A1
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fermentation
ethanol
reaction
hot water
pressurized hot
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PCT/JP2012/083561
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English (en)
Japanese (ja)
Inventor
佐藤　健治
北野　誠
典充 金子
健太郎 成相
伊藤　浩史
矢野　伸一
遠藤　貴士
Original Assignee
株式会社Ihi
独立行政法人産業技術総合研究所
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Publication of WO2013103111A1 publication Critical patent/WO2013103111A1/fr

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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
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00—Bioreactors or fermenters specially adapted for specific uses
    • C12M21/12—Bioreactors or fermenters specially adapted for specific uses for producing fuels or solvents
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M45/00—Means for pre-treatment of biological substances
    • C12M45/09—Means for pre-treatment of biological substances by enzymatic treatment
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M45/00—Means for pre-treatment of biological substances
    • C12M45/20—Heating; Cooling
    • 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
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/02—Monosaccharides
    • 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
    • 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
    • C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
    • 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 relates to a method and apparatus for producing ethanol, and in particular, a method for producing ethanol that produces biomass ethanol by saccharification of lignocellulosic material and microbial fermentation using plant waste such as wood and wheat straw as biomass, and It relates to a manufacturing apparatus.
  • Non-Patent Document 1 discloses a process for producing ethanol by saccharifying cellulose in biomass into glucose using cellulase, which is widely known as a saccharifying enzyme, and fermenting the obtained glucose.
  • Patent Document 1 listed below describes a method for producing ethanol in which fine bark that has been subjected to treatment with an alkali solution of bark raw material and refined by mechanical treatment is prepared into a slurry having an appropriate pH and then subjected to concurrent saccharification and fermentation. .
  • patent document 2 describes the treatment of biomass having a step of decomposing hemicellulose by treating cellulosic biomass with pressurized hot water
  • patent document 3 uses pressurized hot water treatment.
  • Non-Patent Document 2 In order to improve the efficiency of ethanol production from cellulosic biomass, development of microorganisms with high fermentation efficiency has been promoted, and various genetically modified yeasts have been proposed (for example, Non-Patent Document 2 below).
  • Cellulose contained in the wood material used as lignocellulosic biomass is saccharified to glucose using cellulase and converted to ethanol by fermentation with yeast, etc., but the monosaccharide obtained from hemicellulose contained in the wood material is In addition, the conversion efficiency to ethanol in fermentation by natural yeast or the like is not so high, and there is a problem of alcohol resistance.
  • the proportion of hemicellulose in the wood depends on the type of plant, it is generally around 30% and is not negligible. Therefore, in order to efficiently produce biomass ethanol at low cost, it is necessary to be able to efficiently perform hemicellulose saccharification and fermentation.
  • the problem to be solved by the present invention is to solve the above-mentioned problems and to provide a method for producing ethanol, which has high conversion efficiency in saccharification / fermentation of hemicellulose and can efficiently purify biomass ethanol.
  • the present inventors have conducted extensive research. As a result, in the saccharification / fermentation of hemicellulose, an efficient method for producing biomass ethanol using xylose ethanol fermentation by genetically modified yeast is proposed. The present inventors have found that it can be configured and completed the present invention.
  • the ethanol production apparatus comprises a pressurized hot water reactor that selectively decomposes hemicellulose contained in biomass by causing pressurized hot water to act on the biomass, and the pressurized heat.
  • the decomposition product of the water reactor is heated to 90 to 110 ° C. to act on a solid acid catalyst to obtain a saccharification product containing xylose, and the saccharification product obtained by the catalyst reaction device is subjected to xylose.
  • the gist of the present invention is to have a fermentation apparatus that produces ethanol by causing a microorganism having fermentation ability to act.
  • the schematic block diagram which shows one Embodiment of the ethanol manufacturing apparatus which concerns on this invention.
  • the graph which shows the relationship between the xylose ratio at the time of fermenting the mixture of xylose and glucose, and an ethanol yield.
  • Graphs (a) to (f) showing temporal changes in the amounts of sugar and ethanol produced by the enzyme reaction in the samples (1) to (6) of the plots constituting the graph of FIG.
  • saccharified products obtained by hydrolysis of cellulose and hemicellulose are ethanol fermented.
  • saccharification of lignocellulosic biomass that is, hydrolysis
  • a pressurized hydrothermal reaction selective hydrolysis of hemicellulose proceeds
  • a saccharifying enzyme reaction hydrolysis of cellulose, which is a residue of pressurized hot water reaction, proceeds.
  • hydrolysis of cellulose which is a residue of pressurized hot water reaction
  • the primary saccharified solution resulting from the hydrolysis reaction By subjecting the primary saccharified solution resulting from the hydrolysis reaction to a solid acid catalytic reaction, it is sufficiently saccharified to produce monosaccharides such as glucose and xylose (secondary saccharification). Monosaccharides obtained by such a saccharification process are fermented to produce ethanol.
  • Glucose fermentation proceeds easily with conventionally known fermentation microorganisms such as natural yeast, but the microorganisms that can be used for fermentation of hemicellulose-derived xylose are limited, and the yield of ethanol is low.
  • a saccharification condition of hemicellulose is set so that a saccharified product suitable for the fermentation can be obtained by utilizing a recently developed microorganism having excellent xylose fermentability.
  • the device 5 hydrolyzes (saccharifies) a partially saccharified product derived from cellulose
  • the second catalytic reaction device 7 hydrolyzes (saccharifies) a partially saccharified product derived from hemicellulose.
  • the fermentation apparatus includes a first fermentation apparatus 6 that ferments a saccharified product derived from cellulose to produce ethanol, and a second fermentation apparatus 8 that ferments a saccharified product derived from hemicellulose to produce ethanol, which are generated from each.
  • the fermentation products F1 and F2 are distilled by the distillation apparatus 9 to separate and purify ethanol.
  • the pressurized hot water reactor 1 includes a pump 1a, a heater 1b, a water amount adjusting valve 1c, a pressure-resistant reaction tank 1d, and a control device 1e.
  • the pump 1a pressurizes and heats water supplied from the outside.
  • the heater 1b heats the pressurized water flowing from the pump 1a to 150 to 230 ° C., preferably about 200 to 230 ° C., in accordance with a temperature control signal input from the control device 1e, and pressurizes hot water W ′ (pressure Hot water in a subcritical state of about 0.47 to 2.8 MPa, preferably about 1.6 to 2.8 MPa), which is supplied to the reaction tank 1d containing the biomass via the water amount adjusting valve 1c.
  • hot water W ′ pressure Hot water in a subcritical state of about 0.47 to 2.8 MPa, preferably about 1.6 to 2.8 MPa
  • the water amount adjusting valve 1c is an electronic control valve whose opening degree can be adjusted in accordance with a flow rate control signal input from the control device 1e, and the flow rate of the pressurized hot water W ′ supplied from the heater 1b to the reaction tank 1d. Adjust appropriately.
  • the control device 1e adjusts the temperature and flow rate of the pressurized hot water W ′ supplied to the reaction tank 1d by the temperature control signal output to the heater 1b and the water amount control signal output to the water amount adjustment valve 1c.
  • the biomass hydrolysis conditions in the reaction tank 1d are controlled as described above.
  • the hemicellulose contained in the biomass is selectively partially decomposed and solubilized to become a hydrous liquid of polysaccharides containing oligosaccharides.
  • the reaction product is a mixture of a water-containing liquid containing oligosaccharides derived from hemicellulose and a solid residue containing cellulose and lignin that do not decompose.
  • the supply form of pressurized hot water in the reaction tank 1d may be a continuous water supply system or a batch system, but is configured so that the pressurized hot water can stay in the tank for about 5 to 120 minutes. If pressurized hot water of about 120 to 200 ° C. is supplied before the above-mentioned pressurized hot water is supplied, lignin can be easily separated.
  • the cooler 3 cools the high-temperature solid residue S after the pressurized hot water reaction, adjusts it to a temperature suitable for the subsequent enzyme reaction, and generally cools it to about 50 to 100 ° C. Energy efficiency is improved by providing a heat exchanger that recovers thermal energy from the refrigerant used in the cooler 3 and makes it available for heating water in the pressurized hot water reactor 1.
  • the solid residue S adjusted to an appropriate temperature by the cooler 3 is supplied to the enzyme reaction device 4.
  • the enzyme reaction apparatus 4 is equipped with a stirrer and a temperature control mechanism, and cellulase, which is a saccharifying enzyme, is added to and mixed with the solid residue S whose water content has been adjusted so that stirring is possible as necessary, so that the enzyme is activated at a temperature.
  • cellulase which is a saccharifying enzyme
  • cellulose in the solid residue S is hydrolyzed by the action of cellulase, and a degradation product mainly composed of a suspended polysaccharide or cellobiose (a dimer of glucose) that is a partial saccharified product of cellulose. Is obtained as the primary saccharified solution C1.
  • Cellulase is generally known as an assembly of a plurality of types of saccharifying enzymes, and contains ⁇ -glucanase as a main component.
  • ⁇ -glucanase is known as a saccharifying enzyme that hydrolyzes cellulose into insoluble suspended polysaccharide (having a higher degree of polymerization than water-soluble oligosaccharide) and water-soluble oligosaccharide (glucose dimer to hexamer).
  • the primary saccharified liquid C1 contains a water-soluble oligosaccharide (mainly cellobiose) and a water-insoluble suspended polysaccharide, and is a fluid liquid in which the suspended polysaccharide is dispersed in a water-containing liquid of the water-soluble oligosaccharide.
  • the suspended polysaccharide is a partially decomposed product of cellulose, specifically, suspended particles containing cellohexaose crystals that are a glucose polymer having a polymerization degree of 7 or more and a hexamer of glucose. It can be decomposed into glucose by a catalytic reaction.
  • the temperature of the enzyme reaction apparatus 4 is appropriately adjusted within the optimum pH and the optimum temperature range of about 40 to 90 ° C. so as to obtain an appropriate enzyme activity according to the saccharifying enzyme to be used.
  • the temperature of the solid residue S introduced into the enzyme reaction apparatus 4 is about 90 to 100 ° C., and the temperature is appropriately adjusted by the cooler 3 in the previous stage. .
  • the cooling capacity of the cooler can be reduced.
  • the specific surface area of the solid residue increases and the saccharification of the saccharifying enzyme is facilitated.
  • the amount used can be reduced, and the saccharification efficiency in the cellulosic saccharification process including the subsequent solid acid catalysis is improved.
  • the primary saccharified solution C1 of cellulose produced in the enzyme reaction apparatus 4 is supplied to the first catalytic reaction apparatus 5.
  • a separation device such as a belt press may be provided in front of the first catalytic reactor 5 as a means for removing solid residues (lignin and the like) that may remain in the primary saccharified liquid C1.
  • the first catalytic reaction device 5 includes a first mixing device 5a having a temperature control mechanism and a first solid-liquid separation device 5b, and the primary saccharified solution C1 is 90 ° C. or higher and lower than 120 ° C. in the first mixing device 5a. Mix and stir with solid acid catalyst X at temperature.
  • the oligosaccharide and the suspended polysaccharide of the primary saccharified liquid C1 are hydrolyzed by the action of the solid acid catalyst X to produce glucose (monosaccharide constituting cellulose), and the reaction product contains glucose as a main component.
  • a mixture of the secondary saccharified solution C2 and the solid acid catalyst X is obtained.
  • the reaction product that has finished the hydrolysis reaction in the first mixing device 5a is charged into the first solid-liquid separation device 5b and separated into solid and liquid. Thereby, the secondary saccharified solution C2 containing glucose as a main component is separated as a supernatant and sent to the first fermentation apparatus 6.
  • the solid acid catalyst X that has settled and separated is recovered and then returned to the first mixing device 5a to be used again.
  • the 1st solid-liquid separation apparatus 5b should just be what can generally be used as a sedimentation tank.
  • the purified product F1 discharged from the first fermentation apparatus 6 is supplied to the distillation apparatus 9 and distilled to recover purified ethanol.
  • the fermentation product F1 contains a solid substance, and may be distilled as it is without removing it. If necessary, if a filtration device for removing solids (lignin, fermentation microorganisms, etc.) from the fermentation product F1 is provided, only the liquid product can be distilled.
  • the solid matter separated from the fermentation product F1 by filtration or the like may be introduced into the biomass saccharification step.
  • the hemicellulose-derived primary saccharified solution H1 separated by the solid-liquid separator 2 is supplied to the second catalytic reaction device 7.
  • a separation device for removing a solid dispersion (such as lignin) that may be mixed in the primary saccharified solution H1 may be provided in the front stage of the second catalytic reaction device 7.
  • the second catalytic reaction device 7 includes a second mixing device 7a having a temperature control mechanism and a second solid-liquid separation device 7b, and the primary saccharified solution H1 is 90 ° C. or higher and lower than 120 ° C. in the second mixing device 7a. Mix and stir with solid acid catalyst X at temperature.
  • the hemicellulose-derived oligosaccharides in the primary saccharified solution H1 are hydrolyzed by the action of the solid acid catalyst X to produce monosaccharides including xylose, arabinose (pentose sugar constituting hemicellulose), etc., and secondary saccharification including these Since the liquid H2 is obtained, the reaction product is a mixture of the secondary saccharified liquid H2 containing xylose and the solid acid catalyst X.
  • the solid acid catalyst X used in the second catalytic reactor 7 may be appropriately selected from the same or different from those usable in the first catalytic reactor 5.
  • the reaction product that has finished the hydrolysis reaction in the second mixing device 7a is charged into the second solid-liquid separation device 7b, and the solid acid catalyst X in the charged reaction product is allowed to settle, so that The secondary saccharified liquid H2 is separated and sent to the second fermentation apparatus 8.
  • the solid acid catalyst X that has settled and separated is recovered and then returned to the second mixing device 7a to be used again.
  • the second solid-liquid separator 7b may be anything that can generally be used as a precipitation tank.
  • the secondary saccharified solution H2 supplied from the second solid-liquid separation device 7b to the second fermentation device 8 is appropriately adjusted in water content and pH so as to be in a condition suitable for fermentation, inoculated with fermenting microorganisms, and the fermentation stock solution And xylose or the like is converted into ethanol by the action of the fermentation microorganism.
  • the fermentation microorganism used is a microorganism having xylose fermentation ability. It is preferable to add a nutrient source necessary for the propagation and activity of fermenting microorganisms. If necessary, a temperature control mechanism for maintaining the temperature at which fermentation is likely to proceed may be provided.
  • the purified product F2 discharged from the second fermentation apparatus 8 is supplied to the distillation apparatus 9 and distilled to recover purified ethanol.
  • Fermentation product F2 contains a solid substance and may be distilled as it is without removing it. If necessary, if a filtration device for removing solids (lignin, fermentation microorganisms, etc.) from the fermentation product F2 is provided, only the liquid product can be distilled.
  • the solid matter separated from the fermentation product F2 by filtration or the like may be introduced into the biomass saccharification step.
  • the distillation of the fermentation product F2 can be performed together with the fermentation product F1 obtained from the first fermentation apparatus 5 or individually.
  • the biomass B used as a raw material may be any lignocellulosic material, for example, woody materials such as wood, thinned wood, bark, herbs such as rice straw, wheat straw, rice husk, pulp, waste paper, cotton cloth, linen And fiber materials such as artificial cellulose materials, and in particular, plant materials such as wood materials containing hemicellulose can be efficiently saccharified and fermented. From the viewpoint of reaction efficiency, it is preferable to pulverize such biomass B into a granular or powder form in advance, and it is preferable to prepare particles having a particle diameter of about 5 mm or less.
  • pressurized hot water reactor 1 a certain amount of biomass supplied as a raw material from the outside is accommodated in the reaction tank 1d, the heater 1b is adjusted by a temperature control signal input from the controller 1e, and the pump 1a
  • the pressurized water flowing in from is heated to about 150 to 230 ° C., preferably about 190 to 210 ° C., to form pressurized hot water W ′ (for example, subcritical hot water having a pressure of about 1.3 to 1.9 MPa). It is supplied to the reaction tank 1d containing the biomass through the regulating valve 1c.
  • a reaction product obtained by treating a wooden material with a pressurized hydrothermal reactor contains a xylooligosaccharide partially decomposed and solubilized from hemicellulose.
  • a solid-liquid mixture containing a saccharide-containing liquid and a solid residue of cellulose and lignin that does not decompose is obtained.
  • Pressurized hot water may be supplied either continuously or batchwise. However, in the case of continuous water flow, the water flow rate should be set so that the residence time in the tank is 5 to 120 minutes. Adjust and react for about 10 to 120 minutes.
  • the reaction product of the pressurized hot water reactor 1 is supplied to the solid-liquid separator 2 and separated into the liquid portion of the hemicellulose decomposition product and the solid residue S containing cellulose and lignin.
  • the liquid part is supplied to the second catalytic reactor 7, and the solid residue S is supplied to the cooler 3.
  • the solid residue S supplied from the solid-liquid separator 2 is cooled and adjusted to a temperature suitable for the subsequent enzyme reaction.
  • the temperature of the solid residue S introduced into the enzyme reaction apparatus 4 is about 50 to 100 ° C. Adjust as appropriate.
  • the cooling capacity of the cooler can be reduced.
  • the solid residue S whose temperature has been adjusted by the cooler 3 is supplied to the enzyme reaction apparatus 4, and an aqueous liquid containing cellulase, which is a saccharifying enzyme, is added and mixed to maintain the enzyme at an active temperature.
  • the cellulose in the solid residue S is decomposed by the action of cellulase, and as a primary saccharified solution C1 of cellulose, a decomposition product mainly containing cellobiose (a dimer of glucose) which is a water-soluble oligosaccharide is obtained.
  • Cellulase is generally known as an assembly of a plurality of types of saccharifying enzymes, and contains ⁇ -glucanase as a main component.
  • ⁇ -glucanase is known as a saccharification enzyme that hydrolyzes cellulose into water-soluble oligosaccharides (glucose dimer to hexamer).
  • Cellobiose which is a part of the water-soluble oligosaccharide, is decomposed into glucose by ⁇ -glucosidase contained in cellulase.
  • the primary saccharified liquid C1 contains a water-soluble oligosaccharide and a water-insoluble suspended polysaccharide, and is a fluid liquid in which the suspended polysaccharide is dispersed in a water-containing liquid of the water-soluble oligosaccharide.
  • the saccharifying enzyme used in the enzyme reaction apparatus 4 a commercially available saccharifying enzyme can be used, and a commercially available saccharifying enzyme can also be used.
  • the normal saccharifying enzyme has the maximum enzyme activity at about 40 to 50 ° C.
  • the thermostable enzyme has the maximum enzyme activity at about 70 to 90 ° C. Therefore, the temperature of the enzyme reaction apparatus 4 depends on the saccharifying enzyme used. Depending on the conditions, appropriate adjustments may be made to obtain an appropriate enzyme activity.
  • the cooling capacity of the cooler can be reduced, and the temperature of the enzyme reaction device 4 and the temperature of the first mixing device 5a can be brought close to each other. Can improve.
  • the amount of saccharifying enzyme used in the enzyme reaction apparatus 4 is set at a rate of 0.025 to 0.15 g / g, preferably 0.5 to 0.1 g / g, based on the mass (dry) of the solid residue S. Unreacted cellulose can be substantially exhausted by the reaction for 12 to 72 hours, preferably 24 to 48 hours. When the solid residue before the enzyme reaction is subjected to beating treatment and defibration and softening, the enzyme reaction can be completed within about 12 hours using a small amount of enzyme of 0.25 g or less per gram of cellulose. The amount of monosaccharide from the suspended polysaccharide of the primary saccharified solution C1 is increased by the subsequent solid acid catalyzed reaction, and the monosaccharide recovery rate is increased.
  • the solid acid catalyst X to be used examples include inorganic solid acids such as zeolite, alumina and silica, and those in which acidic groups are introduced by sulfonation treatment of organic materials such as resins.
  • a powdered or particulate solid acid catalyst is used.
  • a sulfonated carbon type obtained by carbonizing an organic carbon material and then sulfonated is preferable.
  • the sulfonated carbon-based solid acid catalyst is an amorphous black solid (carbide) obtained by heat-treating organic carbon materials such as woods or herbs in an inert gas atmosphere such as nitrogen. It is obtained by heat treatment in order to add a sulfone group to the carbide skeleton and washing with hot water.
  • Carbonization and sulfonation may be performed at the same time, and the treatment temperature for carbonization and sulfonation is appropriately selected depending on the type of organic substance used.
  • the amount of the solid acid catalyst X used is preferably 5 to 30% by mass with respect to the primary saccharified liquid C1.
  • the reaction time may generally be about 2 to 10 hours.
  • the reaction product that has finished the hydrolysis reaction in the first mixing device 5a is supplied to the first solid-liquid separation device 5b, and the solid acid catalyst X in the reaction product is precipitated.
  • the secondary saccharified solution C2 mainly composed of glucose is separated as a supernatant, sent to the first fermentation apparatus 6, and the solid acid catalyst X separated by settling is recovered and then returned to the first mixing apparatus 5a to be used again.
  • the secondary saccharified solution C2 supplied from the first solid-liquid separation device 5b to the first fermentation device 6 is appropriately adjusted in water content and pH so as to be in a condition suitable for fermentation, and inoculated with fermenting microorganisms, and the fermentation stock solution
  • the glucose is converted into ethanol by the action of the fermentation microorganism.
  • known ethanol fermentation microorganisms such as yeast can be used. Examples include Zymomonas mobilis and Kluyveromyces marxianus.
  • flocculent yeast is advantageous in solid-liquid separation after fermentation because of good sedimentation, and it is advantageous for yeast to use amino acids and the like degraded by hydrolyzing enzymes of surrounding microorganisms as nutrient sources. Since it is also a form, it is useful for improving fermentation efficiency.
  • a nutrient source necessary for the propagation and activity of the fermenting microorganisms and adjust to an optimum pH.
  • essential nutrients such as phosphorus, nitrogen and vitamins, and required trace elements such as Co, Ni, and Zn are necessary, and yeast used for the production of biomass ethanol is The ability to synthesize vitamins or amino acids may be low or lacking.
  • yeast extract, polypeptone and the like can be generally used as a nutrient source for fermentation microorganisms to which such necessary components are added from the outside.
  • plant waste such as tea husk and coffee husk and algal crushed material may be used, and components contained in these cell protoplasts can be used as the nutrient source.
  • the saccharified product (glucose) concentration in the fermentation stock solution is adjusted to be about 1 to 20% by mass, preferably about 10% by mass.
  • the addition amount of the nutrient source for microorganisms (in terms of dry matter) is appropriately adjusted according to the type of fermenting microorganism, and is generally set to about 0.1 to 1% by mass, preferably about 0.2 to 0.5% by mass. Good.
  • the pH of the fermentation stock solution is adjusted to about 2.5 to 5.5, preferably about 3.0 to 5.5, inoculated with fermenting microorganisms at a rate of about 1 to 30 g / L, and a temperature of 30 to 37 ° C.
  • the fermentation proceeds by holding for about 2 to 48 hours.
  • ethanol can be produced at a rate of about 20 to 25 g-ethanol / (L ⁇ h) using a fermentation stock solution having a glucose concentration of about 10% by mass.
  • the fermentation product F1 that has undergone fermentation in the first fermentation apparatus 6 as described above is subjected to distillation apparatus 9 after removing solids (lignin, fermentation microorganisms, etc.) from the fermentation product F1 as necessary, by filtration or the like.
  • the ethanol is recovered by distillation at You may distill as it is, without removing solid content from fermentation product F1. You may introduce
  • the hemicellulose-derived primary saccharified liquid H1 separated by the solid-liquid separator 2 is supplied to the second catalytic reactor 7 and the solid acid catalyst X and the primary acid catalyst X at a temperature of 90 ° C. or higher and lower than 120 ° C. in the second mixing device 7a. Mix and stir.
  • the hemicellulose-derived oligosaccharide of the primary saccharified solution H1 and the polysaccharide which is a partial decomposition product are hydrolyzed by the action of the solid acid catalyst X to produce monosaccharides including xylose and arabinose (pentose sugar constituting hemicellulose).
  • a secondary saccharified solution H2 containing these is obtained.
  • the solid acid catalytic reaction In order to suppress a decrease in ethanol production efficiency in the subsequent fermentation in the second fermentation apparatus 8, it is preferable to perform the solid acid catalytic reaction at a temperature of 90 to 110 ° C, particularly around 100 ° C. At temperatures of 120 ° C. or higher, xylose decomposition tends to proceed.
  • the solid acid catalyst X used in the second catalytic reactor 7 can be appropriately selected from the same or different from those that can be used in the first catalytic reactor 5, and after the carbonization treatment of the woods or herbs, the sulfonation treatment is performed. Use of the resulting sulfonated carbon material is preferred.
  • the amount of the solid acid catalyst X to be used is preferably 5 to 30% by mass with respect to the primary saccharified liquid H1 as in the first catalytic reactor 5, and the reaction time may be generally about 1 to 5 hours.
  • the reaction product that has finished the hydrolysis reaction in the second mixing device 7a is charged into the second solid-liquid separation device 7b, where the solid acid catalyst X in the reaction product is allowed to settle, and the secondary saccharified solution H2 is used as a supernatant. To be separated. This is sent to the second fermentation apparatus 8. The solid acid catalyst X that has settled and separated is recovered and then returned to the second mixing device 7a to be used again.
  • the secondary saccharified liquid H2 is a monosaccharide liquid mainly composed of xylose.
  • the secondary saccharified solution H2 supplied from the second solid-liquid separation device 7b to the second fermentation device 8 is appropriately adjusted in water content and pH so as to be in a condition suitable for fermentation, inoculated with fermenting microorganisms, and the fermentation stock solution And xylose or the like is converted into ethanol by the action of the fermentation microorganism.
  • microorganisms having xylose fermentability include Pichia and Rhizopus oryzae.
  • Xylose-fermenting yeast tends to decrease the fermentation rate of xylose in the presence of glucose, but the use of a genetically modified yeast having xylose-fermenting ability can improve the efficiency of producing ethanol from semi-herulose secondary saccharified solution H2.
  • XR genes genes encoding enzymes that catalyze the conversion reaction from xylose to xylitol
  • XDH genes genes encoding enzymes that catalyze the conversion reaction from xylitol to xylulose
  • XK genes xylose and A genetically modified yeast introduced with a gene encoding an enzyme that catalyzes the conversion reaction from ATP to xylulose 5-phosphate and ADP can ferment xylose well in the presence of glucose.
  • Such genetically modified yeasts include, for example, industrial strain IR-2 (FERM BP-754), Type-II (baker yeast) and shochu 3 (association yeast), experimental strain D452-2, It is obtained by transforming the host organism using a vector in which the above gene is incorporated according to a general molecular biological technique, using yeast such as INVSc1 strain as the host organism (see US Patent Publication No. 2011 / 0027847A1), Alternatively, it can be obtained as a genetically modified yeast (N-WT strain, N-ARSdR strain, R-WT strain, R-ARSdR strain, MA-R4 strain) provided by the National Institute of Advanced Industrial Science and Technology. Saccharomyces yeast 424A (LNH-ST) (according to Dr.
  • flocculent yeast is advantageous in solid-liquid separation after fermentation because of good sedimentation, and it is advantageous for yeast to use amino acids and the like degraded by hydrolyzing enzymes of surrounding microorganisms as nutrient sources. Since it is also a form, it is useful for improving fermentation efficiency.
  • the yield of ethanol in fermentation with yeast having xylose fermentation ability is higher from glucose than that from xylose (see FIG. 2), and the fermentation rate is also related to the consumption rate of xylose than the consumption rate of glucose.
  • it is pure xylose, it will be completed in about several hours, and will be somewhat slower due to the coexistence of glucose.
  • There are other by-products in the hemicellulose-based saccharified liquid produced from cellulosic biomass and if the amount is large, the xylose fermentation rate is further reduced and the fermentation by-products are increased.
  • the yeast when the yeast is cultured using a medium containing a low-concentration diluted solution of the secondary saccharified liquid H2, the secondary saccharified liquid concentration of the medium is gradually increased when the propagated yeast is taken out and repeated. By this, the tolerance of the cultured yeast is gradually strengthened.
  • the fermentation product F2 that has undergone fermentation in the second fermentation apparatus 8 as described above is subjected to distillation apparatus 9 after removing solids (lignin, fermentation microorganisms, etc.) from the fermentation product F2 as necessary, by filtration or the like. Purified ethanol is recovered by distillation in You may distill as it is, without removing solid content from fermentation product F2.
  • the solid separated from the fermentation product F2 may be introduced into the biomass saccharification step.
  • the distillation of the fermentation product F2 can be performed together with or separately from the fermentation product F1 obtained from the first fermentation apparatus 6.
  • Solid acid catalysts include powders and pellets.
  • the solid acid catalyst may be made of a mesh or the like through which the liquid flows easily.
  • the solid acid catalyst can be held in the permeable container and fixed in the primary saccharified liquids H1 and C1, and the primary saccharified liquid can be flowed between the solid acid catalyst pellets by flowing the primary saccharified liquid. .
  • By adopting such a fixed bed type solid acid catalyst it is possible to simplify the apparatus configuration relating to solid-liquid separation in the first catalytic reaction apparatus and the second catalytic reaction apparatus.
  • each of the first fermentation apparatus 6 and the second fermentation apparatus 8 when microorganisms such as Clostridium acetobutylicum, Clostridium begerinki, Clostridium auranticylicum, Clostridium tetanomorphum are used as fermentation microorganisms, butanol or the like is obtained by fermentation.
  • microorganisms such as Clostridium acetobutylicum, Clostridium begerinki, Clostridium auranticylicum, Clostridium tetanomorphum are used as fermentation microorganisms, butanol or the like is obtained by fermentation.
  • Solid acid catalyzed reaction of primary saccharified solution 75 g of a carbon-based solid acid catalyst obtained by sulfonating amorphous carbide was prepared, and the temperature was maintained at 90 to 100 ° C. in addition to 500 g of the primary saccharified solution obtained by performing the above-mentioned pressurized hot water reaction.
  • the solid acid catalyst reaction was carried out for 2 hours by using and stirring at a speed of 10 rpm.
  • the solid acid catalyst was removed by sedimentation to obtain 400 g of a secondary saccharified solution derived from hemicellulose.
  • xylose and glucose contained in the secondary saccharified solution were quantified by HPLC analysis, the xylose concentration was 0.75% by mass and the glucose concentration was 0.36% by mass.
  • a hemicellulose-derived secondary saccharified solution was prepared from herbaceous biomass, and the ratio of xylose and glucose contained was examined.
  • Sample (1) was 0.67
  • sample (2) was 0.66 and sample (3) were 0.47.
  • Samples of the secondary saccharified solutions (1) to (3) obtained above and purified monosaccharides are commercially available glucose reagent (sample (4)), xylose reagent (sample (5)), and glucose.
  • FIG. 2 is a graph showing the relationship between the xylose ratio of the fermentation stock solution of each sample and the ethanol yield at the end of fermentation using these results.
  • the present invention uses a resource that can efficiently saccharify and ferment hemicellulose contained in wood and other materials to produce ethanol when producing biomass ethanol using plant waste as biomass, and there is no risk of food price increases. Therefore, it can be treated economically and rationally, contributing to waste treatment and resource production, and can contribute to promoting recycling, protecting the environment, and solving energy problems.

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Abstract

La présente invention concerne un procédé et un dispositif permettant de saccharifier et de fermenter efficacement l'hémicellulose contenu dans des matériaux ligneux et similaires et de produire de l'éthanol qui peut être converti en éthanol de biomasse. De l'eau chaude sous pression est prévue pour agir sur une biomasse, l'hémicellulose contenue dans la biomasse est sélectivement dégradée, un catalyseur d'acide solide est prévu pour agir sur le produit de dégradation à une température de 90 à 110°C, et un produit saccharifié contenant du xylose est obtenu. Des microorganismes ayant la capacité de fermenter le xylose sont amenés à agir sur le produit saccharifié résultant, et de l' éthanol est produit.
PCT/JP2012/083561 2012-01-06 2012-12-26 Procédé et dispositif pour produire de l'éthanol WO2013103111A1 (fr)

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CN103555379A (zh) * 2013-11-05 2014-02-05 济南开发区星火科学技术研究院 一种纤维素液体燃料的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009195220A (ja) * 2008-01-24 2009-09-03 National Institute Of Advanced Industrial & Technology キシロース発酵能が優れた六炭糖・五炭糖同時発酵酵母およびそれを用いたエタノールの高効率生産方法
JP2010279255A (ja) * 2009-06-02 2010-12-16 Idemitsu Kosan Co Ltd バイオマスの糖化方法
JP2011068578A (ja) * 2009-09-24 2011-04-07 Ihi Corp バイオマス処理装置及び方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009195220A (ja) * 2008-01-24 2009-09-03 National Institute Of Advanced Industrial & Technology キシロース発酵能が優れた六炭糖・五炭糖同時発酵酵母およびそれを用いたエタノールの高効率生産方法
JP2010279255A (ja) * 2009-06-02 2010-12-16 Idemitsu Kosan Co Ltd バイオマスの糖化方法
JP2011068578A (ja) * 2009-09-24 2011-04-07 Ihi Corp バイオマス処理装置及び方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103555379A (zh) * 2013-11-05 2014-02-05 济南开发区星火科学技术研究院 一种纤维素液体燃料的制备方法

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