WO2015005410A1 - セルロース含有バイオマスからのアルコールの製造方法 - Google Patents
セルロース含有バイオマスからのアルコールの製造方法 Download PDFInfo
- Publication number
- WO2015005410A1 WO2015005410A1 PCT/JP2014/068385 JP2014068385W WO2015005410A1 WO 2015005410 A1 WO2015005410 A1 WO 2015005410A1 JP 2014068385 W JP2014068385 W JP 2014068385W WO 2015005410 A1 WO2015005410 A1 WO 2015005410A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alcohol
- cellulose
- containing biomass
- reverse osmosis
- osmosis membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Images
Classifications
-
- 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
- C12P7/16—Butanols
-
- 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
-
- 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
- C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
-
- 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 for producing alcohol from cellulose-containing biomass.
- the technology for producing bioethanol by fermentation is sustainable by reducing the consumption of petroleum resources and reducing carbon dioxide emissions against the background of rising global environmental awareness and rising crude oil prices. In recent years, it has attracted attention as a technology capable of producing various fuels and industrial raw materials.
- Non-patent Document 1 D. Humbird et al., “Process Design Design and Ecoconomics Conversion for Bioligs Cellulosic Biomass Etool” , NREL Report No. TP-5100-47764, May 2011, a method for producing ethanol from cellulose-containing biomass is disclosed.
- the cellulose-containing biomass is first pretreated with water vapor, acid, or alkali to facilitate the saccharification enzyme treatment in a later step (pretreatment step). ).
- the pretreated cellulose-containing biomass is supplied to the saccharification / fermentation tank, saccharification enzymes (for example, cellulase) and nutrients are added to the saccharification / fermentation tank, and then ethanol-fermenting bacteria are inoculated to simultaneously perform saccharification and fermentation. Perform (saccharification process and fermentation process). Thereby, a fermented liquor is obtained.
- the fermentation broth contains saccharification residue solids (mostly lignin and the like), ethanol fermentation bacteria, and the like.
- the obtained fermentation broth is distilled to purify and recover ethanol (distillation step).
- the saccharification step and the fermentation step are simultaneously performed, the number of necessary tanks can be reduced, so that the capital investment can be suppressed and the method is considered to be a competitive method.
- an aqueous sugar solution obtained by hydrolyzing cellulose-containing biomass is filtered to remove fermentation inhibitors contained in the aqueous sugar solution, and then a purified aqueous sugar solution is used. It is disclosed that ethanol fermentation is possible (Patent Document 1).
- the ethanol concentration obtained in the fermentation process depends on the amount of cellulose-containing biomass that can be charged into the saccharification / fermentation tank. Therefore, with the amount of cellulose-containing biomass that can be supplied to the saccharification / fermentation tank, it is difficult to increase the ethanol concentration obtained in the fermentation process to, for example, 5.5 wt% or more, and a large amount of distillation residue liquid is produced after the distillation process (for example, The amount of waste water treatment of this distillation residue is large.
- an ethanol fermentation liquid can be obtained from an aqueous sugar solution, but further improvement of the method for producing ethanol is disclosed. In order to achieve this, it is necessary to further improve the treatment of the distillation residue produced when the ethanol fermentation liquid obtained is distilled to recover ethanol.
- the present invention provides a method for producing alcohol from cellulose-containing biomass, which can greatly reduce the amount of wastewater that is required for wastewater treatment that occurs when alcohol is produced from cellulose-containing biomass.
- the present inventors diligently studied the above problems. As a result, in producing alcohol from cellulose-containing biomass, a step of removing saccharification residue solids contained in the saccharified product obtained by hydrolyzing cellulose-containing biomass, and an aqueous saccharide solution contained in the saccharified product as a fermentation raw material
- a step of removing saccharification residue solids contained in the saccharified product obtained by hydrolyzing cellulose-containing biomass, and an aqueous saccharide solution contained in the saccharified product as a fermentation raw material By performing the process of removing the alcohol-fermenting microorganisms from the culture broth containing the alcohol-fermenting microorganisms obtained at a suitable stage, the distillation residue liquid after the distillation process can be treated with a reverse osmosis membrane. It was found that the amount of wastewater generated during production can be greatly reduced.
- the present invention has been completed based on such findings.
- Step (1) a step of pretreating cellulose-containing biomass
- Step (2) a step of saccharifying the cellulose-containing biomass after the pretreatment obtained in the step (1) with a saccharifying enzyme
- Step (3) a step of removing saccharification residue solids from the saccharification product obtained in Step (2)
- Step (4) a step of culturing an alcohol-fermenting microorganism using the aqueous sugar solution obtained in Step (3) as a fermentation raw material
- Step (5) a step of removing the alcohol-fermenting microorganisms from the culture solution containing the alcohol-fermenting microorganisms obtained in the step (4).
- Step (6) a step of distilling the alcohol fermentation liquor obtained in step (5) to recover the alcohol
- Step (7) Step of filtering the distillation residue liquid obtained in Step (6) through a reverse osmosis membrane
- Step (8) Step of draining the non-permeated liquid obtained in Step (7),
- the step (5) is a step of filtering the culture solution containing the alcohol-fermenting microorganisms obtained in the step (4) through a microfiltration membrane.
- [3] The method for producing alcohol from cellulose-containing biomass according to [1] or [2], wherein the step (3) is a step by a filter press.
- the saccharified residue solid in the saccharified product is removed in advance in step (3)
- the alcohol fermentation microorganisms in the culture solution are removed in advance in the step (5), so that the alcohol with a small amount of impurities is obtained.
- a fermentation broth is obtained.
- FIG. 1 It is a figure which shows the flow of the manufacturing process of alcohol from the cellulose containing biomass by this invention. It is a figure which shows the ethanol manufacturing process flow from the cellulose containing biomass of the comparative example 1. It is a figure which shows the ethanol manufacturing process flow from the cellulose containing biomass of the comparative example 2. FIG. It is a figure which shows the ethanol manufacturing process flow from the cellulose containing biomass of the comparative example 3. It is a figure which shows the ethanol manufacturing process flow from the cellulose containing biomass of Example 1. FIG. It is a figure which shows the ethanol manufacturing process flow from the cellulose containing biomass of Example 2. FIG.
- the alcohol is an alcohol produced from sugar by microbial fermentation, and is not particularly limited as long as it is an alcohol that is isolated and purified in a distillation step.
- Specific examples include methanol, ethanol, propanol, and butanol.
- propanol may be 1-propanol or 2-propanol.
- the butanol may be 1-butanol, 2-methyl-1-propanol, 2-butanol, or 2-methyl-2-propanol.
- Cellulose-containing biomass refers to natural resources that contain cellulose components. Specifically, herbaceous biomass such as bagasse, switchgrass, napiergrass, Eliansus, corn stover, beet pulp, cottonseed husk, palm husk, rice straw, straw, bamboo, straw, birch, beech, etc. Woody biomass such as wood and waste building materials, and biomass derived from aquatic environment such as algae and seaweed. These cellulose-containing biomass contains cellulose or hemicellulose, which is a polysaccharide obtained by dehydrating and condensing sugar, and can be used as a fermentation raw material by hydrolyzing such polysaccharide.
- herbaceous biomass such as bagasse, switchgrass, napiergrass, Eliansus, corn stover, beet pulp, cottonseed husk, palm husk, rice straw, straw, bamboo, straw, birch, beech, etc.
- Woody biomass such as wood and waste building materials, and biomass derived from aquatic environment such as algae and seaweed.
- Sugars are generally classified according to the degree of polymerization of monosaccharides, monosaccharides such as glucose and xylose, oligosaccharides obtained by dehydration condensation of 2 to 9 monosaccharides, and polysaccharides obtained by dehydration condensation of 10 or more monosaccharides. Classified as a saccharide.
- Step (1) the cellulose-containing biomass is pretreated to obtain a pretreated product.
- the hydrolysis efficiency of the cellulose-containing biomass can be improved by pre-treating the cellulose-containing biomass in advance before being processed in the saccharification step described below.
- the pretreatment method of cellulose-containing biomass is not particularly limited, and a conventionally known pretreatment method can be used. Examples of the pretreatment method include fine pulverization treatment, hydrothermal treatment, ammonia treatment, alkali treatment, acid treatment, sulfuric acid treatment, dilute sulfuric acid treatment, acetic acid treatment, caustic soda treatment, explosion treatment, subcritical water treatment, and steaming treatment. However, any of these may be used, or a combination of these may be used.
- Step (2) Saccharification step
- the pretreated product obtained in the step (1) is hydrolyzed to monosaccharides or oligosaccharides obtained by dehydration condensation of 2 to 9 monosaccharides. Thereby, a saccharification processed material is obtained.
- a saccharifying enzyme is preferably used for hydrolysis of the pretreated product.
- the reaction conditions for hydrolysis with a saccharifying enzyme may be performed according to the preferable reaction conditions for a saccharifying enzyme.
- the pH of the hydrolysis reaction is preferably in the range of 3 to 7, more preferably 4 to 5.5, and even more preferably around pH 5.
- the reaction temperature is preferably 40 to 70 ° C, more preferably around 50 ° C.
- the saccharifying enzyme refers to an enzyme component having an activity of hydrolyzing cellulose and / or hemicellulose to saccharify, or an enzyme component that assists hydrolysis of cellulose and / or hemicellulose.
- a cellulase derived from a filamentous fungus as the saccharifying enzyme.
- the cellulase derived from filamentous fungi includes Trichoderma, Aspergillus, Cellulomonas, Clostridium, Streptomycins, Humimola, and Humikola. And cellulases derived from microorganisms such as genus Irpex, genus Mucor, genus Talaromyces, genus Phanerochaete, white rot gold, and brown rot fungi.
- a cellulase derived from a mutant strain in which cellulase productivity has been improved by subjecting these microorganisms to a mutation treatment or irradiation with ultraviolet rays or the like may be used.
- these filamentous fungus-derived cellulases it is preferable to use Trichoderma genus-derived cellulase, which produces a large amount of enzyme components with high specific activity in the hydrolysis of cellulose.
- Trichoderma-derived cellulase is an enzyme composition mainly composed of cellulase derived from Trichoderma microorganisms.
- the microorganism of the genus Trichoderma is not particularly limited, but Trichoderma reesei (Trichoderma reesei) is preferable, and specifically, Trichoderma reesei QM9414 (Trichoderma reesei QM9414), Trichoderma reesei QM9123 (Trichoderma reesei QM9123) reeseiRut C-30), Trichoderma reesei PC3-7 (Trichoderma reesei PC3-7), Trichoderma reesei CL-847 (Trichoderma reeseiCL-847), Trichoderma reesei MCG77 (Trichoderma MCe 77) Ma reesei MCG80 (Trichoderma reeseiMCG80), can be exempl
- saccharifying enzymes examples include cellobiohydrolase, endoglucanase, exoglucanase, ⁇ -glucosidase, xylanase, and xylosidase.
- One or more kinds of saccharifying enzymes may be used.
- an enzyme mixture containing a plurality of types of the above saccharifying enzymes is preferable.
- Cellobiohydrase is a general term for cellulases that start hydrolysis of cellulose from the terminal portion and release cellobiose, and an enzyme group belonging to cellobiohydrase as EC number: EC 3.2.1.91. Is described. Cellulolytic activity can be measured from the amount of glucose liberated when an enzyme is allowed to act on cellulose as a substrate, and specific methods are described in “Pure & Appl. Chem., Vol. 59, No. 2”. 257-268 page, "FILTER PAPER ASSAY FOR SACCHARIFYING CELLULASE" can be used.
- Endoglucanase is a general term for cellulases having an activity of hydrolyzing from the central part of a cellulose molecular chain, and EC numbers: EC 3.2.1.4, EC 3.2.1.6, EC 3.2.1.39. EC 3.2.1.73 describes an enzyme group belonging to endoglucanase.
- Cellulolytic activity can be measured from the amount of reducing sugar released when an enzyme is allowed to act using carboxymethylcellulose (CMC) as a substrate.
- CMC carboxymethylcellulose
- Exoglucanase is a general term for cellulases that hydrolyze from the ends of cellulose molecular chains, and the enzyme groups belonging to exoglucanase are described as EC numbers: EC3.2.1.74 and EC3.2.1.58. ing.
- ⁇ -glucosidase is a general term for cellulases that hydrolyze cellooligosaccharides or cellobiose, and describes an enzyme group belonging to ⁇ -glucosidase as EC number: EC 3.2.1.21.
- Cellobiose degrading activity (hereinafter also referred to as “BGL activity”) can be measured from the amount of glucose released when an enzyme is allowed to act on cellobiose as a substrate.
- BGL activity Cellobiose degrading activity
- Xylanase is a general term for cellulases characterized by acting on hemicellulose or especially xylan, and an enzyme group belonging to xylanase is described as EC number: EC3.2.1.8.
- Xylosidase is a general term for cellulases characterized by acting on xylo-oligosaccharides, and an enzyme group belonging to xylosidase is described as EC number: EC 3.2.1.37.
- saccharifying enzymes are separated by known methods such as gel filtration, ion exchange, and two-dimensional electrophoresis, and amino acid sequences (N-terminal analysis, C-terminal analysis, mass spectrometry) of the separated components are identified and identified by comparison with a database. can do.
- the culture solution may be used as it is as a saccharifying enzyme (crude enzyme), or the enzyme group purified by a known method and saccharified. It may be used as an enzyme (a filamentous fungus-derived cellulase mixture).
- a substance added with substances other than enzymes such as protease inhibitors, dispersants, dissolution promoters and stabilizers is used as a saccharifying enzyme (cellulase preparation) May be.
- a crude enzyme product is preferably used as the filamentous fungus-derived cellulase.
- the crude enzyme product is derived from the culture supernatant obtained by culturing the microorganism for an arbitrary period in a medium adjusted so that the microorganism of the genus Trichoderma produces cellulase.
- the medium components to be used are not particularly limited, but in order to promote the production of cellulase, a medium to which cellulose is added can be generally used.
- the culture supernatant is preferably used as it is or from the culture supernatant obtained by removing Trichoderma cells.
- the weight ratio of each enzyme component in the crude enzyme product is not particularly limited.
- the culture solution derived from Trichoderma reesei contains 50 to 95% by weight of cellobiohydrase, and the rest.
- the endoglucanase, ⁇ -glucosidase, etc. are contained in the components.
- Trichoderma microorganisms produce a strong cellulase component in the culture solution, while ⁇ -glucosidase has low ⁇ -glucosidase activity in the culture solution because it is retained in the cell or on the cell surface. Therefore, you may add a different type or the same type of beta-glucosidase to the crude enzyme product.
- ⁇ -glucosidase derived from Aspergillus can be preferably used.
- ⁇ -glucosidase derived from the genus Aspergillus include Novozyme 188 commercially available from Novozyme.
- a method of adding a heterologous or homologous ⁇ -glucosidase to a crude enzyme product a gene is introduced into a Trichoderma microorganism, and the Trichoderma microorganism that has been genetically modified so as to be produced in the culture solution is cultured. A method of isolating the culture solution may also be used.
- the saccharified product obtained in step (2) contains an aqueous saccharide solution and saccharification residue solids.
- the saccharification residue solid refers to a solid that does not dissolve in water, that is, a component that scatters light when present in water. For example, it refers to a substance that precipitates in an ultrahigh-speed centrifugation state of 10,000 G, and a colloid component substance that does not settle in an ultrahigh-speed centrifugation state but the supernatant portion forms a colloidal state.
- Step (3) Solid-liquid separation step
- the saccharification product obtained in step (2) is separated into an aqueous saccharide solution and a saccharification residue solid, and the saccharification residue solid is removed from the saccharification treatment.
- a conventionally known general separation apparatus can be used as a method for separating the saccharified product in the step (3).
- the separation device include a screw decanter, a separation plate type centrifuge, a centrifugal type such as a shear press type centrifuge, a vertical type centrifuge, a filter press, a pressure filter, a centrifugal filter, a screw press, and a belt.
- Examples include a pressure filtration type such as a press, a suction filter type device such as a belt filter, a precoat filter, a drum type filtration filter, and a vacuum filtration filter. These separation devices may be used alone or in combination. Among these, in particular, a pressure filtration type filter press is used from the viewpoint that the recovery rate of the aqueous sugar solution is excellent and more sugar components can be recovered by one solid-liquid separation and a clear filtrate can be easily obtained. It is preferable.
- the filter press is a pressure filtration treatment method using a filter cloth using a woven fabric or a non-woven fabric, and can be easily performed using a commercially available filter cloth and apparatus.
- the pressing pressure when performing the filter press is not particularly limited, but is about 0.01 to 2 MPa, preferably about 0.05 to 1 MPa.
- the type of the filter press may be a vertical type or a horizontal type.
- the liquid feeding method may be carried out with a pump or may be pumped with compressed gas.
- PNEUMAPRESS registered trademark
- Lars Filter registered trademark
- AUTOPAC registered trademark
- Step (4) Fermentation step
- alcohol fermentation microorganisms are cultured using the aqueous sugar solution obtained in step (3) as a fermentation raw material to obtain a culture solution containing alcohol fermentation microorganisms.
- the aqueous sugar solution obtained in the step (3) contains monosaccharides that can be used by alcohol-fermenting microorganisms such as glucose and xylose as a carbon source, by using this aqueous sugar solution as a fermentation raw material, the alcohol-fermenting microorganisms To obtain a culture solution that produces alcohol and contains alcohol-fermenting microorganisms.
- Alcohol-fermenting microorganisms only have to have the ability to produce alcohol from sugar.
- yeasts such as baker's yeast often used in the fermentation industry
- bacteria such as Escherichia coli and coryneform bacteria, filamentous fungi, actinomycetes and the like can be mentioned.
- the alcohol-fermenting microorganism to be used may be one isolated from the natural environment, or one partially modified in nature by mutation or genetic recombination.
- pentose such as xylose
- alcohol-fermenting microorganisms with enhanced pentose metabolic pathway can be preferably used.
- a liquid medium containing a nitrogen source, inorganic salts, and if necessary, organic micronutrients such as amino acids and vitamins as appropriate is preferably used.
- Nitrogen sources include ammonia gas, aqueous ammonia, ammonium salts, urea, nitrates, and other supplementary organic nitrogen sources such as oil cakes, soybean hydrolysates, casein degradation products, other amino acids, vitamins, Corn steep liquor, yeast or yeast extract, meat extract, peptides such as peptone, various fermented cells and hydrolysates thereof are used.
- inorganic salts phosphates, magnesium salts, calcium salts, iron salts, manganese salts, and the like can be appropriately added.
- the nutrient when an alcohol-fermenting microorganism requires a specific nutrient for growth, the nutrient may be added as a standard or a natural product containing it. Moreover, you may use an antifoamer as needed.
- Alcohol-fermenting microorganisms are usually cultured in the range of pH 4-8 and temperature 20-50 ° C.
- the pH of the culture solution is usually adjusted to a predetermined value within a pH range of 4 to 8 with an inorganic or organic acid, an alkaline substance, urea, calcium carbonate, ammonia gas, or the like.
- nitrogen or carbon dioxide may be aerated.
- oxygen is added to the air to maintain the oxygen concentration at 21% or higher, or the oxygen supply required by using means such as pressurizing the culture, increasing the stirring speed, and increasing the aeration rate. You can get speed.
- the fermentation method may be batch, fed-batch or continuous fermentation that recycles microorganisms.
- it is important to provide a step of removing microorganisms from the fermentation broth before the distillation step of the fermentation broth containing the microorganisms obtained in the fermentation step.
- Step (5) Microbe removal step
- the alcohol-fermenting microorganism is removed from the culture solution containing the alcohol-fermenting microorganism obtained in step (4) to obtain an aqueous solution (alcohol fermentation solution) containing alcohol.
- the removal of the alcohol-fermenting microorganism from the culture solution may be a method that can be separated into the alcohol-fermenting microorganism and the alcohol-fermenting solution.
- Examples of the method for removing alcohol-fermenting microorganisms from the culture liquid include, for example, a method of performing centrifugation using a separation plate centrifuge, a shear press type centrifuge, a vertical centrifuge, and the like, and a culture liquid and alcohol using a microfiltration membrane.
- Examples thereof include a method for separating from a fermenting microorganism, or a method for continuous fermentation by combining the fermentation method as in the above step (4) and the separation method.
- the separation method of the culture solution and alcoholic microorganisms using a microfiltration membrane is preferably applied.
- the format of the microfiltration membrane is not particularly limited as long as it is a format in which filtration is performed by sweeping over the membrane surface, a flat membrane, a hollow fiber membrane, Any of a tubular film or the like may be used.
- the material of the membrane is, for example, ceramic such as alumina, titania, zirconia, inorganic membrane such as glass, metal, or cellulose acetate, nitrocellulose, aliphatic polyamide, polysulfone, polyolefin, polyacrylonitrile, poly Examples of the organic film include ether sulfone, polyvinyl chloride, polyvinyl alcohol, and fluorine polymers.
- the conditions for filtration of the culture solution using a microfiltration membrane will be described.
- the greater the membrane surface velocity for conducting the sweep on the separation membrane surface the greater the sweep effect on the membrane surface.
- the pressure loss increases, the gel layer is consolidated in the vicinity of the membrane, and the membrane permeation flux and the recovery rate of the alcoholic fermentation broth in the culture solution decrease.
- the film surface speed is suitably 0.5 to 3 m / s.
- the transmembrane pressure difference during filtration of the culture solution through a microfiltration membrane refers to the average transmembrane pressure difference between the inlet and outlet, and is usually preferably 2.0 kgf / cm 2 or less, more preferably 0.2 to 1.5 kgf / cm 2 . If the transmembrane pressure difference is 0.2 kgf / cm 2 or more, it is possible to suppress a decrease in the permeation flux and to prevent the processability from deteriorating. In addition, when the transmembrane pressure difference is 2.0 kgf / cm 2 or less, it is possible to suppress membrane clogging due to consolidation of the gel layer on the membrane surface and the like, and it is possible to suppress a decrease in permeation flux. Further, the method for applying the transmembrane pressure difference may be a stock solution side pressurization method, a permeate side decompression method, or a combination thereof.
- the operating temperature during the filtration of the culture solution with a microfiltration membrane is usually 0 to 40 ° C, preferably 5 to 30 ° C. If the operating temperature is 0 ° C. or higher, it is possible to suppress an increase in the viscosity of the culture solution, and thus it is possible to suppress a decrease in the membrane permeation flux. Moreover, if the operation temperature is 40 ° C. or lower, it is possible to suppress deterioration of the properties of the culture solution.
- Step (6) Distillation step
- the alcohol fermentation liquid obtained in the step (5) is distilled and separated into the purified alcohol and the distillation residue liquid, thereby recovering the purified alcohol.
- a conventionally known distillation method can be used for the distillation of the alcohol in the step (6).
- the alcohol when the alcohol is ethanol, the ethanol is an azeotrope with water (for example, the composition of the azeotropic ethanol is 95.6% by weight of ethanol and about 4.4% by weight of water at normal pressure). Therefore, the anhydride cannot be obtained by ordinary distillation. Therefore, when absolute ethanol is obtained from azeotropic ethanol by distillation, a method in which azeotropic distillation is performed using an azeotropic solvent such as pentane or cyclohexane, and a method in which extraction distillation is performed using an extraction solvent such as ethylene glycol are conventional. Has been done. In the case of an azeotropic mixture formed by two components of ethanol and water, in the extractive distillation method, only the ethanol can be distilled by changing the gas-liquid equilibrium due to the effect of the extraction solvent.
- Step (7) Reverse Osmosis Membrane Step
- the distillation residue liquid obtained in the step (6) is filtered to be separated into a permeate and a non-permeate, and the non-permeate is recovered.
- the distillation residue liquid is preferably filtered using a reverse osmosis membrane.
- the alcohol fermentation liquid is distilled in a state where impurities such as solid substances and turbid substances are reduced. Therefore, the distillation residue liquid obtained in the step (6) has much less impurities than the distillation residue liquid obtained by the conventional process, and the COD of the distillation residue liquid is low. It is known that there is an upper limit for the COD concentration that can be biologically processed. According to the present invention, the compression rate of the distillation residue liquid obtained by filtering the distillation residue liquid obtained in step (6) through the reverse osmosis membrane in step (7) is higher than the distillation residue liquid obtained in the conventional process. Can also be high. Thereby, in the process (8) mentioned later, the quantity of the non-permeated liquid processed by waste water is reduced significantly.
- a reverse osmosis membrane is a membrane generally defined as “a membrane having a desalting function including monovalent ions” and has an ultra-fine void of about several angstroms to several nanometers. This membrane is thought to be used mainly for removing ionic components such as seawater desalination and ultrapure water production.
- a composite membrane using a cellulose acetate-based polymer as a functional layer (hereinafter, also referred to as a cellulose acetate-based reverse osmosis membrane) or a composite membrane using a polyamide as a functional layer (hereinafter referred to as a cellulose acetate-based reverse osmosis membrane) And a polyamide-based reverse osmosis membrane).
- cellulose acetate-based polymer organic acid esters of cellulose such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate and the like, or a mixture thereof and those using mixed esters can be mentioned. It is done.
- the polyamide includes a linear polymer or a crosslinked polymer having an aliphatic and / or aromatic diamine as a monomer.
- a polyamide-based reverse osmosis membrane is preferably used. This is because if a cellulose acetate reverse osmosis membrane is used for a long time, a part of the saccharifying enzyme used in the previous step, particularly a cellulase component, may permeate to decompose cellulose as a membrane material.
- the membrane form an appropriate form such as a flat membrane type, a spiral type, and a hollow fiber type can be used.
- Examples of the reverse osmosis membrane used in the present invention include ultra-low pressure type SUL-G10, SUL-G20, low pressure type SU-710, SU-720, SU, which are polyamide-based reverse osmosis membrane modules manufactured by Toray Industries, Inc.
- the filtration pressure is preferably in the range of 0.1 to 8 MPa. If the filtration pressure is 0.1 MPa or more, a decrease in the membrane permeation rate can be suppressed, and if the filtration pressure is 8 MPa or less, damage to the membrane can be suppressed. Also, if the filtration pressure is in the range of 0.5 to 7 MPa, the membrane permeation flux is high, the distillation residue liquid can be efficiently permeated, and there is little possibility of affecting the membrane damage. More preferably, it is in the range of 1 to 6 MPa.
- filtering a distillation residue solution through a reverse osmosis membrane means filtering the distillation residue solution through a reverse osmosis membrane without performing a treatment for reducing COD in the distillation residue solution in advance.
- filtering the distillation residue liquid through the reverse osmosis membrane means that the distillation residue liquid is subjected to solid-liquid separation treatment in advance in addition to filtering the distillation residue liquid directly through the reverse osmosis membrane.
- solid-liquid separation treatment in advance in addition to filtering the distillation residue liquid directly through the reverse osmosis membrane.
- filtration of the distillation residue liquid after the solid-liquid separation treatment is also performed by “Distillation residue liquid”. Is filtered through a reverse osmosis membrane ".
- a preferred embodiment of “filtering the distillation residue solution through a reverse osmosis membrane” includes filtering the distillation residue solution directly through a reverse osmosis membrane.
- the non-permeate obtained by filtering the distillation residue liquid through the reverse osmosis membrane is supplied to the subsequent step (8).
- the permeate permeated through the reverse osmosis membrane can be reused as process water.
- it can be used as water or steam in step (1), or as water in step (2) or step (4).
- Step (8) Wastewater treatment process
- the reverse osmosis membrane non-permeate obtained in the step (7) is drained so that it can be discharged out of the process.
- the non-permeate drainage treatment method include an anaerobic treatment step and an aerobic treatment step in which biological treatment is performed. In the present invention, an anaerobic treatment step and an aerobic treatment step are used.
- Biological treatment is a step of decomposing BOD and COD by microorganisms.
- An anaerobic treatment step includes, for example, a methane fermentation method, and an aerobic treatment step is, for example, an activated sludge method. Is mentioned.
- the non-permeated liquid is drained out of the process after being drained.
- the saccharification residue solids in the saccharification-treated product are removed in advance in the step (3) before fermenting the aqueous saccharide solution in the step (4), and the step (6 ),
- the alcoholic fermentation broth with a small amount of impurities can be distilled by previously removing the alcoholic fermentation microorganisms in the culture broth in step (5) before distilling the alcoholic fermentation broth.
- the amount of impurities in the distillation residue remaining after the alcohol is recovered from the alcohol fermentation liquid can be greatly reduced.
- the distillation residue liquid obtained in step (6) has much less impurities than the distillation residue liquid obtained by the conventional process, and the COD of the distillation residue liquid is low. Therefore, the compression rate by the reverse osmosis membrane can be increased. It is possible to greatly reduce the amount of non-permeated liquid to be drained in step (8).
- FIG. 2 to FIG. 6 are diagrams showing ethanol production process flows from cellulose-containing biomass of Examples or Comparative Examples.
- COD Measurement Method COD was measured according to the following procedure. 1. A 100 ml sample was accurately measured with a whole pipette. 2. 10 ml of 5% sulfuric acid and 10 ml of 0.02 / 5M potassium permanganate aqueous solution measured with a whole pipette were added and heated for 10 minutes. 3. 10 ml of 0.01M oxalic acid measured with a whole pipette was added. Titration with 4.02 / 5 M potassium permanganate aqueous solution.
- the seed culture intake was 10% of the fermentation medium.
- the fermentation process was maintained at a temperature of 30 ° C. and carried out for 1.5 days without aeration and stirring.
- the liquid obtained after such a fermentation process is called a culture liquid (including ethanol-fermenting yeast).
- Reference Example 8 Reverse Osmosis Membrane Process
- a reverse osmosis membrane a cross-linked wholly aromatic polyamide-based reverse osmosis membrane UTC80 (manufactured by Toray Industries, Inc.) is used, and the raw water temperature to be supplied is adjusted to 25 ° C. and the pressure of the high pressure pump 3 is adjusted to 3 MPa. And the permeate was removed.
- the compression rate was calculated as follows: volume on the non-permeate side / volume of raw water supplied ⁇ 100 (%).
- the upper limit of the compression of the wastewater by the reverse osmosis membrane process was set until the COD of the concentrated solution reached 100 g / L.
- FIG. 2 is a diagram showing an ethanol production method of this comparative example, which is an aspect of a conventional ethanol production method.
- 1 kg of cellulose-containing biomass was treated in the order of a pretreatment step, a saccharification step, and a fermentation step, and ethanol was purified from the resulting culture solution by a distillation step.
- the distillation residue liquid in the process shown in FIG. 2 became 5.8L.
- the COD was 89 g / L. Since this distillation residue liquid contained ethanol-fermenting yeast and saccharification residue solids, it could not be passed through a reverse osmosis membrane.
- the distillation residue liquid obtained in FIG. 2 was filter-pressed to obtain 4.8 L of a liquid from which saccharification residue solids were removed. This liquid was discharged after reducing COD in the wastewater treatment process.
- FIG. 3 is a diagram showing an ethanol production method of this comparative example.
- a reverse osmosis membrane process is applied after the filter press process in the process of FIG.
- the distillation residue liquid obtained in FIG. 2 was filter-pressed to obtain 4.8 L of a liquid from which saccharification residue solids were removed.
- the liquid after the filter press was filtered through a reverse osmosis membrane according to the operation shown in Reference Example 7, but the permeation rate (the rate at which the permeate emerges) suddenly decreased, and finally 100 ml or more due to clogging of the reverse osmosis membrane.
- the permeate could not be obtained. Therefore, the compression rate in the reverse osmosis membrane process was 97.9%, which was hardly compressed.
- FIG. 4 is a diagram showing an ethanol production method of this comparative example.
- a microfiltration step and a reverse osmosis membrane step are applied after the filter press step in the process of FIG.
- this liquid was passed through a microfiltration membrane to obtain 4.7 L of a liquid from which finer solids had been removed.
- the amount of the permeated liquid was improved as compared with Comparative Example 2. It reached 100 g / L.
- the COD concentration is higher than this, it can no longer be supplied to the wastewater treatment process. Therefore, the compression rate in the reverse osmosis membrane process is limited to 91.4%, and compression was hardly possible.
- FIG. 5 is a diagram showing the ethanol production method of this example.
- 1 kg of cellulose-containing biomass was treated in the order of a pretreatment step, a saccharification step, a filter press step, a fermentation step, and a microfiltration step, and the ethanol fermentation liquid obtained was purified by a distillation step.
- the distillation residue liquid in the process shown in FIG. 5 was 4.7 L
- the COD was 20 g / L, which were significantly lower than those of the above comparative examples.
- Example 1 As a process before the wastewater treatment process, Example 1 (FIG. 5) is the same process type and number of steps as Comparative Example 3 (FIG. 4), but in the reverse osmosis membrane process.
- the distillation residue liquid could be more efficiently compressed, and the COD of the distillation residue liquid could be greatly reduced.
- the liquid quantity of the non-permeate liquid used for a waste water treatment process was able to be reduced to about 1/4 rather than the comparative example 1 (FIG. 2).
- FIG. 6 is a diagram showing the ethanol production method of this example.
- a culture solution was obtained in the same manner as in Example 1, the obtained culture solution was centrifuged at 150 G to remove yeast in the culture solution and distilled.
- the distillation residue liquid was 4.5 L, and the COD was 25 g / L.
- this distillation residue was passed through a reverse osmosis membrane, 2.4 L of permeate was obtained in only 3 hours.
- the COD of the non-permeate obtained by passing the distillation residue through the reverse osmosis membrane was 50 g / L.
- Example 2 has the same process type and number of steps as Comparative Example 3 (FIG. 4), but in the reverse osmosis membrane process, While being able to compress more efficiently, COD of the distillation residue liquid could be reduced significantly. Moreover, in Example 2, the liquid quantity provided to a waste water treatment process was able to be reduced to about 1/3 rather than the comparative example 1 (FIG. 2).
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
[1] 以下の工程(1)~(8):
工程(1):セルロース含有バイオマスを前処理する工程、
工程(2):工程(1)で得られた前処理後のセルロース含有バイオマスを糖化酵素により糖化する工程、
工程(3):工程(2)で得られた糖化処理物から糖化残渣固形物を除去する工程、
工程(4):工程(3)で得られた糖水溶液を発酵原料としてアルコール発酵微生物を培養する工程、
工程(5):工程(4)で得られたアルコール発酵微生物を含む培養液からアルコール発酵微生物を除去する工程、
工程(6):工程(5)で得られたアルコール発酵液を蒸留し、アルコールを回収する工程、
工程(7):工程(6)で得られた蒸留残渣液を逆浸透膜に通じてろ過する工程、および
工程(8):工程(7)で得られた非透過液を排水処理する工程、
を含むセルロース含有バイオマスからのアルコールの製造方法。
[2] 工程(5)が、工程(4)で得られたアルコール発酵微生物を含む培養液を精密ろ過膜に通じてろ過する工程である、[1]に記載のセルロース含有バイオマスからのアルコールの製造方法。
[3] 工程(3)がフィルタプレスによる工程である、[1]または[2]に記載のセルロース含有バイオマスからのアルコールの製造方法。
[4] 工程(7)の逆浸透膜の透過液を工程(1)、(2)または(4)のプロセス水として再利用する、請求項[1]~[3]のいずれか1つに記載のセルロース含有バイオマスからのアルコールの製造方法。
[5]工程(7)が、工程(6)で得られた蒸留残渣液を直接逆浸透膜に通じてろ過する工程である、[1]~[4]のいずれか1つに記載のセルロース含有バイオマスからのアルコールの製造方法
[6]前記アルコールが、メタノール、エタノール、プロパノールまたはブタノールである、請求項[1]~[5]のいずれか1つに記載のセルロース含有バイオマスからのアルコールの製造方法。
本発明によるセルロース含有バイオマスからのアルコールの製造方法を図1に示す。本発明によるセルロース含有バイオマスからのアルコールの製造方法(以下、単に、アルコールの製造方法という場合もある。)について、以下、工程ごとに説明する。
工程(1)では、セルロース含有バイオマスを前処理して、前処理物を得る。セルロース含有バイオマスを、後述する糖化工程で処理する前に予め前処理を行うことで、セルロース含有バイオマスの加水分解効率を向上させることができる。セルロース含有バイオマスの前処理方法は、特に限定されるものではなく、従来から公知の前処理方法を用いることができる。前処理方法としては、例えば、微粉砕処理、水熱処理、アンモニア処理、アルカリ処理、酸処理、硫酸処理、希硫酸処理、酢酸処理、苛性ソーダ処理、爆砕処理、亜臨界水処理、蒸煮処理などが挙げられるが、これらのいずれを用いてもよいし、これらを組合せて使用してもよい。
工程(2)では、工程(1)で得られた前処理物を単糖または単糖が2~9個脱水縮合したオリゴ糖類にまで加水分解する。これにより、糖化処理物が得られる。前処理物の加水分解には、糖化酵素が好ましく使用される。
工程(3)では、工程(2)で得られた糖化処理物を糖水溶液と糖化残渣固形物とに分離して、糖化処理物から糖化残渣固形物を除去する。工程(3)で糖化処理物を分離する方法は、従来より公知の一般の分離装置を使用することができる。分離装置としては、例えば、スクリューデカンタ、分離板式遠心分離機、シャープレス型遠心分離機、縦型遠心分離機などの遠心分離型、フィルタプレス、加圧ろ過機、遠心ろ過機、スクリュープレス、ベルトプレスなどの加圧ろ過型、ベルトフィルター、プレコートフィルタ、ドラム型ろ過フィルター、真空ろ過フィルターなどの吸引ろ過型の装置などが挙げられる。これらの分離装置は、単独で用いてもよいし、複数を組み合わせて用いてもよい。これらの中でも、特に、糖水溶液の回収率に優れ1回の固液分離でより多くの糖成分を回収できると共に澄明な濾液を容易に得られるという観点から、加圧ろ過型のフィルタプレスを用いることが好ましい。
工程(4)では、工程(3)で得られた糖水溶液を発酵原料としてアルコール発酵微生物を培養して、アルコール発酵微生物を含む培養液を得る。工程(3)で得られた糖水溶液には、炭素源として、グルコース、キシロースなどアルコール発酵微生物が利用可能な単糖を含んでいるため、この糖水溶液を発酵原料として用いることで、アルコール発酵微生物を培養して、アルコールを生産しアルコール発酵微生物を含む培養液を得る。
工程(5)では、工程(4)で得られたアルコール発酵微生物を含む培養液からアルコール発酵微生物を除去して、アルコールを含む水溶液(アルコール発酵液)を得る。培養液からのアルコール発酵微生物の除去は、アルコール発酵微生物と、アルコール発酵液とに分離することができる方法であればよい。培養液からのアルコール発酵微生物の除去方法としては、例えば、分離板式遠心分離機、シャープレス型遠心分離機、縦型遠心分離機などにより遠心分離を行う方法や、精密ろ過膜による培養液とアルコール発酵微生物との分離方法、または上記工程(4)のような発酵方法と前記分離方法とを組み合わせて連続発酵する方法などが挙げられる。これらの中でも、精密ろ過膜による培養液とアルコール微生物との分離方法が好ましく適用される。
工程(6)では、工程(5)で得られたアルコール発酵液を蒸留し、精製されたアルコールと蒸留残渣液とに分離することで、精製されたアルコールを回収する。工程(6)におけるアルコールの蒸留は、従来から公知の蒸留方法を用いることができる。
工程(7)では、工程(6)で得られた蒸留残渣液をろ過することで透過液と非透過液とに分離し、非透過液を回収する。本発明においては、蒸留残渣液のろ過は、逆浸透膜を用いて行われることが好ましい。工程(4)で糖水溶液を発酵する前に、工程(3)で予め糖化処理物中の糖化残渣固形物を除去し、かつ工程(6)でアルコールを蒸留する前に、工程(5)で予め培養液中のアルコール発酵微生物を除去したアルコール発酵液にしている。そのため、アルコール発酵液は、固形物質や濁質物質などの不純物が低減された状態で蒸留されている。よって、工程(6)で得られる蒸留残渣液は、従来のプロセスで得られる蒸留残渣液よりも不純物が遙かに少なく、蒸留残渣液のCODは低い値となる。生物学的処理が可能なCOD濃度には上限値が存在することが知られている。本発明によれば、工程(7)において工程(6)で得られる蒸留残渣液を逆浸透膜に通してろ過することによる蒸留残渣液の圧縮率を、従来のプロセスで得られる蒸留残渣液よりも高くすることができる。これにより、後述する工程(8)において、排水処理される非透過液の量が大幅に削減される。
工程(8)では、工程(7)で得られた逆浸透膜の非透過液をプロセス外に排出できるように排水処理する。非透過液の排水処理方法としては、例えば、生物学的処理が行われる嫌気性処理工程や好気性処理工程などが挙げられる。本発明においては、嫌気性処理工程および好気性処理工程が用いられる。
エタノール濃度は、下記に示すガスクロマトグラフィー(GC)条件で、検出器により検出して算出し、標品との比較により定量した。
ガスクロマトグラフィー装置:Shimadzu GC-2010(株式会社島津製作所製)
キャピラリーカラム:TC-1(内径0.53mm、長さ15m、膜厚1.50μm(GL サイエンス社製)
検出器:水素炎イオン化検出器(FID)
CODの測定は、下記の手順で行った。
1. ホールピペットでサンプル100mlを正確に計った。
2. 5%の硫酸10mlとホールピペットで計った0.02/5Mの過マンガン酸カリウム水溶液10mlを加えて10分間加熱した。
3. ホールピペットで計った0.01Mシュウ酸を10ml加えた。
4.0.02/5Mの過マンガン酸カリウム水溶液で滴定した。
セルロース含有バイオマスの前処理方法として、水熱処理を用いた。セルロース含有バイオマスとして、1kg稲藁を使用した。前記セルロース含有バイオマスを2kg水に浸し、撹拌しながら180℃で20分間オートクレーブ処理(日東高圧株式会社製)し、前処理物を得た。その際の圧力は10MPaであった。
参考例3で得られた前処理物に濃度が15重量%となるように水を添加した後、さらにセルラーゼとして、Trichoderma sp.(トリコデルマ属)由来のセルラーゼ(シグマ・アルドリッチ・ジャパン)およびノボザイム188(アスペルギルスニガー由来βグルコシダーゼ製剤、シグマ・アルドリッチ・ジャパン)を添加し、50℃で1.5日間攪拌混同しながら、糖化反応を行い、糖水溶液と糖化残渣固形物を含む糖化処理物を得た。
参考例4で得られた糖化処理物1kg(図5の場合)または参考例7の蒸留工程後の残渣液1kg(図2の場合)に対して、ろ過処理助剤500gを添加して合計1.5kgとし、攪拌して均一なスラリー液になった後、フィルタプレスを行った(薮田産業株式会社製、小型ろ過装置MO-4を使用。)。初期のろ過液は濁質性が高いので、ろ過開始から1分間で得られたろ過液は原水槽に戻した。ろ布はT2731Cを使用した。ろ過開始1分以降に得られるろ過液を回収し、糖水溶液0.5kg(図5の場合)または蒸留残渣液0.5kg(図2の場合)を得た。
エタノール発酵酵母としてワイン酵母(サッカロマイセス・セレビシエ OC2株)を使用した。前処理工程後に得られた前処理固形分1kgと参考例4に示すようにセルラーゼを添加したもの(図2の場合)または糖水溶液0.5kg(図5の場合)に対して、酵母エキス5gおよび硫酸アンモニウム5gを添加した液体を発酵培地として用いた。発酵工程に植菌する種培養液は、50g/L グルコース、5g/L 酵母エキスおよび5g/L 硫酸アンモニウムを用い、30℃で1日間培養した。種培養液摂取量は、発酵培地の10%で行った。発酵工程は、温度30℃で維持し、通気・攪拌は行わずに1.5日間行った。こうした発酵工程後に得られた液を培養液(エタノール発酵酵母を含む)と呼ぶ。
培養液または該培養液からエタノール発酵酵母を除去したエタノール発酵液を蒸留装置に投入し、120℃まで加熱し、塔頂より37%エタノール溶液を回収した。一方で蒸留残渣液についてCODおよび体積を測定した。
逆浸透膜として、架橋全芳香族ポリアミド系逆浸透膜UTC80(東レ株式会社製)を用い、供給する原水温度を25℃、高圧ポンプ3の圧力を3MPaに調整し、透過液を除去した。圧縮率としては、非透過側の体積/供給する原水体積×100(%)で算出した。また、逆浸透膜工程による排水の圧縮は濃縮液のCODが100g/Lになるまでを上限とした。
処理液(フィルタプレス後の蒸留残渣液(図4の場合)または培養液(図5の場合))100mlを用いて、精密ろ過膜(ミリポア社製“ステリカップHV”0.45μm(登録商標))によるデッドエンドろ過運転を実施した。吸引圧は、80kPaの定圧ろ過運転とした。膜透過側から精密ろ過工程を経た蒸留残渣液を90ml(図4の場合)またはエタノール発酵液を90ml(図5の場合)回収した。
図2は、従来のエタノール製造方法の一態様であり、本比較例のエタノール製造方法を示す図である。上記参考例に従い、セルロース含有バイオマス1kgについて前処理工程、糖化工程・発酵工程の順序で処理を行い、得られた培養液を蒸留工程によりエタノールを精製した。図2に示すプロセスにおける蒸留残渣液は5.8Lとなった。また、CODは89g/Lであった。この蒸留残渣液にはエタノール発酵酵母および糖化残渣固形物が含まれているため、逆浸透膜に通すことはできなかった。図2で得られた蒸留残渣液をフィルタプレスして、糖化残渣固形物を取り除いた液を4.8L取得した。この液を排水処理工程でCODを低減し、排出した。
図3は、本比較例のエタノール製造方法を示す図である。本比較例は、図2のプロセスでのフィルタプレス工程の後に、逆浸透膜工程を適用したものである。図2で得られた蒸留残渣液をフィルタプレスして、糖化残渣固形物を取り除いた液を4.8L取得した。フィルタプレス後の液を参考例7に示す操作により逆浸透膜でろ過したが、急激に透過速度(透過液が出てくる速度)が低下し、最終的に逆浸透膜の詰まりによって100ml以上の透過液を取得できなかった。従って、逆浸透膜工程の圧縮率は、97.9%となり、ほとんど圧縮できなかった。逆浸透膜工程を追加することで、排水処理工程へ供給する排水量の削減はほとんどできなかった。
図4は、本比較例のエタノール製造方法を示す図である。本比較例は、図2のプロセスでのフィルタプレス工程の後に、精密ろ過工程および逆浸透膜工程を適用したものである。図2で得られた蒸留残渣液をフィルタプレスした後、この液を精密ろ過膜に通して、さらに細かな固形物を除去した液を4.7L取得した。得られた液を参考例7に示す操作により逆浸透膜でろ過したところ、比較例2よりも透過液の量は向上したが、15時間経過後に透過液を0.4L取得した段階でCODが100g/Lに達した。これ以上のCODの濃度では排水処理工程へ供給することができなくなった。従って逆浸透膜工程の圧縮率は91.4%が限界であり、ほとんど圧縮できなかった。
図5は、本実施例のエタノール製造方法を示す図である。上記参考例に従い、セルロース含有バイオマス1kgを、前処理工程、糖化工程、フィルタプレス工程、発酵工程、精密ろ過工程の順序で処理を行い、得られたエタノール発酵液を蒸留工程によりエタノールを精製した。その結果、図5に示すプロセスにおける蒸留残渣液は4.7L、CODは20g/Lであり、上記各比較例に比べて大幅に低下した。この蒸留残渣液を逆浸透膜に通したところ、比較例3よりも明らかに透過速度は早く、わずか2時間で透過液2.4Lを取得できた。また、逆浸透膜工程の非透過液のCODは38g/Lであった。非透過液について更に2時間かけて逆浸透膜に通し手濃縮した結果、1.2Lの非透過液を取得でき、そのCODは75g/Lであった。よって、最終的に逆浸透膜工程の圧縮率は25.5%となり、排水処理するべき逆浸透膜の非透過液の体積を顕著に圧縮することができた。
図6は、本実施例のエタノール製造方法を示す図である。実施例1と同様の方法で培養液を得た後、得られた培養液を150Gの遠心分離して培養液中の酵母を除去し、蒸留した。蒸留残渣液は4.5Lとなり、CODは25g/Lであった。次に、この蒸留残渣液を逆浸透膜に通したところ、わずか3時間で透過液2.4Lを取得できた。また、蒸留残渣液を逆浸透膜に通して得られた非透過液のCODは50g/Lであった。非透過液を更に3時間かけて逆浸透膜に通して濃縮した結果、1.5Lの非透過液を取得でき、そのCODは80g/Lであった。よって、最終的に逆浸透膜工程の圧縮率は33.3%となり、排水処理するべき逆浸透膜の非透過液の体積を顕著に圧縮することができた。
Claims (6)
- 以下の工程(1)~(8):
工程(1)セルロース含有バイオマスを前処理する工程、
工程(2):工程(1)で得られた前処理後のセルロース含有バイオマスを糖化酵素により糖化する工程、
工程(3):工程(2)で得られた糖化処理物から糖化残渣固形物を除去する工程、
工程(4):工程(3)で得られた糖水溶液を発酵原料としてアルコール発酵微生物を培養する工程、
工程(5):工程(4)で得られたアルコール発酵微生物を含む培養液からアルコール発酵微生物を除去する工程、
工程(6):工程(5)で得られたアルコール発酵液を蒸留し、アルコールを回収する工程、
工程(7):工程(6)で得られた蒸留残渣液を逆浸透膜に通じてろ過する工程、および
工程(8):工程(7)で得られた非透過液を排水処理する工程、
を含む、セルロース含有バイオマスからのアルコールの製造方法。 - 工程(5)が、工程(4)で得られたアルコール発酵微生物を含む培養液を精密ろ過膜に通じてろ過する工程である、請求項1に記載のセルロース含有バイオマスからのアルコールの製造方法。
- 工程(3)がフィルタプレスによる工程である、請求項1または2に記載のセルロース含有バイオマスからのアルコールの製造方法。
- 工程(7)の逆浸透膜の透過液を工程(1)、(2)または(4)のプロセス水として再利用する、請求項1~3のいずれか1項に記載のセルロース含有バイオマスからのアルコールの製造方法。
- 工程(7)が、工程(6)で得られた蒸留残渣液を直接逆浸透膜に通じてろ過する工程である、請求項1~4のいずれか1項に記載のセルロース含有バイオマスからのアルコールの製造方法。
- 前記アルコールが、メタノール、エタノール、プロパノールまたはブタノールである、請求項1~5のいずれか1項に記載のセルロース含有バイオマスからのアルコールの製造方法。
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14822174.0A EP3020817B1 (en) | 2013-07-12 | 2014-07-10 | Method for producing alcohol from cellulose-containing biomass |
| BR112015032945-4A BR112015032945B1 (pt) | 2013-07-12 | 2014-07-10 | Método de produção de álcool |
| JP2014552419A JP5757443B2 (ja) | 2013-07-12 | 2014-07-10 | セルロース含有バイオマスからのアルコールの製造方法 |
| CN201480039484.9A CN105378091A (zh) | 2013-07-12 | 2014-07-10 | 由含纤维素的生物质制造醇的方法 |
| CA2917413A CA2917413A1 (en) | 2013-07-12 | 2014-07-10 | Method for producing alcohol from cellulose-containing biomass |
| US14/904,449 US10093948B2 (en) | 2013-07-12 | 2014-07-10 | Method of producing alcohol from cellulose-containing biomass |
| AU2014288229A AU2014288229B2 (en) | 2013-07-12 | 2014-07-10 | Method for producing alcohol from cellulose-containing biomass |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-146486 | 2013-07-12 | ||
| JP2013146486 | 2013-07-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015005410A1 true WO2015005410A1 (ja) | 2015-01-15 |
Family
ID=52280088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2014/068385 Ceased WO2015005410A1 (ja) | 2013-07-12 | 2014-07-10 | セルロース含有バイオマスからのアルコールの製造方法 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US10093948B2 (ja) |
| EP (1) | EP3020817B1 (ja) |
| JP (1) | JP5757443B2 (ja) |
| CN (1) | CN105378091A (ja) |
| AU (1) | AU2014288229B2 (ja) |
| BR (1) | BR112015032945B1 (ja) |
| CA (1) | CA2917413A1 (ja) |
| MY (1) | MY172577A (ja) |
| WO (1) | WO2015005410A1 (ja) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017123791A (ja) * | 2016-01-12 | 2017-07-20 | 積水化学工業株式会社 | 発酵装置及び方法 |
| JP2019209286A (ja) * | 2018-06-06 | 2019-12-12 | 株式会社神鋼環境ソリューション | バイオマス処理方法、排水処理方法、及び、排水処理設備 |
| JP2020000230A (ja) * | 2018-06-27 | 2020-01-09 | アンスティテュ ナシオナル ドゥ ラ ルシェルシュ アグロノミク | リグノセルロース系バイオマスを処理するための方法 |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9777303B2 (en) | 2015-07-23 | 2017-10-03 | Fluid Quip Process Technologies, Llc | Systems and methods for producing a sugar stream |
| US11519013B2 (en) | 2018-03-15 | 2022-12-06 | Fluid Quip Technologies, Llc | System and method for producing a sugar stream with front end oil separation |
| US11053557B2 (en) | 2018-03-15 | 2021-07-06 | Fluid Quip Technologies, Llc | System and method for producing a sugar stream using membrane filtration |
| US11505838B2 (en) | 2018-04-05 | 2022-11-22 | Fluid Quip Technologies, Llc | Method for producing a sugar stream |
| US10480038B2 (en) | 2018-04-19 | 2019-11-19 | Fluid Quip Technologies, Llc | System and method for producing a sugar stream |
| US10995351B1 (en) | 2020-09-14 | 2021-05-04 | Fluid Quip Technologies, Llc | System and method for producing a carbohydrate stream from a cellulosic feedstock |
| CN112774443A (zh) * | 2021-01-04 | 2021-05-11 | 农业部沼气科学研究所 | 一种水解液反渗透糖浓缩脱毒回流系统及其使用方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007097260A1 (ja) | 2006-02-24 | 2007-08-30 | Toray Industries, Inc. | 化学品の製造方法、および、連続発酵装置 |
| JP2009184894A (ja) * | 2008-02-08 | 2009-08-20 | Juon:Kk | セルロース系炭化物の製造方法 |
| WO2010067785A1 (ja) | 2008-12-09 | 2010-06-17 | 東レ株式会社 | 糖液の製造方法 |
| JP2013013388A (ja) * | 2011-07-05 | 2013-01-24 | Chikyu Kankyo Solution Kenkyusho:Kk | 放射能付着植物等より放射能除去及び、経済性確立したバイオマスエタノール製造法 |
| JP2013059284A (ja) * | 2011-09-13 | 2013-04-04 | Honda Motor Co Ltd | エタノール製造装置 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460512C (zh) * | 2005-09-13 | 2009-02-11 | 新疆大学 | 甜高粱秆生产乙醇和微贮饲料 |
| DE102006040567A1 (de) * | 2006-08-30 | 2008-03-06 | Bayer Technology Services Gmbh | Verfahren zur Herstellung von Bioethanol |
| WO2011115039A1 (ja) * | 2010-03-15 | 2011-09-22 | 東レ株式会社 | 糖液の製造方法およびその装置 |
| BR112013004261B1 (pt) | 2010-08-31 | 2021-04-06 | Oji Holdings Corporation | Método para o tratamento de sacarificação enzimática de uma matéria-prima a base de lignocelulose |
| CN102465152B (zh) * | 2010-11-05 | 2015-06-17 | 刘贵彬 | 无需预处理的纤维乙醇内循环生产法 |
| FR2974311A1 (fr) | 2011-04-21 | 2012-10-26 | Metabolic Explorer Sa | Recyclage de l'eau par osmose inverse dans un procede de production d'un produit d'interet par fermentation |
-
2014
- 2014-07-10 MY MYPI2016700025A patent/MY172577A/en unknown
- 2014-07-10 AU AU2014288229A patent/AU2014288229B2/en not_active Ceased
- 2014-07-10 CN CN201480039484.9A patent/CN105378091A/zh active Pending
- 2014-07-10 US US14/904,449 patent/US10093948B2/en active Active
- 2014-07-10 CA CA2917413A patent/CA2917413A1/en not_active Abandoned
- 2014-07-10 EP EP14822174.0A patent/EP3020817B1/en not_active Not-in-force
- 2014-07-10 JP JP2014552419A patent/JP5757443B2/ja not_active Expired - Fee Related
- 2014-07-10 BR BR112015032945-4A patent/BR112015032945B1/pt not_active IP Right Cessation
- 2014-07-10 WO PCT/JP2014/068385 patent/WO2015005410A1/ja not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007097260A1 (ja) | 2006-02-24 | 2007-08-30 | Toray Industries, Inc. | 化学品の製造方法、および、連続発酵装置 |
| JP2009184894A (ja) * | 2008-02-08 | 2009-08-20 | Juon:Kk | セルロース系炭化物の製造方法 |
| WO2010067785A1 (ja) | 2008-12-09 | 2010-06-17 | 東レ株式会社 | 糖液の製造方法 |
| JP2013013388A (ja) * | 2011-07-05 | 2013-01-24 | Chikyu Kankyo Solution Kenkyusho:Kk | 放射能付着植物等より放射能除去及び、経済性確立したバイオマスエタノール製造法 |
| JP2013059284A (ja) * | 2011-09-13 | 2013-04-04 | Honda Motor Co Ltd | エタノール製造装置 |
Non-Patent Citations (5)
| Title |
|---|
| "CARBOXYL CELLULASE ASSAY FOR ENDO-P-1.4-GLUCANASE", PURE & APPL. CHEM., vol. 59, no. 2, pages 257 - 268 |
| "Cellobiase assay", PURE & APPL. CHEM., vol. 59, no. 2, pages 257 - 268 |
| "FILTER PAPER ASSAY FOR SACCHARIFYING CELLULASE", PURE & APPL. CHEM., vol. 59, no. 2, pages 257 - 268 |
| D. HUMBIRD ET AL.: "Process Design and Economics for Biochemical Conversion of Lignocellulosic Biomass to Ehanol", NREL REPORT NO. TP-5100-47764, May 2011 (2011-05-01) |
| MITSUHARU FURUICHI: "Utilization of membrane separation techniques in alcohol manufacturing process from biomass", BIOSCIENCE & INDUSTRY, vol. 47, no. 9, 1 September 1989 (1989-09-01), pages 951 - 954, XP055028049 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017123791A (ja) * | 2016-01-12 | 2017-07-20 | 積水化学工業株式会社 | 発酵装置及び方法 |
| JP2019209286A (ja) * | 2018-06-06 | 2019-12-12 | 株式会社神鋼環境ソリューション | バイオマス処理方法、排水処理方法、及び、排水処理設備 |
| JP2020000230A (ja) * | 2018-06-27 | 2020-01-09 | アンスティテュ ナシオナル ドゥ ラ ルシェルシュ アグロノミク | リグノセルロース系バイオマスを処理するための方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3020817A1 (en) | 2016-05-18 |
| AU2014288229A1 (en) | 2016-01-21 |
| US20160160242A1 (en) | 2016-06-09 |
| BR112015032945A2 (ja) | 2020-05-12 |
| CA2917413A1 (en) | 2015-01-15 |
| CN105378091A (zh) | 2016-03-02 |
| MY172577A (en) | 2019-12-03 |
| BR112015032945B1 (pt) | 2022-01-18 |
| EP3020817A4 (en) | 2017-03-22 |
| JP5757443B2 (ja) | 2015-07-29 |
| AU2014288229B2 (en) | 2018-03-08 |
| JPWO2015005410A1 (ja) | 2017-03-02 |
| EP3020817B1 (en) | 2021-09-29 |
| US10093948B2 (en) | 2018-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5757443B2 (ja) | セルロース含有バイオマスからのアルコールの製造方法 | |
| JP5246379B2 (ja) | 糖液の製造方法 | |
| KR101778115B1 (ko) | 당액의 제조방법 및 그 장치 | |
| JP6269061B2 (ja) | 糖液の製造方法 | |
| JP6007791B2 (ja) | 糖液の製造方法 | |
| EP2650384A1 (en) | Method for producing concentrated aqueous sugar solution | |
| CN101815788A (zh) | 用于从预处理过的木质纤维素原料产生醇和葡萄糖的基于纤维素酶的方法 | |
| WO2012077698A1 (ja) | 濃縮糖水溶液の製造法 | |
| JP6459514B2 (ja) | 糖液の製造方法 | |
| JPWO2014129489A1 (ja) | 糖液の製造方法 | |
| JP2013255457A (ja) | 濃縮糖水溶液およびエタノールの製造方法 | |
| CN210419980U (zh) | 一种酒糟酶解提取低聚木糖的装置 | |
| CN107406866B (zh) | 糖液的制造方法 | |
| JP7708482B1 (ja) | バイオエタノールの製造方法及びバイオエタノールの製造装置 | |
| Ohlson et al. | Evaluation of UF and RO in a cellulose saccharification process | |
| WO2024143503A1 (ja) | リグノセルロース系原料からエタノールを製造する方法 | |
| CN119278270A (zh) | 糖液的制造方法 | |
| Mueansichai et al. | SEPARATION OF REDUCING SUGARS AND MICROORGANISM FORM HYDROLYSATE BY ULTRAFILTRATION | |
| WO2018042464A1 (en) | Rapid enzymatic hydrolysis of substrates for production of fermentable sugars | |
| WO2014024220A1 (ja) | セルロース系バイオマスを原料とする糖化液製造方法及び糖化液製造装置 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ENP | Entry into the national phase |
Ref document number: 2014552419 Country of ref document: JP Kind code of ref document: A |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14822174 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2014822174 Country of ref document: EP |
|
| ENP | Entry into the national phase |
Ref document number: 2917413 Country of ref document: CA |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 14904449 Country of ref document: US |
|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112015032945 Country of ref document: BR |
|
| ENP | Entry into the national phase |
Ref document number: 2014288229 Country of ref document: AU Date of ref document: 20140710 Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: IDP00201600936 Country of ref document: ID |
|
| ENP | Entry into the national phase |
Ref document number: 112015032945 Country of ref document: BR Kind code of ref document: A2 Effective date: 20151230 |
|
| ENPC | Correction to former announcement of entry into national phase, pct application did not enter into the national phase |
Ref country code: BR Free format text: ANULADA A PUBLICACAO CODIGO 1.3 NA RPI NO 2429 DE 25/07/2017 POR TER SIDO INDEVIDA. |
|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01E Ref document number: 112015032945 Country of ref document: BR Kind code of ref document: A2 Free format text: APRESENTE TRADUCAO SIMPLES DA CERTIDAO DE DEPOSITO DA PRIORIDADE NO PAIS DE ORIGEM OU DECLARACAO ASSINADA, AMBAS CONTENDO TODOS OS DADOS IDENTIFICADORES DA PRIORIDADE CONFORME ART. 16, 2O, DA LPI. |
|
| ENP | Entry into the national phase |
Ref document number: 112015032945 Country of ref document: BR Kind code of ref document: A2 Effective date: 20151230 |