WO2013190876A1 - バイオマスの処理システム及び処理方法 - Google Patents
バイオマスの処理システム及び処理方法 Download PDFInfo
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- WO2013190876A1 WO2013190876A1 PCT/JP2013/058946 JP2013058946W WO2013190876A1 WO 2013190876 A1 WO2013190876 A1 WO 2013190876A1 JP 2013058946 W JP2013058946 W JP 2013058946W WO 2013190876 A1 WO2013190876 A1 WO 2013190876A1
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- C12M45/00—Means for pre-treatment of biological substances
- C12M45/09—Means for pre-treatment of biological substances by enzymatic treatment
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- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
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- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
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- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/30—Means for regulation, monitoring, measurement or control, e.g. flow regulation of concentration
- C12M41/32—Means for regulation, monitoring, measurement or control, e.g. flow regulation of concentration of substances in solution
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- 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
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- B01J2219/00049—Controlling or regulating processes
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
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- B01J2219/00049—Controlling or regulating processes
- B01J2219/00177—Controlling or regulating processes controlling the pH
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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- 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
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- 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 biomass treatment system and treatment method that are pretreated by hydrothermal treatment, heat treatment, acid / alkali treatment, and the like, and more particularly, after the pretreatment by controlling the operating conditions of the pretreatment apparatus or the properties of the biomass before the pretreatment.
- the present invention relates to a biomass processing system and a processing method for optimizing the amount of undecomposed matter.
- Biomass containing cellulose and hemicellulose such as bagasse, wheat straw, rice straw, palm residue, switchgrass, paper, etc.
- Production of ethanol and organic acid from the biomass is carried out by subjecting fibers such as cellulose and hemicellulose as main components to pretreatment such as hydrothermal treatment, sterilizing the pretreated biomass, and applying saccharifying enzyme to the sterilized biomass.
- a saccharified solution containing sugars such as glucose, xylose, arabinose, galactose, and mannose is reacted, and the sugar is converted into ethanol or an organic acid by fermentation using a microorganism such as yeast.
- a technique of simultaneously performing enzymatic saccharification and fermentation in a simultaneous saccharification and fermentation tank for pretreated and sterilized biomass is often used.
- the biomass is mainly a complex in which three components of cellulose, hemicellulose, and lignin are tightly bound, and the cellulose molecule itself has a hard crystal structure, so that the saccharifying enzyme cellulase cannot approach the cellulose molecule as it is. . Therefore, in the pretreatment device, the biomass is pretreated with any one of heat treatment, hydrothermal treatment, acid treatment, pulverization method, wood decay fungus, etc. to loosen the binding of the three components, and is easily saccharified. Convert to properties.
- the yield of ethanol or organic acid finally obtained is stable, but even when the type and amount of biomass supplied to the pretreatment device and the operating conditions of the pretreatment device are kept constant.
- the yield of final products such as ethanol may vary.
- the cause of this variation will be explained with an example of using bagasse as biomass.
- Bagasse properties change depending on the sugarcane harvest time, sugar production process, bagasse storage method and storage period, etc. There is a difference in sensitivity.
- sugar may be attached to bagasse in the process of squeezing sugarcane, and if left untreated, lactic acid fermentation will produce an acid component.
- the amount of the acid component resulting therefrom varies depending on the bagasse, and the difference in the amount of acid component causes a difference in the progress of the pretreatment process.
- the degree of progress of the pretreatment process varies.
- the amount of by-products generated by the pretreatment varies.
- Patent Document 1 discloses an invention in which amorphous chitin or amorphous chitosan is reduced in molecular weight by decomposing under a certain hydrothermal condition, and the decomposition is controlled by reaction time and reaction temperature. Is disclosed.
- Patent Document 2 discloses that when an organic substance is decomposed by a hydrothermal reaction, the amount of CO in the processing fluid is measured, and the hydrothermal reaction is controlled so that the measured amount of CO becomes a predetermined value or less. Has been.
- Patent Document 3 an organic halide is decomposed by an organic halide decomposing apparatus, and a concentration pattern of the organic halide and / or organic halide decomposing product in waste water is measured by a laser ionization time-of-flight mass spectrometer.
- Patent Document 4 discloses that when a highly water-containing organic substance is decomposed by a hydrothermal reaction using a microwave, the property of the organic substance is measured and the output of the microwave is controlled according to the measured value.
- Patent Document 5 discloses a method for obtaining a good liquid feed by hydrolyzing proteins by high-temperature and high-pressure water treatment. By appropriately controlling reaction conditions such as pressure, the target amino acid can be obtained. It is described that it has been found that there is a possibility of improving the yield.
- the by-product Since the by-product has an effect of inhibiting the growth and metabolism of the fermenting microorganism, if a large amount of by-product is produced by the pretreatment, the amount of the final product is reduced. In addition, the amount of sugar produced by enzymatic saccharification varies depending on the progress of pretreatment. As described above, even when the type and amount of biomass supplied to the pretreatment device and the operating conditions of the pretreatment device are kept constant, the progress of the pretreatment and the amount of by-products generated by the pretreatment vary. Therefore, there is a problem that a large amount of the final product cannot be obtained stably.
- the main problem to be solved by the present invention is that the amount of the final product obtained through the pretreatment and the saccharification and fermentation process even when there is a difference in the properties of the biomass supplied to the pretreatment apparatus and the amount of acid components contained in the biomass. It is to stably increase the yield of.
- a pretreatment device for pretreating biomass A measuring means for measuring at least one selected from the group of pH, acidity, alkalinity, ultraviolet absorption rate, amount of decomposed product and amount of undecomposed product of the pretreated biomass; Control means for controlling the operating conditions of the pretreatment device or the properties of the biomass before pretreatment based on the measurement results;
- a biomass processing system characterized by comprising:
- the amount of decomposed or undegraded products generated by pretreatment and the pH, acidity, alkalinity or UV absorption rate of pretreated biomass are used as a guide for the degree of progress of the pretreatment reaction.
- the sugar yield in the enzymatic saccharification process varies depending on the progress of the pretreatment. Therefore, the sugar yield in the enzymatic saccharification step can be stabilized by appropriately managing the progress of the pretreatment reaction with the amount of degradation product as a guideline.
- the degradation product obtained by the pretreatment contains an inhibitor that inhibits the progress of the fermentation process to be performed later, but the amount of the inhibitor produced can be reduced by appropriately managing the progress of the pretreatment reaction.
- the yield in the fermentation process can be stabilized.
- the yield of the final product obtained through the enzymatic saccharification step and the fermentation step can be stably increased. Similar effects can be obtained in simultaneous saccharification and fermentation in which enzymatic saccharification and fermentation are performed in the same tank.
- control means controls at least one of a reaction time of pretreatment, a reaction temperature, a pH of the biomass before pretreatment, an acidity, and an alkalinity.
- the reaction time and reaction temperature of the pretreatment By controlling the reaction time and reaction temperature of the pretreatment, the amount of the inhibitor produced can be reduced, and the progress of the pretreatment can be brought into an appropriate state.
- the amount of the acid component contained in the biomass before pretreatment becomes an appropriate amount.
- the degree of advancement of the preprocessing can be brought into an appropriate state.
- Pretreated biomass produced under appropriately controlled pretreatment has a low content of inhibitors that inhibit the progress of the fermentation process, and the binding of cellulose, hemicellulose, and lignin in the biomass is sufficiently dissolved.
- the saccharifying enzyme easily approaches the cellulose molecule, the yield of the final product obtained through the enzymatic saccharification process and the fermentation process can be stably increased.
- Saccharification / fermentation means for saccharifying the pretreated biomass by performing the control with a saccharifying enzyme and fermenting the saccharified biomass with a fermentation microorganism
- a saccharification enzyme production apparatus for producing a saccharification enzyme used in the saccharification / fermentation means
- a first processing means for sending a part of the pretreated biomass as it is to the saccharification / fermentation means;
- the remainder of the pretreated biomass is supplied to the saccharifying enzyme production apparatus, the saccharogenic enzyme producing bacteria are cultured by using the supplied pretreated biomass as a medium to produce saccharifying enzyme, and the produced saccharifying enzyme is converted into the saccharification / fermentation Second processing means for sending to the means;
- the biomass processing system according to claim 1 or 2 further comprising:
- Pretreated biomass produced under a properly controlled pretreatment has a low content of inhibitors that inhibit the progress of the saccharification enzyme production process, thus stabilizing the yield of saccharification enzyme obtained through the saccharification enzyme production process. Can get more.
- a step of pretreating biomass with a pretreatment device Measuring at least one selected from the group of pH, acidity, alkalinity, ultraviolet absorption rate, amount of decomposed product, and amount of undegraded product of the pretreated biomass, A step of controlling the operation conditions of the pretreatment device or the properties of the biomass before the pretreatment by the control means based on the measurement results;
- a method for treating biomass characterized by comprising:
- the yield of the final product obtained through the pretreatment and the saccharification and fermentation process can be stabilized even when there is a difference in the properties of the biomass supplied to the pretreatment device and the amount of acid components contained in the biomass. Can do a lot.
- FIG. 1 shows an outline of a biomass processing operation flow according to the present invention.
- the system according to the present invention is preferably used for biomass containing cellulose, hemicellulose, bagasse, straw, palm residue, corn stover, palm palm residue, cassava residue, wood fragments, wood waste, jute, kenaf, switch glass, waste paper, etc. it can.
- Biomass containing cellulose and hemicellulose is separated from foreign substances such as sand and pebbles by the washing process, and much of the water added in the washing process is removed by the dehydration process.
- sterilization is usually performed to prevent contamination, but heat treatment, hydrothermal treatment (steaming, explosion), acid treatment (diluted acid method using sulfuric acid, nitric acid, phosphoric acid, concentrated acid method, SO2 impregnation explosion method) ) And alkali treatment (caustic soda method, sodium sulfite method, ammonia method, calcium hydroxide method), since the pretreatment has a sterilization effect, there is no need to provide a separate sterilization step. There is an advantage of being good. In the case of the concentrated sulfuric acid method, pretreatment and saccharification are possible without using cellulase.
- the pretreated biomass is sent to a saccharification device and saccharified in the saccharification device.
- a typical example of this saccharification apparatus is a bioreactor.
- the pretreated biomass is decomposed mainly by the action of three types of cellulases (endoglucanase (EG), cellobiohydrolase (CBH), and ⁇ -glucosidase (BGL)).
- This cellulase is added in an amount of 3 to 30 FPU / g, preferably 5 to 20 FPU / g, based on the dry weight of the raw material (FPU / g is a unit of cellulase enzyme activity that produces 10.8 mg of glucose from filter paper in 60 minutes).
- the saccharified product is sent to a fermentation apparatus and fermented in the fermentation apparatus.
- Saccharomyces, Schizosaccharomyces, Kluyveromyces, Pichia, Candida yeast, Zymomonas spp., Clostridium spp. Use genetically modified microorganisms.
- this ethanol-fermenting bacterium is inoculated with 1 to 100 g wet-wt / L, preferably 5 to 50 g wet-wt / L per raw material volume.
- filamentous fungi such as Rhizopus oryzae can be used, and in order to convert sugar to succinic acid, for example, Coryneform bacteria (Coryneform bacteria) ), Bacillus bacteria, Rhizobium bacteria, and the like.
- Coryneform bacteria Coryneform bacteria
- Bacillus bacteria Bacillus bacteria, Rhizobium bacteria, and the like.
- the fermented mash produced by the fermentation is sent to a mash tower or an evaporator.
- the fermentation mash is heated at a temperature near the boiling point, and the evaporated ethanol or organic acid is condensed to obtain a high-concentration ethanol liquid or organic acid-containing liquid.
- the concentration of ethanol or organic acid is about 30% or less, more specifically about 3 to 20%.
- a liquid containing a component having a boiling point higher than that of ethanol or organic acid or a solid such as cellulose or lignin that has not been saccharified and fermented is discharged from the bottom of the mash tower and discarded. The same operation as described above is performed in the evaporator.
- the ethanol solution or organic acid-containing solution that has undergone the evaporation step is sent to a rectification column or a distillation column.
- the rectifying column the ethanol solution or organic acid-containing solution is heated at a temperature near the boiling point of the target component, and the evaporated ethanol or organic acid is condensed to obtain a high-concentration ethanol solution or organic acid-containing solution.
- the product is ethanol
- the ethanol concentration in the rectification fraction is 90 to 95% by volume.
- the waste liquid generated by the rectification process is discharged from the bottom of the rectification column.
- the same operation as described above is performed.
- a further rectification process or a dehydration process may be provided to further increase the concentration or remove impurities.
- the operating conditions and pretreatment of the pretreatment device Control the properties of the previous biomass.
- the decomposition product obtained by the pretreatment includes an inhibitor that inhibits the progress of the fermentation process performed later. Therefore, when the amount of the inhibitory substance produced due to the advance of the pretreatment is excessive, the amount of the final product obtained through the fermentation process is reduced. Therefore, the progress of pretreatment is ascertained using the amount of decomposed product or the amount of residual solids as an indicator, and the operating conditions of the pretreatment device and the properties of biomass before pretreatment are determined in order to appropriately manage the progress of the pretreatment reaction. Control. As a result, the production amount of the inhibitor can be reduced, and a large amount of the final product obtained through the saccharification and fermentation process can be stably obtained.
- pretreatment biomass is measured (A) while the pretreated biomass is being transported from the pretreatment device to a saccharification and fermentation device (for example, a bioreactor).
- a saccharification and fermentation device for example, a bioreactor.
- at least one of (1) measurement of acidity and alkalinity with an automatic titrator, (2) measurement of pH value with a pH sensor, and (3) measurement of UV absorption with a UV-VIS spectrophotometer Take one measurement. All the measurements (1) to (3) are performed on the liquid. More specifically, (1) and (2) can be measured for a slurry, but (3) requires pretreatment biomass to be separated into a solid and a liquid, and the separated liquid needs to be measured. .
- the pretreatment biomass in the middle of conveyance has high solid substance concentration, it may be difficult to measure as it is.
- the pretreated biomass is mixed with a large amount of water, the liquid adhering to the pretreated biomass is extracted into water, and this water is applied to each of the measuring means.
- the measurement of the internal liquid of the bioreactor (B) may be performed instead of the measurement (A) or together with the measurement (A). Since the internal liquid of this bioreactor is liquid, it can be measured without the extraction.
- ⁇ Understand the progress of pretreatment based on the measurement results of pH, acidity, alkalinity or UV absorption rate of pretreated biomass.
- a memory is provided in the treatment system according to the present invention, and statistical data on the relationship between the pH, acidity, alkalinity, ultraviolet absorption rate of the pretreated biomass and the progress of the pretreatment is stored in this memory.
- the progress of the preprocessing is grasped by comparing the measurement result with the statistical data in the memory.
- the pretreated biomass preferably has an ultraviolet absorbance of 280 nm in the range of 200 to 450. If the ultraviolet absorbance is lower than 200, the pretreatment conditions become strong, so that the amount of inhibitor produced is increased, the fermentation process is inhibited, and the yield of the final product is reduced. Further, when the ultraviolet absorbance is higher than 450, the pretreatment conditions are weakened, so that the saccharifying enzyme cellulase cannot sufficiently approach the cellulose molecule, and the yield of the final product obtained through the subsequent saccharification and fermentation process is reduced.
- the acidity of the pretreated biomass is preferably in the range of 20 to 45 [g-as acetic acid / kg-solid matter in pretreated product]. If the acidity is lower than 20 [g-as acetic acid / kg-solid matter in pre-treated product], the pre-treatment conditions become weak, so that the saccharifying enzyme cellulase cannot sufficiently access the cellulose molecule, and the subsequent saccharification and fermentation process The yield of the final product obtained through the process is reduced. In addition, when the acidity is higher than 45 [g-as acetic acid / kg-solid matter in the pretreated product], the pretreatment conditions become stronger, so that the amount of inhibitor produced increases and the fermentation process is inhibited, resulting in the yield of the final product. Less.
- the pH of the pretreated biomass is preferably in the range of 3.2 to 3.7. If the pH is lower than 3.2, the pretreatment conditions become strong, so that the amount of inhibitor produced increases, the fermentation process is inhibited, and the yield of the final product decreases. Moreover, since pre-processing conditions will become weak when pH is higher than 3.7, a saccharification enzyme cellulase cannot fully approach a cellulose molecule, and the yield of the final product obtained through a subsequent saccharification fermentation process will decrease.
- the reaction of the pretreatment device Adjust time and reaction temperature.
- the amount of residual solids decreases, the UV absorbance (280 nm) increases, the acidity increases, and the pH decreases. Adjust the reaction conditions while observing the measured values, and keep them within the appropriate range. Is possible.
- the pH, acidity, alkalinity, and ultraviolet absorption rate of the pretreated biomass may be measured for any one of these elements and controlled based on the measurement results. However, it is more preferable to measure two or more elements and perform control based on the measurement result. This is because the progress of the pretreatment can be controlled more reliably by measuring two or more elements.
- the amount of solid matter remaining in the pretreatment can also be measured.
- the amount of solids in the biomass supplied to the pretreatment process and the amount of solids in the biomass after pretreatment are measured.
- the weight of biomass supplied to the pretreatment process is measured with a metric conveyor or the like (weight W1 (ton)), and the moisture is measured with an infrared moisture meter or the like (moisture M1 (%)).
- the weight (W2 (ton)) and moisture (M2 (%)) of biomass after pretreatment are measured.
- the solid residual amount W3 (kg) per 1 ton of supplied biomass solids is obtained from the following calculation formula.
- ⁇ Understand the progress of pretreatment based on the calculated amount of remaining solids.
- a memory is provided in the processing system according to the present invention, and statistical data regarding the relationship between each value of the remaining amount of solid matter and the progress of preprocessing is stored in this memory. Then, the progress of the preprocessing is grasped by comparing the measurement result with the statistical data in the memory.
- the residual amount of solids is in the range of 60 to 75% of the amount of supplied biomass.
- the solid amount remaining after the pretreatment is in the range of 600 to 750 kg. If the amount of solids remaining per 1 ton of supplied biomass is less than 600 kg, pretreatment conditions become strong, so that the amount of inhibitor produced is increased, the fermentation process is inhibited, and the yield of the final product is reduced.
- the pretreatment conditions become weak, so that the saccharifying enzyme cellulase cannot sufficiently approach the cellulose molecules, and the yield of the final product obtained through the subsequent saccharification and fermentation process is reduced. .
- the operating conditions of the pretreatment device are controlled so that the preferable progress is achieved.
- the amount of remaining solids per ton of supplied biomass is less than 600 kg
- control is performed such as shortening the reaction time or lowering the reaction temperature in order to weaken the pretreatment conditions.
- the residual amount of solid matter is higher than 750 kg
- control is performed such as increasing the reaction time and increasing the reaction temperature in order to increase the pretreatment conditions.
- control is performed based on the amount of remaining solid matter, but control may be performed based on the amount of decomposition products.
- saccharifying enzyme production process In the present invention, pretreated biomass produced under appropriately managed pretreatment can also be used in the saccharifying enzyme production process.
- This step is performed by a saccharifying enzyme production apparatus.
- This saccharifying enzyme production step includes a step of culturing an enzyme-producing bacterium and a step of producing an enzyme using the cultured enzyme-producing bacterium. This will be described in detail below.
- a useful strain that produces the target enzyme is prepared.
- useful strains to be produced include strains such as cellulase-producing bacteria that produce cellulase and hemicellulase-producing bacteria that produce hemicellulase. More specifically, any one or more microorganisms of the genus Acremonium, Trichoderma, Penicillium, Aspergillus, and Thermoscus, or eubacteria of the genus Clostridium and Bacillus can be used.
- the saccharifying enzyme-producing bacterium it is preferable to use a bacterium belonging to the genus Acremonium cellulolyticus.
- the enzyme-producing bacteria is Acremonium cellulolyticus
- the same pretreated biomass is used as the raw material for saccharification and enzyme production
- hemicellulose-degrading enzyme is particularly secreted, so the sugar yield in the saccharification process is reduced. This is because it can be increased.
- Specific examples of bacteria belonging to the genus Acremonium cellulolyticus include Acremonium cellulolyticus Y-94, Acremonium cellulolyticus TN, Acremonium cellulolyticus C-1 and Acremonium cellulolyticus CF-2612 Can do. Among these bacteria, Acremonium cellulolyticus C-1 strain and Acremonium cellulolyticus CF-2612 strain have high xylanase activity, and it is particularly preferable to use these two bacteria.
- the produced useful strain is cultured in a medium.
- a medium a solid medium, a semi-fluid medium, or a liquid medium (broth, broth) can be used, but a liquid medium is preferably used.
- pretreated biomass can be used instead. More specifically, when lignocellulosic biomass is pretreated, pretreated biomass containing cellulose is generated, so the second treatment means is used to send the remainder of the pretreated biomass to the saccharifying enzyme production apparatus as a carbon source for the medium. Use. In addition, when utilizing the remainder of pretreatment biomass as a carbon source, a part of pretreatment biomass will be sent to a saccharification apparatus using a 1st process means.
- pretreated biomass may be mixed with inhibitors that inhibit the growth and proliferation of enzyme-producing bacteria.
- the inhibitor include formic acid and acetic acid.
- the culture temperature and culture time in the culture vary depending on the type of enzyme-producing bacteria, but are usually cultured at a temperature of 28 to 32 ° C. for a period of 48 hours to 10 days.
- examples of the fermenter used for culturing of the saccharifying enzyme production apparatus include an aeration stirring type, a bubble column type, a fluidized bed type, and a packed bed type.
- the enzyme-producing bacteria grow and proliferate and the enzyme-producing bacteria produce saccharifying enzymes by culturing the enzyme-producing bacteria.
- the culture solution at the end of the culture of the enzyme-producing bacteria contains saccharifying enzyme.
- This enzyme-containing liquid may be supplied directly to the saccharification tank, or may be supplied to the saccharification tank after purification.
- enzyme-producing bacteria are removed by a method such as filtration or centrifugation to obtain a supernatant.
- a method such as filtration or centrifugation to obtain a supernatant.
- ion exchange chromatography isoelectric point chromatography
- gel filtration chromatography hydrophobic chromatography
- adsorption column chromatography affinity chromatography
- reverse phase column chromatography etc.
- ethanol ethanol
- the target saccharifying enzyme is obtained by using a method such as precipitation separation using methanol, acetone or the like, filtration treatment such as microfiltration, ultrafiltration or reverse osmosis filtration.
- Bagasse was used as raw material biomass, and after pretreatment by hydrothermal treatment, ethanol was produced by simultaneous saccharification and fermentation.
- the bagasse from which foreign substances were removed by washing with water was filled in a pressurized container, heated to 180 to 220 ° C. by blowing a saturated vapor of 25 atm, and pretreated by hydrothermal treatment for 4 to 10 minutes.
- the hydrothermal reaction product thus obtained was subjected to simultaneous saccharification and fermentation using cellulase enzyme produced by Acremonium cellulolyticus C-1 strain (Ferm P-18058) and Saccharomyces cellobici yeast. did.
- the solids concentration of the hydrothermal reaction product is added so as to be 10% (weight / dry basis) with respect to the total amount of the fermentation broth, and cellulase enzyme is 10 FPU / g-solid to the solid,
- the addition amount of the culture solution was set to 5% with respect to the total fermentation solution amount, and the reaction was performed at 35 ° C. for 48 hours.
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Abstract
Description
<請求項1記載の発明>
バイオマスを前処理する前処理装置と、
前処理されたバイオマスのpH、酸度、アルカリ度、紫外線吸収率、分解物量および未分解物量の群から選ばれる少なくとも1つを測定する測定手段と、
前記測定結果に基づいて前処理装置の運転条件または前処理前のバイオマスの性状を制御する制御手段と、
を有することを特徴とするバイオマスの処理システム。
前処理により生じた分解物または未分解物の量や、前処理されたバイオマスのpH、酸度、アルカリ度または紫外線吸収率を前処理反応の進行度合いの指針とし、その測定値に基づいて前処理装置の運転条件または前処理前のバイオマスの性状を制御する。
前処理の進行度合いによって酵素糖化工程の糖収量が変動する。よって、分解物量等を指針として前処理反応の進行を適切に管理することによって、酵素糖化工程での糖収量を安定させることができる。
また、前処理により得られる分解物には、後に行われる発酵工程の進行を阻害する阻害物質が含まれるが、前処理反応の進行を適切に管理することによって、前記阻害物質の生成量を少なくすることができ、発酵工程での収量を安定させることができる。
上記の結果として、酵素糖化工程および発酵工程を経て得られる最終生成物の収量を安定して多く得ることができる。
酵素糖化と発酵を同一槽内で行う同時糖化発酵においても、同様の効果が得られる。
前記制御手段は、前処理の反応時間、反応温度、前処理前のバイオマスのpH、酸度およびアルカリ度の少なくとも1つを制御する請求項1記載のバイオマスの処理システム。
前処理の反応時間、反応温度を制御することで、前記阻害物質の生成量を少なくすることができるとともに、前処理の進行度合いを適切な状態にすることができる。
また、前処理前のバイオマスのpH、酸度およびアルカリ度の少なくとも1つを制御することで、前処理前のバイオマスの含有する酸成分量が適切な量になるため、前記阻害物質の生成量を少なくすることができるとともに、前処理の進行度合いを適切な状態にすることができる。
前記制御を行って前処理したバイオマスを糖化酵素によって糖化させ、糖化したバイオマスを発酵微生物によって発酵させる糖化・発酵手段をさらに有する請求項1または2記載のバイオマスの処理システム。
適切に管理された前処理の下で生成した前処理バイオマスは、発酵工程の進行を阻害する阻害物質の含有量が少ないとともに、バイオマス中のセルロース、ヘミセルロース、リグニンの3成分の結合が十分に解けており、糖化酵素がセルロース分子に接近しやすいため、酵素糖化工程および発酵工程を経て得られる最終生成物の収量を安定して多く得ることができる。
前記制御を行って前処理したバイオマスを糖化酵素によって糖化させ、糖化したバイオマスを発酵微生物によって発酵させる糖化・発酵手段と、
前記糖化・発酵手段で用いる糖化酵素を生産する糖化酵素生産装置と、
前処理したバイオマスの一部をそのまま前記糖化・発酵手段へ送る第1処理手段と、
前処理したバイオマスの残部を前記糖化酵素生産装置に供給し、供給した前処理バイオマスを培地に用いて糖化酵素生産菌を培養して糖化酵素の生産を行い、生産した糖化酵素を前記糖化・発酵手段へ送る第2処理手段と、
をさらに有する請求項1または2記載のバイオマスの処理システム。
適切に管理された前処理の下で生成した前処理バイオマスは、糖化酵素生産工程の進行を阻害する阻害物質の含有量が少ないため、糖化酵素生産工程を経て得られる糖化酵素の収量を安定して多く得ることができる。
バイオマスを前処理装置によって前処理する工程と、
前処理されたバイオマスのpH、酸度、アルカリ度、紫外線吸収率、分解物量および未分解物量の群から選ばれる少なくとも1つを測定手段によって測定する工程と、
前記測定結果に基づき前処理装置の運転条件または前処理前のバイオマスの性状を制御手段によって制御する工程と、
を有することを特徴とするバイオマスの処理方法。
請求項1と同様の作用効果を有する。
図1に本発明にかかるバイオマスの処理操作フローの概略を示す。
なお、本発明にかかるシステムは、バガス、麦わら、パーム残渣、コーンストーバー、パームヤシ残渣、キャッサバ残渣、木片、木質廃材、ジュート、ケナフ、スイッチグラス、古紙等のセルロース、ヘミセルロースを含むバイオマスについて好適に使用できる。
セルロース、ヘミセルロースを含むバイオマスは、洗浄工程により、砂、小石等の異物と分離され、脱水工程により洗浄工程で添加された水分の多くが除去される。
前記バイオマスは、主にセルロース、ヘミセルロース、リグニンの3成分が固く結合した複合体となっているうえ、セルロース分子自体も固い結晶構造を取っているため、そのままでは糖化酵素セルラーゼがセルロース分子に接近できない。そのため、前処理装置内で、脱水後のバイオマスを、熱処理、水熱処理、酸処理、アルカリ処理、微粉砕法、木材腐朽菌などのどれかで前処理して、前記3成分を解離させる。その後、通常はコンタミネーションを防ぐために滅菌処理を行うが、熱処理、水熱処理(蒸煮、爆砕)、酸処理(硫酸、硝酸、リン酸などを用いた希酸法、濃酸法、SO2含浸爆砕法)並びにアルカリ処理(苛性ソーダ法、亜硫酸ソーダ法、アンモニア法、水酸化カルシウム法)のいずれかの前処理を行った場合は、その前処理が滅菌効果を有するため、別途滅菌工程を設けなくても良いという利点がある。なお、濃硫酸法の場合はセルラーゼを用いずに前処理と糖化まで可能である。
前処理したバイオマスは糖化装置へ送られ、糖化装置内で糖化される。この糖化装置の代表例としては、バイオリアクターを挙げることができる。この糖化装置内で、前処理したバイオマスが主に3種類のセルラーゼ(endoglucanase(EG)、cellobiohydrolase(CBH)、β-glucosidase(BGL))の作用によって分解される。このセルラーゼは、原料の乾燥重量あたり3~30FPU/g、好ましくは5~20FPU/g添加する(FPU/gは60分間にろ紙からグルコースを10.8mg生成するセルラーゼ酵素活性の単位)。
糖化物は発酵装置へ送られ、発酵装置内で発酵される。糖をエタノールに変換するためには、サッカロマイセス属、シゾサッカロマイセス属、クルイベロマイセス属、ピキア属、キャンジダ属の酵母、ザイモモナス属、クロストリディウム属の細菌、あるいはそれらの特定遺伝子を組み込んだ遺伝子組換微生物を用いる。このエタノール発酵菌は、例えばサッカロマイセス セレビジエの場合、原料容積あたり1~100g wet-wt/L、好ましくは5~50g wet-wt/L接種する。また、糖を乳酸に変換するためには、例えばリゾプス・オリザエ(Rhizopus oryzae)のような糸状菌等を用いることができ、糖をコハク酸に変換するためには、例えばコリネ型細菌(Coryneform bacterium)、バチルス属細菌、リゾビウム属細菌等を用いることができる。
前記では、糖化と発酵を別々の装置で行うケースを示したが、糖化と発酵を一つの装置内で同時に行うようにしても良い。
前記発酵によって生成された発酵もろみは、もろみ塔または蒸発缶へ送られる。もろみ塔では発酵もろみを沸点付近の温度で加熱し、蒸発したエタノールまたは有機酸を凝縮させて濃度の高いエタノール液または有機酸含有液を得る。このエタノールまたは有機酸の濃度は約30%以下、より詳しくは3~20%程度である。一方、エタノールや有機酸よりも沸点が高い成分や糖化発酵されなかったセルロースやリグニン等の固形物を含む液は、もろみ塔のボトムから排出され廃棄される。なお、蒸発缶においても前記と同様の操作が行われる。
蒸発工程を経たエタノール液または有機酸含有液は、精留塔または蒸留塔へ送られる。精留塔ではエタノール液または有機酸含有液を目的成分の沸点近傍の温度で加熱し、蒸発したエタノールまたは有機酸を凝縮させて濃度の高いエタノール液または有機酸含有液を得る。生成物がエタノールの場合、精留塔留分中のエタノール濃度は90~95容積%である。一方、精留工程によって生じる廃液は、精留塔のボトムから排出される。なお、蒸留塔においても前記と同様の操作が行われる。
最終製品の要求品質によっては、更なる高濃度化または不純物除去のため、更なる精留工程を設けたり、脱水工程を設けたりする場合がある。
セルロースおよびヘミセルロースを含むバイオマスが前処理されると、主にヘミセルロースの一部が分解して液化する。前処理の条件が強いと分解生成物の量が多くなるため、本発明においてはこの分解生成物量を基に前処理の進行具合を判断する。同様に、分解していない残存固形物量を基に前処理の進行具合を判断しても良い。
上記の内容を以下に、具体例を挙げて本発明を詳述する。
そして、以下の計算式より、供給バイオマス固形物1ton当たりの、固形物残存量W3(kg)を求める。
本発明においては、適切に管理された前処理の下で生成した前処理バイオマスを糖化酵素生産工程で利用することもできる。この工程は糖化酵素生産装置によって行われる。この糖化酵素生産工程は、酵素生産菌を培養する工程と、培養した酵素生産菌を用いて酵素を生産する工程とからなる。以下に、この内容を詳述する。
水洗浄して異物を除去したバガスを、加圧容器内に充填し、25気圧の飽和蒸気を吹き込むことにより180~220℃まで加熱し、4~10分間水熱処理する前処理を行った。このようにして得られた水熱反応物を、アクレモニウム・セルロリティカス(Acremonium cellulolyticus)C-1株(Ferm P-18058)によって生産されたセルラーゼ酵素と、サッカロマイセス・セロビシエ属酵母で同時糖化発酵した。同時糖化発酵は、水熱反応物の固形物濃度が発酵液総量に対し10%(重量・乾ベース)となるように添加し、セルラーゼ酵素を固形物に対して10FPU/g-固形物、酵母培養液の添加量を全発酵液量に対し5%として、35℃、48時間行った。
エタノールの最大収量を100%としたとき、エタノール収量が80%以上になる場合は、固形物残存量が600~750kgの場合、紫外線吸光度が180~400nmの場合、酸度が20~40g/kg-固形物の場合、pHが3.2~3.8の場合であった。つまり、前処理バイオマス1000kg当たりの固形物残存量が600~750kg、紫外線吸光度が180~400nmの場合、酸度が20~40g/kg-固形物の場合、pHが3.2~3.8になるように前処理を制御することにより、エタノールを安定的に多く得ることができる。
Claims (5)
- バイオマスを前処理する前処理装置と、
前処理されたバイオマスのpH、酸度、アルカリ度、紫外線吸収率、分解物量および未分解物量の群から選ばれる少なくとも1つを測定する測定手段と、
前記測定結果に基づいて前処理装置の運転条件または前処理前のバイオマスの性状を制御する制御手段と、
を有することを特徴とするバイオマスの処理システム。 - 前記制御手段は、前処理の反応時間、反応温度、前処理前のバイオマスのpH、酸度およびアルカリ度の少なくとも1つを制御する請求項1記載のバイオマスの処理システム。
- 前記制御を行って前処理したバイオマスを糖化酵素によって糖化させ、糖化したバイオマスを発酵微生物によって発酵させる糖化・発酵手段をさらに有する請求項1または2記載のバイオマスの処理システム。
- 前記制御を行って前処理したバイオマスを糖化酵素によって糖化させ、糖化したバイオマスを発酵微生物によって発酵させる糖化・発酵手段と、
前記糖化・発酵手段で用いる糖化酵素を生産する糖化酵素生産装置と、
前処理したバイオマスの一部をそのまま前記糖化・発酵手段へ送る第1処理手段と、
前処理したバイオマスの残部を前記糖化酵素生産装置に供給し、供給した前処理バイオマスを培地に用いて糖化酵素生産菌を培養して糖化酵素の生産を行い、生産した糖化酵素を前記糖化・発酵手段へ送る第2処理手段と、
をさらに有する請求項1または2記載のバイオマスの処理システム。 - バイオマスを前処理装置によって前処理する工程と、
前処理されたバイオマスのpH、酸度、アルカリ度、紫外線吸収率、分解物量および未分解物量の群から選ばれる少なくとも1つを測定手段によって測定する工程と、
前記測定結果に基づき前処理装置の運転条件または前処理前のバイオマスの性状を制御手段によって制御する工程と、
を有することを特徴とするバイオマスの処理方法。
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TOMOKI HAYAKAWA ET AL.: "Mokushitsu Biomass kara no Alcohol Seizo Gijutsu", ECO INDUSTRY, vol. 9, no. 2, 2004, pages 45 - 52 * |
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JP2014003914A (ja) | 2014-01-16 |
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US20150306559A1 (en) | 2015-10-29 |
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