WO2012128359A1 - バイオマスを原料とする糖液製造装置 - Google Patents
バイオマスを原料とする糖液製造装置 Download PDFInfo
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- WO2012128359A1 WO2012128359A1 PCT/JP2012/057567 JP2012057567W WO2012128359A1 WO 2012128359 A1 WO2012128359 A1 WO 2012128359A1 JP 2012057567 W JP2012057567 W JP 2012057567W WO 2012128359 A1 WO2012128359 A1 WO 2012128359A1
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M43/00—Combinations of bioreactors or fermenters with other apparatus
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/12—Bioreactors or fermenters specially adapted for specific uses for producing fuels or solvents
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/18—Apparatus specially designed for the use of free, immobilized or carrier-bound enzymes
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
- C12M47/10—Separation or concentration of fermentation products
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B20/00—Purification of sugar juices
- C13B20/16—Purification of sugar juices by physical means, e.g. osmosis or filtration
- C13B20/165—Purification of sugar juices by physical means, e.g. osmosis or filtration using membranes, e.g. osmosis, ultrafiltration
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/002—Xylose
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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
- 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 sugar liquid production apparatus using biomass as a raw material.
- Patent Document 1 and Patent Document 2 Conventionally, after saccharification treatment of biomass such as wood with dilute sulfuric acid and concentrated sulfuric acid, solid-liquid separation, neutralization of the liquid phase, and production technology such as ethanol used as a raw material for ethanol fermentation have been put into practical use ( Patent Document 1 and Patent Document 2). Moreover, chemical industrial raw material production (for example, lactic acid fermentation etc.) is also considered using sugar as a starting material.
- the biomass refers to the accumulation of organisms incorporated into the material circulation system of the earth biosphere or organic substances derived from the organisms (see JIS K 3600 1258).
- sugarcane, corn, etc. which are currently used as alcohol raw materials, are originally provided for food.
- it is effective food products to make these edible resources long-term and stable for industrial use. From the viewpoint of life cycle, it is not preferable.
- Cellulose resources vary from 38 to 50% for cellulose, 23 to 32% for hemicellulose components, and 15 to 22% for lignin components that do not become fermentation raw materials.
- the raw materials are assumed to be fixed, and there is no disclosure of production system technology considering the versatility of raw materials.
- Patent Documents 1 to 3 a phenomenon occurs in which the side reaction product causes enzyme saccharification inhibition and the saccharide yield decreases. Therefore, the enzyme saccharification inhibitor is removed and enzyme saccharification mainly by cellulose is performed.
- the proposal of the hydrothermal decomposition apparatus which improves property was made first (patent documents 4 and 5).
- JP-T 9-507386 Japanese National Patent Publication No. 11-506934 JP 2005-168335 A JP 2009-183805 A JP 2009-183154 A
- biomass and pressurized hot water are supplied so as to face each other and are subjected to a hydrothermal reaction by internal heat exchange. Since it is in a high temperature state of 240 ° C. and is decomposed by applying a pressure higher by 0.1 to 0.4 MPa to the saturated steam of water at each temperature, the biomass high-temperature treatment liquid after the reaction ( The hydrothermal discharge liquid) contains decomposition products such as lignin.
- the hot water-soluble component dissolved in the biomass high-temperature treatment liquid is cooled to the enzyme saccharification temperature (for example, 60 ° C. or lower) in the subsequent saccharification step. It has been found that a part of the precipitate precipitates to produce a solidified or colloidal poorly water-soluble substance. Furthermore, in this invention, it discovered that this poorly water-soluble substance had an inhibitory effect
- the above-mentioned problem a device that efficiently removes a poorly water-soluble substance generated when a biomass raw material is decomposed under high temperature and high pressure conditions after enzymatic saccharification, and a saccharide using biomass containing sugar concentration as a raw material.
- a liquid manufacturing apparatus is provided.
- the first invention of the present invention is a hydrothermal decomposition apparatus that performs high-temperature and high-pressure treatment in a temperature range of 180 ° C. to 240 ° C. while bringing a biomass raw material containing at least cellulose, hemicellulose, and lignin into contact with pressurized hot water.
- Cooling means for cooling the biomass high-temperature treatment liquid discharged from the hydrothermal decomposition apparatus, an enzyme saccharification tank that saccharifies with an enzyme using the cooled treatment liquid, and poorly water-soluble water contained in the sugar liquid extracted from the enzyme saccharification tank Water is added to the sugar solution that is provided on the downstream side of the solid-liquid separation device that removes substances, a microfiltration (MF) membrane, and a foreign substance removal unit that removes the poorly water-soluble substance. And a dilution tank for dilution, and a reverse osmosis (RO) membrane (116a) that removes water from the diluted sugar solution to obtain a concentrated sugar solution.
- MF microfiltration
- RO reverse osmosis
- a sugar solution purification tank storing the sugar solution extracted from the enzyme saccharification tank, and a sugar extracted and interposed in the first circulation line from the sugar solution purification tank
- MF microfiltration
- a foreign substance removing unit provided with a membrane.
- the third invention resides in a sugar liquid production apparatus using biomass as a raw material, wherein the enzyme saccharification tank and the sugar liquid purification tank are integrated in the second invention.
- a dilution tank for adding and diluting the sugar solution treated with the foreign matter removing unit and removing the poorly water-soluble fermentation inhibitor, and separating water from the water-diluted sugar solution
- a water separation unit having a reverse osmosis (RO) membrane.
- the invention has a first measurement unit that measures one or both of turbidity and absorbance of a sugar solution from which a hardly soluble substance is removed. It is in the sugar liquid production apparatus using biomass as a raw material.
- the poorly water-soluble fermentation inhibiting substance produced when the biomass raw material containing at least cellulose, hemicellulose, and lignin is subjected to high-temperature and high-pressure treatment at 180 ° C. to 240 ° C. while being brought into opposite contact with each other completely. It can be removed to obtain a sugar solution with few impurities.
- the sugar solution can be concentrated by the reverse osmosis membrane in the latter stage, and a sugar solution having a higher concentration than conventional can be produced. With the improvement of the sugar solution, fermentation inhibition can be suppressed.
- FIG. 1 is a schematic diagram of a sugar liquid production apparatus using biomass as a raw material according to the first embodiment.
- FIG. 2 is a schematic diagram of a fermentation apparatus using biomass according to Example 2 as a raw material.
- FIG. 3 is a schematic view of a sugar liquid production fermentation apparatus using biomass as a raw material according to Example 3.
- FIG. 4 is a schematic view of a sugar liquid production fermentation apparatus using biomass as a raw material according to Example 4.
- FIG. 5 is a measurement chart of high performance liquid chromatography.
- FIG. 6 is a diagram showing the results of the amount of carbon dioxide reduction in the ethanol fermentation test.
- FIG. 7 is a diagram showing the results of the amount of carbon dioxide reduction in the ethanol fermentation test.
- FIG. 8 is a schematic diagram illustrating the biomass hydrothermal decomposition apparatus according to the first embodiment.
- FIG. 8 is a schematic diagram illustrating the biomass hydrothermal decomposition apparatus according to the first embodiment.
- a hydrothermal decomposition apparatus 50
- the hydrothermal decomposition apparatus 50 is a vertical apparatus as shown in FIG. 8, but the present invention is not limited to this, and may be an inclined or horizontal hydrothermal decomposition apparatus.
- the hydrothermal decomposition apparatus is more preferably an inclined type or a vertical type. This is because the gas generated in the hydrothermal decomposition reaction, the gas brought into the raw material, and the like can be quickly removed from above, which is preferable. Further, since the decomposition product is extracted with the pressurized hot water 55, the concentration of the extract increases from the upper side to the lower side in terms of extraction efficiency, which is preferable.
- the conveying screw means 54 by providing the conveying screw means 54, 1) the solid content can be conveyed by the solid-liquid counterflow. 2) Solid-liquid separation can be performed in the apparatus main body 53. 3) Mixing of the solid surface and pressurized hot water 55 in the solid progresses in the apparatus main body 53, and the reaction is promoted.
- the hydrothermal decomposition apparatus 50 supplies a biomass raw material (for example, straw in the present embodiment) 51 from a normal pressure to a pressurized pressure by a biomass supply apparatus 52, and is different from the supply of the biomass raw material 51.
- the pressurized hot water 55 is supplied into the apparatus main body 53 from the part side, hydrothermally decomposed while the biomass raw material 11 and the pressurized hot water 55 face each other, and the lignin component and the hemicellulose component are contained in the pressurized hot water 55.
- the lignin component and the hemicellulose component are separated from the biomass raw material 51, and the biomass solids 56 is extracted from under pressure to normal pressure by the biomass extraction device 57.
- Reference numeral 58 in the figure indicates pressurized nitrogen.
- the biomass raw material supplied to the hydrothermal decomposition apparatus 50 is not particularly limited, and refers to the accumulation of organisms incorporated into the material circulation system of the earth biosphere or organic matter derived from organisms ( JIS K 3600 1258), however, in the present invention, it is particularly preferable to use woody resources such as hardwood, herbaceous cellulosic resources, agricultural waste, food waste, and the like.
- the pretreatment device may be pretreated using, for example, a pulverizer. Moreover, you may make it wash
- the reaction temperature in the hydrothermal decomposition apparatus 50 is preferably in the range of 180 ° C. to 240 ° C. More preferably, the temperature is 200 ° C to 230 ° C. This is because at a low temperature of less than 180 ° C., the hydrothermal decomposition rate is low, a long decomposition time is required, leading to an increase in the size of the apparatus, which is not preferable. On the other hand, when the temperature exceeds 240 ° C., the decomposition rate becomes excessive, and the cellulose component increases from the solid to the liquid side, and the excessive decomposition of the hemicellulose saccharide is promoted, which is not preferable.
- the hemicellulose component dissolves from about 140 ° C., the cellulose from about 230 ° C., and the lignin component from about 140 ° C., but the cellulose remains on the solid side, and the hemicellulose component and the lignin component have a sufficient decomposition rate. It should be in the range of 180 ° C to 240 ° C.
- reaction pressure is preferably set to a pressure higher by about 0.1 to 0.5 MPa than the saturated vapor pressure of water at each temperature at which the inside of the apparatus main body 53 is in the state of pressurized hot water 55.
- the reaction time is preferably 20 minutes or less and 3 to 10 minutes. This is because if the reaction is carried out too long, the proportion of the overdecomposed product increases, which is not preferable.
- the hydrothermal decomposition apparatus 50 makes a uniform pressurized hot water flow when the biomass raw material 51 and the pressurized hot water 55 are brought into contact with each other.
- the biomass high temperature treatment liquid 101A in the present invention can be obtained.
- the pressurized hot water 55 may be any of alkaline, neutral, and acidic pH.
- alkaline sodium hydroxide, slaked lime, ammonia and the like can be used, and if acidic, diluted sulfuric acid, Hydrochloric acid, phosphoric acid, etc. can be used.
- acidic, diluted sulfuric acid, Hydrochloric acid, phosphoric acid, etc. can be used.
- the pressurized hot water 55 is alkaline or acidic, it has an advantage that the pretreatment of biomass can proceed efficiently.
- it is necessary to adjust the pH before introducing the enzyme and there is a disadvantage that a pH adjusting chemical or a pH adjusting device must be installed.
- FIG. 1 is a schematic diagram of a sugar liquid production apparatus using biomass as a raw material according to the first embodiment.
- a cooling means 90 for cooling the biomass high temperature treatment liquid 101A discharged from the hydrothermal treatment apparatus 50 of FIG. 8, an enzyme saccharification tank 103 for saccharifying with an enzyme using the cooled treatment liquid 101B, and the enzyme saccharification
- a foreign matter removing unit 113 having a solid-liquid separation device 112 and a microfiltration (MF) membrane 113a for removing poorly water-soluble substances contained in the sugar liquid 104 extracted from the tank 103, and a downstream side of the foreign matter removing unit 113
- a dilution tank 132 for adding and diluting the sugar solution from which the poorly water-soluble substance has been removed, and reverse osmosis (RO) for removing the water 114 from the diluted sugar solution to obtain a concentrated sugar solution 115.
- a sugar solution manufacturing apparatus using biomass as a raw material having a water separation unit 116 provided with a membrane 116a will be
- Biomass high-temperature treatment that occurs when biomass raw materials are decomposed under high-temperature and high-pressure conditions by providing a foreign matter removal unit 113 including a solid-liquid separator 112 that removes poorly water-soluble substances and a microfiltration (MF) membrane 113a.
- a foreign matter removal unit 113 including a solid-liquid separator 112 that removes poorly water-soluble substances and a microfiltration (MF) membrane 113a.
- the poorly water-soluble substance as shown in the test examples described later, has not been elucidated in detail.
- furfural HMF (5-hydroxymethyl) is known as a fermentation inhibitor. It was confirmed by the present inventors that the substance is different from furfural.
- biomass and pressurized hot water are supplied so as to face each other and hydrothermally react by internal heat exchange, and the reaction conditions at that time are internal. Since it is in a high temperature state at a temperature of 180 ° C. to 240 ° C. and a pressure higher by 0.1 to 0.4 MPa is applied to the saturated steam of water at each temperature,
- the hot water discharge liquid contains a reaction decomposition product such as lignin.
- the hot water-soluble component dissolved in the biomass high-temperature treatment liquid is cooled to the enzyme saccharification temperature (for example, 60 ° C. or lower) in the subsequent saccharification step. Part of this precipitates, becomes solidified or colloidal, and becomes a poorly water-soluble substance. That is, when the biomass raw material is decomposed at room temperature, this poorly water-soluble substance does not exist on the liquid side, and thus is presumed to be a unique substance in the biomass high-temperature treatment liquid.
- the enzyme saccharification temperature for example, 60 ° C. or lower
- such a poorly water-soluble substance is removed by the sugar liquid purification means 110, whereby purification in the saccharification treatment is performed, and in the subsequent step, for example, the subsequent fermentation step, a good fermentation treatment is performed.
- the fermentation efficiency of alcohol fermentation can be improved.
- the sugar liquid purification means 110 includes a solid-liquid separation device 112 that separates a solid residue such as lignin containing a poorly water-soluble substance 111 from a sugar liquid 104 extracted from the enzyme saccharification tank 103, and a solid-liquid separation device 112. And a foreign matter removing unit 113 having a microfiltration (MF) membrane 113a for further removing the hardly water-soluble substance remaining from the sugar liquid 104 separated by the liquid separation device 112.
- MF microfiltration
- the solid-liquid separator 112 can be, for example, a screw decanter, a sand filter, an MF membrane, or the like, thereby removing solids and protecting the RO membrane 116a.
- the sugar liquid production apparatus 100A using biomass as a raw material has a dilution tank 132 for adding water (RO water) 131 to dilute the sugar liquid 104 from which the hardly water-soluble fermentation inhibitor is removed.
- symbol P 6 illustrates a liquid feed pump that feeds the dilution water 133 to the water separation unit 116.
- the diluted water 133 diluted in the dilution tank 132 is separated into water 114 by a water separator 116 having an RO (Reverse Osmosis: RO) membrane 116a and concentrated to a predetermined concentration to obtain a concentrated sugar solution 115. .
- RO Reverse Osmosis
- a loose RO membrane may be used for the water separation unit 116.
- NF membrane nanofiltration membrane
- the solid-liquid separation process of the solid-liquid separation device 112 and the film process of the foreign substance removal unit 113 are effectively performed. It is possible to remove poorly water-soluble substances.
- the hot water discharge liquid of the present invention mainly contains a hemicellulose component
- the sugar liquid is purified when performing C5 saccharification / membrane treatment for enzymatic saccharification of this hot water soluble component into pentose sugar (C5 sugar) or the like. Is what you do.
- a biomass high-temperature treatment liquid (hot water discharge liquid) 101A is introduced, the enzyme 102 is added, and saccharification is performed by an enzyme reaction in the enzyme saccharification step.
- the sugar liquid 104 is stored in the first sugar liquid tank 121. Thereafter, the solid residue 111 such as lignin containing a hardly water-soluble substance is separated by the solid-liquid separator 112, and then the sugar liquid 104 is stored in the second sugar liquid tank 122.
- the foreign substance such as the solid residue 111 such as lignin containing the poorly water-soluble substance is further membrane-separated from the sugar liquid 104 by the foreign substance removing unit 113 including the MF film 113a, and then the sugar liquid 104 is stored in the dilution tank 132. Is done.
- the sugar liquid 104 containing foreign substances that are not removed is returned to the first sugar liquid tank 121 or the second sugar liquid tank 122.
- the diluted water 133 is obtained by removing the water 114 by the water separator 116 provided with the RO membrane 116a to obtain a concentrated sugar solution 115.
- This concentrated sugar solution 115 obtains various organic raw materials in a later step.
- symbols M 1 to M 3 denote motors that drive the agitation means of the enzyme saccharification tank 103 and the first to second sugar solution tanks 121 to 122, and P 1 to P 3 denote the sugar solution 104.
- the sugar liquid purification means 110 removes the poorly water-soluble substance and the like contained in the biomass high temperature treatment liquid 101A generated when the biomass raw material is decomposed under high temperature and high pressure conditions.
- the sugar liquid purification means 110 removes the poorly water-soluble substance and the like contained in the biomass high temperature treatment liquid 101A generated when the biomass raw material is decomposed under high temperature and high pressure conditions.
- a first measurement unit for example, a turbidimeter and / or a turbidimeter and / or an absorbance measuring the turbidity and / or absorbance of the concentrated sugar liquid 115 purified by the sugar liquid purification means 110 and having removed the poorly water-soluble substance or the like).
- An absorptiometer for example, a turbidimeter and / or a turbidimeter and / or an absorbance measuring the turbidity and / or absorbance of the concentrated sugar liquid 115 purified by the sugar liquid purification means 110 and having removed the poorly water-soluble substance or the like.
- the purpose of measuring the turbidity and / or the absorbance in the first measuring unit is to monitor the degree of impurity removal of the concentrated sugar solution 115 (a measure of the clarity of the sugar solution 104).
- FIG. 2 is a schematic diagram of a fermentation apparatus using biomass according to Example 2 as a raw material.
- an alcoholic fermentation apparatus 200 using biomass as a raw material includes a sugar solution manufacturing apparatus 100A using biomass as a raw material shown in FIG. 1 and a concentrated sugar obtained by a sugar liquid manufacturing apparatus 100A using biomass as a raw material.
- a fermenter 140 that performs ethanol fermentation using the liquid 115.
- Yeast 142 is added to the fermentation tank 141 of the fermenter 140 to obtain an ethanol fermentation solution 143.
- the ethanol fermentation liquid 143 is separately distilled to obtain the target ethanol.
- symbol M 5 is a motor that drives a stirring unit that stirs the fermentation tank 141
- P 5 is a liquid feed pump that feeds the ethanol fermentation liquid 143.
- the poorly water-soluble fermentation inhibiting substance can be removed by the sugar liquid purification means 110, purification in the saccharification treatment is performed, and in the subsequent alcohol fermentation process, it is possible to perform a favorable fermentation treatment. .
- examples of the chemical product based on the sugar solution include lactic acid in addition to alcohol. Therefore, the sugar solution derived from biomass can be efficiently used as a substitute for a chemical product derived from crude oil, which is a depleted fuel, and as a raw material for producing the substitute.
- FIG. 3 illustrates a sugar liquid production apparatus using the biomass high-temperature treatment liquid according to Example 3 with reference to the drawings.
- symbol is attached
- a sugar solution producing apparatus 100B using biomass as a raw material is provided with a sugar solution purifying means 110 having a configuration different from that of the first embodiment shown in FIG.
- a sugar liquid purification tank 151 that stores the sugar liquid 104 extracted from the enzyme saccharification tank 103 and a first circulation line L 1 from the sugar liquid purification tank 151.
- a solid-liquid separation device 112 that removes a poorly water-soluble substance (solid residue such as lignin) 111 and the second circulation line L 2 from the sugar solution refining tank 151.
- a foreign matter removing unit 113 having a microfiltration (MF) film 113a for removing a poorly water-soluble substance from the liquid 104.
- symbol M 6 indicates a motor that drives the stirring means of the sugar liquid refining tank 151.
- the membrane treatment was sequentially performed.
- two circulation lines (first circulation line L) were provided in the sugar liquid purification tank 151. 1 and the second circulation line L 2 ), it is possible to perform treatment according to the concentration of the poorly water-soluble substance (solid residue 111 such as lignin).
- the ratio of the hardly water-soluble substance solid residue 111 such as lignin
- the combined treatment with the first circulation line L 1 and the second circulation line L 2 is performed, and the hardly water-soluble substance is removed. Try to remove.
- membrane process using the 2nd circulation line L2 can be performed.
- FIG. 4 is a schematic diagram of a sugar liquid production apparatus using biomass as a raw material according to Example 4.
- a sugar solution producing apparatus 100C using biomass as a raw material is a sugar solution refining tank in which the enzyme saccharification tank 103 and the sugar solution refining tank 151 in the sugar liquid refining means 110 of Example 4 are integrated.
- a symbol M 7 illustrates a motor that drives the stirring means of the sugar liquid refining tank 161.
- Example 3 although the enzyme saccharification tank 103 and the sugar liquid refinement tank 151 were installed separately, in this Example, the installation space can be omitted by integrating them. .
- various fermentations can be performed by providing the fermenter 140 that performs, for example, ethanol fermentation described in Example 2. At this time, since the poorly water-soluble substance is removed, a favorable fermentation process can be performed in the subsequent fermentation process.
- the biomass high-temperature treatment liquid was obtained by hydrothermally decomposing rice straw under a pressurized condition of 180 ° C. using the hydrothermal decomposition apparatus 50 shown in FIG. 8, and the hot water discharge liquid 101A was used.
- the solvents used are acetonitrile, acetone, and methanol, all of which are polar solvents.
- pure water filtered with “Milli-Q” (trade name) was used.
- the operation was performed by mixing the high-temperature biomass-treated liquid after cooling with these solvents and water, and allowing them to stand overnight in a refrigerator (4 ° C.). Then, centrifugation operation (15,000 rpm, 10 minutes, 4 ° C.) was performed, and the supernatant was collected and treated with a filter (0.45 ⁇ m).
- test liquid after this filter treatment (Test 1-1: Acetonitrile, Test 1-2: Acetone, Test 1-3: Methanol, Test 1-4: Pure water) was analyzed by high performance liquid chromatography (HPLC).
- HPLC high performance liquid chromatography
- an ODS column (synergy 4 ⁇ Hydro-RP80A 4.6 ⁇ 250 mm: manufactured by Phenomenex) was used.
- the eluent was water-acetonitrile solvent and the acetonitrile concentration was gradient-treated from 8% to 100%.
- the detection wavelength was 220 nm.
- FIG. 5 is a measurement chart of high performance liquid chromatography.
- HMF 5-hydroxymethylfurfural: elution time around 6.5 minutes
- furfural elution time around 10.5 minutes
- unknown peak components were confirmed in tests 1-1 to 1-3 at an elution time of around 22.6 minutes. In Test 1-4, this unknown peak component was not detected. Therefore, it was proved that a poorly water-soluble substance was mixed in the biomass high-temperature treatment liquid.
- Pichia stipitis NBRC1687 (standard strain) was used.
- Pre-culture conditions were as follows: 10 mL YPD (1% yeast extract, 2% peptone, 2% glucose) was used as a medium and cultured with shaking at 30 ° C. and 120 rpm. Fermentation was carried out by preparing a pre-fermented liquid filtered with a filter (0.45 ⁇ m) and a liquid not filtered with the filter (0.45 ⁇ m). The ethanol fermentation conditions were 100 mL of fermentation broth, and 120 rpm shaking culture was performed at 30 ° C.
- 6 and 7 are graphs showing the results of the amount of carbon dioxide reduction in the ethanol fermentation test.
- the horizontal axis is time, and the vertical axis is CO 2 reduction.
- test 2-2 no nutrient source, no filter
- test 2-1 no nutrient source, no filter
- Test 2-3 with nutrient source and without filter
- Test 2-4 with nutrient source and with filter
- test 2-2 was 11%
- the fermentation efficiency of test 2-4 was 38%.
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Abstract
Description
また、糖を出発原料として、化学工業原料生産(例えば乳酸発酵等)も考えられる。
ここで、バイオマスとは、地球生物圏の物質循環系に組み込まれた生物体又は生物体から派生する有機物の集積をいう(JIS K 3600 1258参照)。
図8は、実施例1に係るバイオマスの水熱分解装置を示す概略図である。
まず、「少なくともセルロース、ヘミセルロース及びリグニンを含むバイオマス原料と加圧熱水とを対向接触させつつ180℃~240℃の温度範囲で高温高圧処理する水熱分解装置(50)」に関して図8を使用して説明する。
水熱分解装置50は、図8に示すように垂直型の装置としているが、本発明はこれに限定されるものではなく、傾斜型や水平型の水熱分解装置としてもよい。なお、水熱分解装置としては、傾斜型又は垂直型がより好ましい。これは、水熱分解反応において発生したガスや原料中に持ち込まれたガス等が上方から速やかに抜けることができ好ましいからである。また、加圧熱水55で分解生成物を抽出するので、抽出効率の点において上方から下方に向かって抽出物の濃度が高まることとなり、好ましいものとなるからである。
本実施例では、バイオマスの供給前において、前処理装置として、例えば粉砕装置を用いて前処理するようにしてもよい。また、洗浄装置により洗浄するようにしてもよい。
なお、バイオマス原料として、例えば籾殻等の場合には、粉砕処理することなく、そのまま水熱分解装置50に供給することができるものとなる。
これは、180℃未満の低温では、水熱分解速度が小さく、長い分解時間が必要となり、装置の大型化につながり、好ましくないからである。一方240℃を超える温度では、分解速度が過大となり、セルロース成分が固体から液体側へ移行を増大すると共に、ヘミセルロース系糖類の過分解が促進され、好ましくないからである。
また、ヘミセルロース成分は約140℃付近から、セルロースは約230℃付近から、リグニン成分は140℃付近から溶解するが、セルロースを固形分側に残し、且つヘミセルロース成分及びリグニン成分が十分な分解速度を持つ180℃~240℃の範囲とするのがよい。
また、反応時間は20分以下、3分~10分とするのが好ましい。これはあまり長く反応を行うと過分解物の割合が増大し、好ましくないからである。
次に、前記図8の水熱処理装置50で排出されたバイオマス高温処理液101Aを冷却する冷却手段90と、冷却された処理液101Bを用いて酵素により糖化する酵素糖化槽103と、前記酵素糖化槽103から抜き出した糖液104に含まれる水難溶性物質を除去する固液分離装置112および精密濾過(Microfiltlation:MF)膜113aを備えた異物除去部113と、前記異物除去部113の後流側に設けられ、水難溶性物質を除去した糖液に水を添加して希釈する希釈槽132と、希釈した糖液から水114を除去して、濃縮糖液115を得る逆浸透(Reverse Osmosis:RO)膜116aを備えた水分分離部116とを有するバイオマスを原料とする糖液製造装置に関して図1を用いて説明する。
すなわち、常温でバイオマス原料を分解処理するような場合には、この水難溶性物質は液体側には存在しないものであるので、バイオマス高温処理液における特異な物質であると推定される。
本発明の熱水排出液は主にヘミセルロース成分を含むので、この熱水可溶分を五炭糖(C5糖)等に酵素糖化するC5糖化・膜処理を行う際に、糖液の精製を行うものである。
先ず、前記酵素糖化槽103において、バイオマス高温処理液(熱水排出液)101Aが導入され、酵素102が添加され、酵素糖化工程における酵素反応による糖化がなされる。
次に、糖液104は第1の糖液タンク121に貯留される。その後、固液分離装置112により水難溶性物質を含むリグニン等固形残渣111が分離され、その後糖液104は第2の糖液タンク122に貯留される。
次に、糖液104は、MF膜113aを備えた異物除去部113によりさらに残存する水難溶性物質を含むリグニン等固形残渣111等の異物が膜分離され、その後糖液104は希釈槽132に貯留される。
除去されない異物を含む糖液104は、第1の糖液タンク121又は第2の糖液タンク122に戻すようにしている。
次に、水難溶性発酵阻害物質を除去した糖液104は、希釈槽132で水(RO水)131が添加されて希釈水133を得る。
次に、希釈水133は、RO膜116aを備えた水分分離部116により水114が除去され、濃縮糖液115を得る。
この濃縮糖液115は、後工程において、各種有機原料を得る。
なお、図1中、符号M1~M3は、酵素糖化槽103、第1~第2の糖液タンク121~122の攪拌手段を駆動するモータ、P1~P3は、糖液104を送液する送液ポンプである。
図2は、実施例2に係るバイオマスを原料とする発酵装置の概略図である。
図2に示すように、バイオマスを原料とするアルコール発酵装置200は、図1に示すバイオマスを原料とした糖液製造装置100Aと、バイオマスを原料とした糖液製造装置100Aで得られた濃縮糖液115を用いてエタノール発酵を行う発酵槽140とを有するものである。
この発酵槽140の発酵タンク141には酵母142が添加され、エタノール発酵液143が得られる。エタノール発酵液143は、別途蒸留処理がなされて目的のエタノールが得られる。
なお、図2中、符号M5は、発酵タンク141を攪拌する攪拌手段を駆動するモータ、P5は、エタノール発酵液143を送液する送液ポンプである。
図3は、実施例3に係るバイオマス高温処理液を用いた糖液製造装置について、図面を参照して説明する。
なお、実施例1の装置と同一部材については、同一符号を付してその説明は省略する。
図3に示すように、バイオマスを原料とする糖液製造装置100Bは、図1に示す実施例1と異なる構成の糖液精製手段110を設けたものである。
図3に示す糖液精製手段110は、酵素糖化槽103から抜き出した糖液104を貯留する糖液精製槽151と、前記糖液精製槽151からの第1の循環ラインL1に介装され、抜き出した糖液104から水難溶性物質(リグニン等固形残渣)111を除去する固液分離装置112と、前記糖液精製槽151からの第2の循環ラインL2に介装され、抜き出した糖液104から水難溶性物質を除去する精密濾過(Microfiltlation:MF)膜113aを備えた異物除去部113とを有するものである。
なお、図3中、符号M6は、糖液精製槽151の攪拌手段を駆動するモータを図示する。
なお、水難溶性物質が少ない場合には、第2の循環ラインL2を用いての膜処理のみを行うことができる。なお、必要に応じて固液分離処理を行うようにしてもよい。
図4は、実施例4に係るバイオマスを原料とする糖液製造装置の概略図である。なお、実施例1及び3の装置と同一部材については、同一符号を付してその説明は省略する。
図4に示すように、バイオマスを原料とする糖液製造装置100Cは、実施例4の糖液精製手段110における前記酵素糖化槽103と前記糖液精製槽151とを一体化した糖液精製槽161としている。
図中、符号M7は、糖液精製槽161の攪拌手段を駆動するモータを図示する。
この際、水難溶性物質を除去しているので、その後の発酵工程においては、良好な発酵処理を行うことが可能となる。
<水難溶性発酵阻害物の確認試験>
冷却したバイオマス高温処理液と各種溶媒とを1対9の割合で混合し、高速液体クロマトグラフィー装置を用いて、その確認を行った。
その後、遠心分離操作(15,000rpm、10分、4℃)を行い、その上澄み液を回収して、フィルター(0.45μm)で処理した。
用いたカラムは、ODSカラム(synergi 4μ Hydro-RP80A 4.6x250mm:Phenomenex社製)を用いた。
溶離液は、水-アセトニトリル溶剤で、アセトニトリルの濃度を8%から100%にグラジェント処理した。
検出波長は220nmとした。
図5及び表1に示すように、既知の発酵阻害物質であるHMF(5-ヒドリキシメチルフルフラール:溶離時間が6.5分付近)、フルフラール(溶離時間が10.5分付近)については、試験1-1~1-4の全てにおいて検出された。
これに対し、溶離時間が22.6分付近において、試験1-1~1-3では未知のピーク成分が確認された。なお、試験1-4ではこの未知のピーク成分は検出されなかった。
よって、バイオマス高温処理液中には、水難溶性の物質が混在していることが判明した。
<水難溶性物質の有無による発酵試験>
冷却後のバイオマス高温処理液を用いた糖化液用いて、発酵を行い、この発酵の際におけるCO2の減少量を比較した。
前培養条件は、培地として10mL YPD(1% イースト抽出液、2%ペプトン、2%グルコース)を用いて、30℃、120rpmで振とう培養した。
発酵は、前発酵した液をフィルター(0.45μm)で濾過したものと、該フィルター(0.45μm)で濾過しないものとを準備し、発酵を行った。
エタノール発酵条件は、発酵液100mLとし30℃で120rpm振とう培養を行った。
51 バイオマス原料
52 バイオマス供給部
53 装置本体
54 搬送スクリュー手段
55 加圧熱水
56 バイオマス固形分
57 バイオマス抜出装置
90 冷却手段
100A~100C バイオマスを原料とする糖液製造装置
101A バイオマス高温処理液(熱水排出液)
101B 冷却された処理液
102 酵素
103 酵素糖化槽
104 糖液
110 糖液精製手段
140 発酵槽
200 バイオマスを原料とするアルコール発酵装置
Claims (5)
- 少なくともセルロース、ヘミセルロース及びリグニンを含むバイオマス原料と加圧熱水とを対向接触させつつ180℃~240℃の温度範囲で高温・高圧処理する水熱分解装置と、
前記水熱分解装置で排出したバイオマス高温処理液を冷却する冷却手段と、
冷却された処理液を用いて酵素により糖化する酵素糖化槽と、
前記酵素糖化槽から抜き出した糖液に含まれる水難溶性物質を除去する固液分離装置と、
精密濾過(Microfiltlation:MF)膜を備えた異物除去部と、
前記異物除去部の後流側に設けられ、水難溶性物質を除去した糖液に水を添加して希釈する希釈槽と、
希釈した糖液から水を除去して、濃縮糖液を得る逆浸透(Reverse Osmosis:RO)膜を備えた水分分離部とを有することを特徴とするバイオマスを原料とする糖液製造装置。 - 請求項1において、
前記酵素糖化槽から抜き出した糖液を貯留する糖液精製槽と、
前記糖液精製槽からの第1の循環ラインに介装され、抜き出した糖液から水難溶性物質を除去する固液分離部と、
前記糖液精製槽からの第2の循環ラインに介装され、抜き出した糖液から水難溶性発酵阻害物質を除去する精密濾過(Microfiltlation:MF)膜を備えた異物除去部とを有することを特徴とするバイオマスを原料とした糖液製造装置。 - 請求項2において、
前記酵素糖化槽と前記糖液精製槽とを一体化してなることを特徴とするバイオマスを原料とする糖液製造装置。 - 請求項3において、
前記異物除去部で処理され、水難溶性発酵阻害物質を除去した糖液に水を添加して希釈する希釈槽と、
水希釈糖液から水を分離する逆浸透(RO)膜を有する水分分離部とを有することを特徴とするバイオマスを原料とする糖液製造装置。 - 請求項1乃至4のいずれか一つにおいて、
水難溶解物質を除去した糖液の濁度又は吸光度のいずれか一方又は両方を測定する第1の測定部を有することを特徴とするバイオマスを原料とする糖液製造装置。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007129921A1 (en) * | 2006-05-08 | 2007-11-15 | Biojoule Ltd. | Process for the production of biofuel from plant materials |
WO2008017145A1 (en) * | 2006-08-07 | 2008-02-14 | Emicellex Energy Corporation | Process for recovery of holocellulose and near-native lignin from biomass |
JP2009183154A (ja) * | 2008-02-01 | 2009-08-20 | Mitsubishi Heavy Ind Ltd | バイオマスの水熱分解装置及び方法、バイオマス原料を用いた有機原料の製造システム |
JP2009183153A (ja) * | 2008-02-01 | 2009-08-20 | Mitsubishi Heavy Ind Ltd | バイオマス原料を用いた有機原料の製造システム及び方法 |
JP2009183805A (ja) * | 2008-02-01 | 2009-08-20 | Mitsubishi Heavy Ind Ltd | バイオマスの水熱分解装置及び方法、バイオマス原料を用いた有機原料の製造システム |
WO2009110374A1 (ja) * | 2008-03-05 | 2009-09-11 | 東レ株式会社 | 多糖類系バイオマス由来化合物の製造方法 |
JP2011223975A (ja) * | 2010-03-30 | 2011-11-10 | Toray Ind Inc | 糖液の製造方法及び製造装置 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09507386A (ja) | 1993-12-23 | 1997-07-29 | コントロールド・エンヴァイロンメンタル・システムズ・コーポレーション | 工業用エタノールの製造方法 |
JPH11506934A (ja) | 1995-06-07 | 1999-06-22 | アーケノール,インコーポレイテッド | 強酸加水分解法 |
US6355110B1 (en) * | 1999-11-17 | 2002-03-12 | Tate & Lyle Industries, Limited | Process for purification of low grade sugar syrups using nanofiltration |
JP2005168335A (ja) | 2003-12-09 | 2005-06-30 | National Institute Of Advanced Industrial & Technology | 各種リグノセルロース資源からのエタノール生産システム |
WO2010038302A1 (ja) | 2008-10-02 | 2010-04-08 | 三菱重工業株式会社 | バイオマス原料を用いた有機原料の製造システム及び方法 |
CA2746504C (en) | 2008-12-09 | 2016-09-20 | Toray Industries, Inc. | Method for producing sugar liquid |
BR112012022332A2 (pt) | 2010-03-10 | 2019-09-24 | Toray Industries | "método de produção de solução de açucar refinado aquosa e ,étodo de produção de um produto quimico" |
JP5728817B2 (ja) | 2010-03-30 | 2015-06-03 | 東レ株式会社 | キシロース糖液の製造方法 |
-
2011
- 2011-03-24 JP JP2011066769A patent/JP5901128B2/ja active Active
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- 2012-03-23 CA CA2825542A patent/CA2825542C/en active Active
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007129921A1 (en) * | 2006-05-08 | 2007-11-15 | Biojoule Ltd. | Process for the production of biofuel from plant materials |
WO2008017145A1 (en) * | 2006-08-07 | 2008-02-14 | Emicellex Energy Corporation | Process for recovery of holocellulose and near-native lignin from biomass |
JP2009183154A (ja) * | 2008-02-01 | 2009-08-20 | Mitsubishi Heavy Ind Ltd | バイオマスの水熱分解装置及び方法、バイオマス原料を用いた有機原料の製造システム |
JP2009183153A (ja) * | 2008-02-01 | 2009-08-20 | Mitsubishi Heavy Ind Ltd | バイオマス原料を用いた有機原料の製造システム及び方法 |
JP2009183805A (ja) * | 2008-02-01 | 2009-08-20 | Mitsubishi Heavy Ind Ltd | バイオマスの水熱分解装置及び方法、バイオマス原料を用いた有機原料の製造システム |
WO2009110374A1 (ja) * | 2008-03-05 | 2009-09-11 | 東レ株式会社 | 多糖類系バイオマス由来化合物の製造方法 |
JP2011223975A (ja) * | 2010-03-30 | 2011-11-10 | Toray Ind Inc | 糖液の製造方法及び製造装置 |
Non-Patent Citations (5)
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015029463A (ja) * | 2013-08-02 | 2015-02-16 | 国立大学法人神戸大学 | 単糖類濃縮液の製造方法 |
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