JP2010115116A - Method for producing monosaccharide from inedible lignocellulose-based biomass, and method for producing alternate fuel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing lignin and holocellulose of inedible lignocellulose-based biomass by efficiently and individually selecting them, to provide a method for making a monosaccharide from the holocellulose by a microorganism, an enzyme or an inorganic acid, to provide a method for producing 2,3-butanediol, bioethanol, acetic acid or the like by the fermentation of a monosaccharide solution, and to provide methyl ethyl ketone of an alternate fuel having high additional value from 2,3-butanediol. <P>SOLUTION: The method includes a flow for producing the methyl ethyl ketone by regulating the obtained holocellulose material so as to be a medium concentration (7-15%) at a filter, sending the resultant product to a monosaccharide-forming reaction column of a third step to form the monosaccharide by the hydrolysis with the microorganism, the enzyme or the inorganic acid, subjecting the product to pretreatment, sending the pretreated product to a fermentation vessel of a fourth step to produce 2,3-butanediol, bioethanol, acetic acid or the like by the microorganism, and transporting the product to a solid acid-catalyzed reactor of a fifth step to produce methyl ethyl ketone. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

    The present invention relates to a technology for individually separating and producing lignin of non-edible lignocellulosic biomass and holocellulose composed of hemicellulose and cellulose, and more specifically, by hydrolysis of a hardly degradable polysaccharide in the holocellulose material. The present invention relates to a technique for producing pentose and hexose monosaccharides, and further relates to a method for producing alternative fuels such as 2,3-butanediol and methyl ethyl ketone.

    Carbon dioxide gas is generated by the use of energy generated from petroleum (thermal power generation, gazolin, kerosene, etc.), which causes global warming, and various countries are taking measures. In Brazil, bioethanol is industrially produced from sugarcane sucrose, and it is put into practical use as a partial alternative fuel for automobiles. In the United States, bioethanol is produced using monosaccharide glucose obtained from saccharification of corn starch, and it is used as an alternative fuel up to 15% of automobile gazolin. Furthermore, India, Thailand, etc. have put forth a dramatic production plan for bioethanol using sugarcane, cassava, etc.

Conventionally, sugarcane is a raw material for sugar. However, when bioethanol is produced, the unit price of sugar becomes expensive. Similarly, by using it for the production of bioethanol, food for humans such as corn, livestock, etc. , Cattle, pigs, etc.) and dairy products (cheese, milk, butter, etc.) are also rising.
Therefore, when producing bioethanol, it is necessary to use non-edible lignocellulosic biomass as an alternative to avoid edible sugarcane, cereals, potatoes and the like. Non-edible lignocellulosic biomass 1) Woody biomass such as broad-leaved trees, conifers, waste wood, sawdust, etc. 2) Non-woody biomass such as bamboo, kenaf, bagasse, rice / straw straw, bananas, etc. 3) Firewood, elephant Grass, such as glass, 4) Collected waste paper such as newspapers, magazines, ledgers, cardboard.

The main composition of non-edible lignocellulosic biomass is (1) hemicellulose formed from pentose xylan, arabinan, rhamnan and hexose mannan, galactan, glucan, (2) cellulose formed from glucan, (3) Lignin, and (4) Extract components and ash.
A conventional method for producing an alternative fuel (main bioethanol) based on the biomass is generally composed of two steps. In the first step, hemicellulose and cellulose polysaccharide are converted into monosaccharides. In the second step, the monosaccharide is fermented to produce bioethanol.

    The method of monosaccharideizing hemicellulose and cellulose polysaccharide in the first step is divided into three groups as follows.

Group 1: Physical processing methods These methods are generally divided into two subgroups.

    In the first subgroup, high-temperature (140 ° C.-230 ° C.) high-pressure (1-3 times the saturated vapor pressure) water vapor (JP 2008-184421, JP 2002-59118) or more than 1000-4000 Under pressure (Japanese Patent Laid-Open No. 2002-128802), the polysaccharides of biomass are decomposed and extracted, but there is no description of a post-treatment method for decomposing the resulting oligosaccharides into monosaccharides. On the other hand, in other Japanese Unexamined Patent Publication, hemicellulose obtained by decomposing and extracting biomass polysaccharides is further decomposed into monosaccharides with saturated steam ((Japanese Patent Laid-Open No. 2005-23041)), or high-temperature high-pressure steam. This treatment is performed in the presence of a lanthanoid metal halide or trifluoromethanesulfonic acid as a lanthanoid ion supply substance (Japanese Patent Laid-Open No. 2002-85100).

The second subgroup includes a method for decomposing and extracting biomass polysaccharides using supercritical water and subcritical water under an additive. The additives are (1) silver, copper, ferric (Fe ³⁺ ), tin sulfate, nitrate, hydrochloride, acetate salt compounds (Japanese Patent Laid-Open No. 2007-20555), (2) hydrogen peroxide ( JP2007-39368), (3) benzoquinone (JP2005-40025), and the like. The hydrolyzate obtained from the supercritical water and subcritical water treatment is treated with the wood-based carbide produced by the heat treatment method, and the furfural, 5-hydroxymethylfurfural, which is an obstacle for the enzyme for ethanol fermentation, is treated. It is removed (Japanese Patent Laid-Open No. 2005-270056).

Group 2: Microbial treatment method In this group, cellulosic materials such as wood, waste paper, corrugated cardboard, etc., with or without pretreatment, hydrolyze polysaccharides with white rot fungi or cellulase, and the resulting monosaccharides are ethanol-fermented. (JP 2008-6372, JP 2008-92910, JP 2008-161137, JP 2006-88136, JP 2006-149343).

Group 3: Chemical treatment method Group 3 is divided into the following three subgroups.

In the first subgroup, biomass is modified with polysaccharides by chemical treatment in advance, and then hydrolyzed to low molecular sugars or monosaccharides with strong acid, enzyme, supercritical water, or subcritical water. In decrystallization chemicals, JP 2008-35853 A, urea, calcium thiocyanate, sodium thiocyanate, zinc chloride, calcium chloride, magnesium chloride and other metal salts, JP 2007-202560 A, sulfuric acid, hydrochloric acid, hydrofluoric acid. Strong acid of phosphoric acid, Japanese Patent Application Laid-Open No. 2006-223152, an aldehyde-based, SO ₂ / amine-based, NOX-based, lithium chloride-based, sulfur-containing, nitrogen-containing, organic acid, organic salt, organic solvent cellulose solvent JP-A-H8-299000 described 70% by weight or more of phosphoric acid, phosphonic acid, phosphinic acid, metaphosphoric acid and the like.

    In the second subgroup, biomass is saccharified by chemical single treatment or multistage treatment of chemicals and enzymes without changing fiber crystals, and then fuel substitutes, chemicals, etc. are produced by microorganisms. The treatment chemicals are (1) hydrolyzing hemicellulose and cellulose by a two-stage treatment with hydrogen peroxide, and the obtained substance is heated at high temperature under aluminum phosphate to monosaccharideize (Japanese Patent Laid-Open No. 2008-54608). (2) Woody biomass is decomposed and delignified using hydrogen peroxide containing tungstic acid and molybdate to obtain a sugar solution from hemicellulose, and the residue is saccharified with cellulase (Japanese Patent Application Laid-Open No. 2006). -149343), or (3) peroxides (hydrogen peroxide, urea peroxide water, benzoyl peroxide, peracetic acid, persulfate, percarbonate, permanganate), superoxide and its salts, hypochlorous acid Sugars obtained by hydrolyzing biomass with chloric acid and its salts, osmium tetroxide, chromium oxide, dodecylbenzene sulfonic acid, etc. are enzymes (cellulase, xylanase, Guninaze, amylase, glucuronidase, protease, and treated with lipase), to produce lactic acid, fuel, organic acids, industrial enzymes, pharmaceuticals, amino acids, etc. (JP 2006-519606). Furthermore, (4) JP 2008-43328 A obtains a first sugar solution and a first residue after woody biomass is decomposed with dilute sulfuric acid. The nuclear first residue is treated with alkaline hydrogen peroxide to generate alkaline drainage and a second residue. The second nuclear residue is hydrolyzed with cellulase to obtain a second sugar solution. The first sugar solution and the second sugar solution are subjected to ethanol fermentation to produce ethanol. Japanese Patent Application Laid-Open Nos. 2005-229821 and 2005-229822 are methods in which biomass is saccharified by performing a multistage (2-3 stage) sulfuric acid treatment.

    In the third sub-group, the biomass component is continuously extracted with high-temperature and high-pressure hot water. In Japanese Patent Application Laid-Open No. 2007-301472, biomass is continuously charged at the top introduction part of the reactor, and pressurized hot water at 100 to 140 ° C. is supplied to the lignin and its decomposition substance, and intracellular Extract components. In the middle of the reactor, 140-230 ° C. hot pressurized water is added to extract xylooligosaccharides and xylose. The temperature of the high-pressure hot water at the bottom of the reactor is raised to 230-374 ° C. to extract cellooligosaccharides and glucose. Biomass residues are discharged from the discharge path at the bottom of the continuous reactor.

The common problems of the saccharification method are as follows.
(1) Except for Japanese Patent Application Laid-Open No. 2007-202560, in other Japanese Patent Application, lignocellulosic biomass is pulverized to a particle size of 2 mm or less, or cooking / bleaching process when using alkali (kraft) pulp raw material Etc. are required, so much energy for pulverization, cooking and bleaching is consumed, which is higher than the energy obtained from the target bioethanol.
(2) The lignin residue described in JP-A-2005-229822 is collected and washed with a filter. However, since this lignin is very fine, collection, washing, and feeding to the boiler are technical and technical. It is a new challenge. In the other JP, the composition of lignocellulosic biomass (hemicellulose, lignin, cellulose) is not used completely, so that the processing method of the lignin residue after saccharification or the residue sharing lignin / cellulose and the treatment of waste water from the saccharification step The method is not mentioned and it becomes an environmental problem.
(3) The obtained monosaccharide is a low-value-added final product such as low-energy bioethanol or lactic acid and other organic acids by fermentation.

    Bioethanol is generally used as an alternative fuel for transportation and transportation, but the energy generated from fermented bioethanol is lower than that for producing bioethanol (Hammerschlag, R., Ethanol's energy return on investment: A survey of the literature 1990-present. Environmental Science & Technology 40 (6): 1744-1750 (2006)), and the disadvantage of bioethanol is that it has less energy in the same capacity than petroleum gazoline.

In Japanese Patent Application Laid-Open No. 2007-301472, it was described that lignin, its decomposition substances, and intracellular components were extracted from the upper part of the continuous reactor with pressurized hot water at 100-140 ° C. However, from the viewpoint of optimal utilization of hemicellulose, there has been a research result that xylan is first extracted with heated hot water at 100-150 ° C., and then lignin as a wood-based material is removed by kraft cooking. (Heiningen, A. v., Converting a kraft pulp mill into an integrated forest biorefinery. Presentation no. 2 at the Solander Symposium, Pitea, Sweden, March 29 th, 2007). Furthermore, lignin is generally measured at 205 nm or 280 nm in the UV absorption spectrum, but hemicellulose dissolved in the hot water extract contains by-products such as furfural and 5-hydroxymethylfurfural. In principle, dissolved lignin is measured at 205 nm in order to absorb near 280 nm. Japanese Patent Application Laid-Open No. 2007-301472 describes that lignin is measured in the UV absorption spectrum, but the measurement wavelength is not clear. For this reason, it is doubtful whether pressurized hot water at 100-140 ° C. will completely extract lignin.
JP 2008-43328 PR JP 2008-54608 PR JP 2007-202560 A JP 2007-301472 A Japanese Laid-Open Patent Publication No. 2005-229822

    The present invention relates to (1) a method for efficiently separating and producing lignin and holocellulose separately by chipping or deinking / recovered non-edible lignocellulosic biomass by chemical treatment, and (2) lignin in waste liquid. A method of recovering and reusing energy in a dissolved concentration process and a boiler, (3) a method in which holocellulose is mono-saccharified with microorganisms / enzymes or inorganic acids, and (4) a monosaccharide solution by fermentation A method for producing 2,3-butanediol, bioethanol, acetic acid, etc., and (5) a method for producing methyl ethyl ketone, a high-value-added alternative fuel from 2,3-butanediol through a solid acid catalyst. Objective.

The present invention has the following configuration to achieve the above object.
In chip formation in the first step, woody lignocellulosic biomass is made into chips and then fed to a chlorine dioxide treatment reactor for producing holocellulose in the second step. Since the biomass slurry concentration in the reactor is low (7% or less) because it is produced at L- ¹ or less, the obtained holocellulose material is made a medium concentration (7% -15%) with a filter, It is sent to the monosaccharification reaction tower of the third step, monosaccharified by hydrolysis of microorganisms / enzymes or inorganic acids, pretreated, then sent to the fermenter of the fourth step, and 2,3-butanediol, bio This is a flow for producing methyl ethyl ketone by producing ethanol, acetic acid and the like and then feeding it to the solid acid catalyst reactor in the fifth step. On the other hand, the dissolved lignin obtained in the chlorine dioxide treatment process concentrates chlorine dioxide waste liquid containing lignin decomposition substances to 55% or more of total solid (TS) with an evaporator, and burns it with the next boiler to recover energy. ·Reuse.
Chlorine dioxide is an unstable gas, and the absorption concentration in water and the concentration that can be stored are up to about 1%, so the chlorine dioxide water used in the present invention is produced on the production site based on a commercially available method. And The commercially available methods are Mathieson method, Solvay method, R2 method, R5-R8 method, R10-R13 method, SVP method and the like. (Fredette, MC, Bleaching Chemicals: Chlorine dioxide. In “Pulp Bleaching: Principles and Practice”, Eds., Dence, CW, Reeve, DW, Tappi Press, 1996, Atlanta, GApp. 59-69).

    The present invention relates to the first step of chip formation, the third step of saccharification, the fourth step of 2,3-butanediol fermentation and the fifth step of methyl ethyl ketone production, all of which can be operated continuously, the second step of holocellulose. The production is a monosaccharide production method and an alternative fuel production method of non-edible lignocellulosic biomass, which can adopt a batch method or a continuous method.

    In the present invention, the saccharification in the third step can use any of microorganisms / enzymes or inorganic acids, and the efficiency of the fourth (2,3-butanediol fermentation) step and the fifth (methyl ethyl ketone production) step in the subsequent step. In order to improve the process, the raw materials of each step are pretreated, that is, 2,3-butanediol solution to the dehydration reaction to produce 2,3-butanediol fermentation inhibitor and methyl ethyl ketone in the monosaccharide solution It is a monosaccharide manufacturing method and an alternative fuel manufacturing method of non-edible lignocellulosic biomass which removes an inhibitory substance therein.

(1) In order to efficiently separate and produce lignin and holocellulose and to infiltrate the chemical, the biomass is first chipped, that is, the wood-based lignocellulose log is chipped with a chipper, or Using the purchased chip, any oversized chip is sent to the slicer, the average thickness of the obtained chip is 2-3 mm, and the upper screen has a round hole with a particle diameter of 50 mm or less or a square hole of 50 mm or less The chip remaining in the lower screen having a round hole with a particle diameter of 5 mm or more passing through the gas is degassed with low-pressure steam of 200 kPa or less, and treated with chlorine dioxide alone, so that the solid holocellulose and waste liquid composed of hemicellulose and cellulose Of non-edible lignocellulosic biomass that efficiently separates and produces two poles of lignin dissolved in It is a manufacturing method and alternative fuel production process.
In the raw material of corrugated cardboard and waste paper, pulp pulp used in the pulp and paper industry is used to disaggregate, deink, select, concentrate, etc., and then treat with chlorine dioxide alone to efficiently separate holocellulose and dissolved lignin. It is a monosaccharide manufacturing method and an alternative fuel manufacturing method of non-edible lignocellulosic biomass to manufacture.

  (2) The present invention provides a multistage evaporator (concentrator) after obtaining the lignin dissolved in the waste liquid when the woody biomass chip or the deinked and recovered waste paper pulp raw material is treated with chlorine dioxide alone. ) To concentrate to a total solid content (total solid: TS) concentration of 55% or more, burn in a boiler, and recover and reuse heat efficiently. This is a method for producing a monosaccharide of biomass and a method for producing an alternative fuel.

(3) In the present invention, the saccharification of the holocellulose substance can use a two-hydrolysis method of an inorganic acid (sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.) and a microorganism / enzyme.
The present invention uses sulfuric acid having a concentration of 65% -80%, preferably 65% -72%, and decomposes the holocellulose material to produce an oligosaccharide. It is then diluted with 2-6% sulfuric acid, preferably 3% -4%, at a temperature of 100 ° C-140 ° C, preferably 110 ° C-120 ° C, 30 minutes-90 minutes, preferably 45-60 minutes. This is a method of completely saccharifying under the conditions of When sulfuric acid with a concentration of 65% or less does not completely dissolve the holocellulose material, and when sulfuric acid with a concentration of 80% or more is used, the amount of water required in the next dilution step increases, and the concentration energy of the monosaccharide liquid and the sulfuric acid Cost increases.

In the hydrolysis method using microorganisms / enzymes, almost no lignin remains in the holocellulose substance, and the crystallinity of cellulose is changed, so that the saccharides are easily saccharified by microorganisms or enzymes. To decompose hemicellulose in holocellulose, xylanase, mannanase, and galactanase each monosaccharideize xylan, mannan, and galactan into xylos, mannose, and galactose.
Microorganisms that excrete xylanase are fungi, yeasts, and bacteria, and fungi are Agaricus bisporus, Aspergillus niger, Cephalosporium sacchari, Ceratocystis paradoxa, Oxiporus sp. And bacteria include Bacillus circulans, Bacillus subtilis, Streptomyces exfoliatus and the like. In mannanase, exo β-mannanase is produced from Aeromonas sp., Endo β-mannanase is isolated from Aspergillus niger, and Bacillus subtilis excretes endo β-galactanase. (Dekker, RFH, Biodegradation of Hemicelluloses. In “Biosynthesis and Biodegradation of Wood Components”, Higuchi, T., ed., Academic Press, New York, 1985, pp. 505-533).
In order to monosaccharideize cellulose, endo β-glucanase, exo β-glucanase, and β-glucosidase enzymes are required. Endo β-glucanase breaks down the amorphous part of cellulose into oligosaccharides, exo β-glucanase breaks down the cellulose ends into cellobiose, and β-glucosidase breaks down oligosaccharides and cellobiose into monosaccharides Hydrolyzes to glucose. Fungi having the most cellulases that share endo β-glucanase, exo β-glucanase, and β-glucosidase are white rot fungi (Sporotrichum pulverulentum, Sporotrichum thermophile, Trichoderma reesei, etc.). Cellulases from soft-rot fungi (Trichoderma koningii, Fusariumsalani, Penicillium funiculosum, Myrothecium verrucaria, Stachybotrys atra, Gliocladium roseum, Memmoniella echinata, etc.) modify the cellulose crystals and decompose them, similar to those from white-rot fungi. Do. On the other hand, a cellulase isolated from brown rot fungi (eg, Poriaplacenta), which lacks exo β-glucanase, severely degrades cellulose crystals. Similarly, exo-β-glucanase is not present in bacterial (Ruminococcus albus, Ruminococcus flavefaciens, Bacteroides succinogenes, etc.) cellulases. (Eriksson, K.-E., Wood, TM, Biodegradation of Cellulose. In “Biosynthesis and Biodegradation of Wood Components”, Higuchi, T., ed., Academic Press, New York, 1985, pp. 469-503).
The hemicellulase and cellulase are commercially available (Novozyme, Genencor, etc.) and can be used industrially. The present invention uses (1) hemicellulase and 2-3 enzyme of cellulase, or (2) a microorganism that degrades hemicellulose and a microorganism that hydrolyzes cellulose, or (3) a microorganism that degrades cellulase and hemicellulose at the same time. The lignin-free holocellulose is hydrolyzed to form a monosaccharide.

The monosaccharide solution produced by hydrolysis of microorganisms / enzymes or inorganic acids is neutralized in the range of pH 5-6 by adding quick lime after treatment with mixed bed ion resin for the purpose of improving the efficiency of the post-fermentation process, It is then possible to ferment bioethanol with yeasts such as Zymomonas mobilis bacteria, Saccharomyces cerevisiae, Pichiasstipitis. (Example: Tran, AV, Chambers, RP, Ethanol fermentation of red oak acid prehydrolyzate by the yeast Pichiastipitis CBS 5776, Enzyme Microbiology and Technology 8 (7): 439-446 (1986)). On the other hand, methyl ethyl ketone has a higher heat of combustion than ethanol (584.2 vs. 326.7 kcal. Mol- ¹ ), and 25% (v.v- ¹ ) of gazoline has a high octane number of 96.7. The invention is a method for producing methyl ethyl ketone that replaces fuel for transportation and traffic. Therefore, the monosaccharide liquid is a monosaccharide production method and non-edible lignocellulosic biomass production method for producing 2,3-butanediol, which is a precursor of methyl ethyl ketone.

  (4) The present invention is a method for fermenting 2,3-butanediol using Klebsiella pneumoniae belonging to the genus Klebsiella. Furthermore, by adding a microorganism belonging to the genus Klebsiella together with a monosaccharification enzyme in the monosaccharification reactor of the third step of the present invention, monosaccharification of the holocellulose substance and fermentation of 2,3-butanediol are performed simultaneously, It is a monosaccharide production method and an alternative fuel production method for non-edible lignocellulosic biomass produced by 2,3-butanediol, which can shorten the production process.

  (5) The present invention is a non-edible ligno that produces methyl ethyl ketone by subjecting the produced 2,3-butanediol to activated carbon and dehydration reaction with a solid acid catalyst of a silica / aluminum carrier that covalently binds a sulfone group. It is a monosaccharide manufacturing method and an alternative fuel manufacturing method of cellulosic biomass.

    The non-edible lignocellulosic biomass of the present invention is capable of producing holocellulose by producing the same chip as used in the paper and pulp industry without crushing, and a chipper that is an apparatus that produces chips compared to crushing equipment, The energy consumption of slicers, chip thickness selectors, chip screens, etc. is low, saving energy.

    Since the present invention can be continuously operated from the chipping process to the holocellulose production process, the monosaccharification process, the 2,3-butanediol production process, and the methyl ethyl ketone production process, production efficiency and yield are improved.

    In the present invention, when the saccharification and 2,3-butanediol production are carried out with microorganisms / enzymes, the two steps are performed because the saccharification enzyme and the 2,3-butanediol production microorganism are used together. The process can be shortened, and the benefits of simplified production flow and reduced equipment costs can be achieved.

    In the present invention, holocellulose is isolated from chips of non-edible lignocellulosic biomass and then monosaccharified, that is, an alternative fuel is produced using the whole sugar of the plant, and further obtained from the holocellulose production process. Water-soluble lignin degradation products are the most effective use of biomass over conventional techniques because energy is recovered by concentration and combustion and reused in production lines.

The present invention provides a part of the extract from the holocellulose manufacturing process in which the chip flow from the chip forming process to the holocellulose manufacturing process is chlorine dioxide water and a make-up liquid, and 2,3-butane A part of the distillate (condensate) obtained from the process of purifying diol, bioethanol, acetic acid, etc. is reused as make-up water for the holocellulose production process, monosaccharification process, etc., and the remaining condensate is COD, It is a monosaccharide production method and alternative fuel production method of non-edible lignocellulosic biomass that is discharged as a small amount of industrial wastewater after removing BOD and has a low environmental burden.
In the present invention, when the saccharification step is carried out with an enzyme, this step and the next 2,3-butanediol production step are combined, the two steps are shortened to one step, and industrial water is used as water for the combined step. The generated waste water is the same as the industrial waste water described above, and since all the waste water has a small capacity and has almost no biomass fouling, the method for producing monosaccharides of non-edible lignocellulosic biomass and alternative fuel of the present invention The manufacturing method is environmentally friendly.

    Conventionally, corrugated cardboard and waste paper are saccharified after being pulverized, so the cutting energy is high and the residual lignin in the raw material is high. In addition, holocellulose obtained from chlorine dioxide treatment is lignin-free and has high saccharification efficiency, and dissolved lignin can recover energy when concentrated and burned. Even in such a case, the monosaccharide production method and the alternative fuel production method of the non-edible lignocellulosic biomass of the present invention are superior to the conventional technology.

    Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a process diagram showing the flow of a monosaccharide production method and an alternative fuel production method for non-edible lignocellulosic biomass according to this embodiment. FIG. 1 shows a total of 7 steps including the woody biomass chipping step, holocellulose production step, monosaccharification step, 2,3-butanediol, bioethanol, acetic acid production step, purification step, methyl ethyl ketone production step, and methyl ethyl ketone purification step. Is included. The description of each process is as follows.

(1) Chip making process The non-edible wood lignocellulosic biomass monosaccharide production method and alternative fuel production method of the present invention are the same as the wood chips used in the paper and pulp industry without crushing the non-edible wood lignocellulosic biomass. To manufacture. That is, the woody biomass log 1 is chipped with a chipper 2 to produce chips and stocked as chip piles 3. Similarly, purchased wood chips need to be stocked as chip piles. For the purpose of clarifying the amount used, the chip is transferred to the chip silo 4 having a chip meter and stored by Convert. The chips need to be sized before being sent to the next holocellulose manufacturing process. After being selected by the chip thickness selector 5, the upper screen 6 having a round hole with a particle diameter of 50 mm or less or a square hole with a diameter of 50 mm or less and Screening is performed on the lower screen 6 having a round hole having a particle diameter of 5 mm or more, and the excessive chip is sent to the slicer and reused, and the skin and the small chip are burned with a boiler to recover heat. The average size of the aligned chips is 2 mm-3 mm in thickness, 20-35 mm in length, and 10-25 mm in width.

(2) Holocellulose manufacturing process The chip is sent from the chip screen 6 to the chip bin 7 and passes through a chip meter 8 whose rotation speed is set according to the production volume of holocellulose, and is steamed to enhance the penetration of chemicals. The vessel 9 is charged and degassed with low-pressure steam of 200 kPa or less, preferably 100-150 kPa. Then, it passes through the chip chute 10 and is conveyed to the holocellulose production reactor by the pump 11. There are two types of holocellulose production reactors, a batch system and a continuous system. In either case, the produced holocellulose is put in the blow tank 15. Note that the residence time of the batch type and continuous type reactors is 12 hours minimum.

(2-1) Batch Production (A) Method A constant chip weight is charged into the reactor 12 according to the production volume of holocellulose and the capacity of the batch reactor, and the concentration is 10 g while maintaining the pressure at 150 kPa or less. L- ¹ or less, preferably 7-8.5 g. L- ¹ chlorine dioxide water is added and adjusted with caustic soda to have a pH of 1.0-2.5, preferably 1.7-2.2. The batch reactor is preferably heated to 65-85 ° C., and a liquid circulation facility and a heater are attached to the batch reactor. When the residual chlorine dioxide of the added chlorine dioxide liquid is exhausted, the liquid is abolished and a new chlorine dioxide liquid is obtained. The chlorine dioxide treatment is continued until the holocellulose having a copper number of 10 or less is obtained. Although this chlorine dioxide treatment occurs even at room temperature, the chlorine dioxide basic unit for obtaining the final holocellulose having a kappa number of 10 or less is higher and the reaction time is longer than the reaction at 65-85 ° C. The chlorine dioxide basic unit is the consumption (kg) of chlorine dioxide with respect to 1 ton of air-dry ton (ADT) of the produced holocellulose. Incidentally, 1 ADT is equivalent to 0.9 tons of oven-dry ton (ODT).
The present invention uses the kappa number as the index of residual lignin in holocellulose, and the kappa number is measured so that half of the fixed amount of potassium permanganate is consumed. Is used as a standard method by various pulp and paper technology associations around the world (Dence, CW, In ”Methods in Lignin Chemistry”, Eds. Lin, SY, Dence, CW , Springer-Verlag, Berlin, 1992, pp. 48-52).

(2-2) Continuous production (B) method The continuous production method of holocellulose is the same as the batch production method pressure, chlorine dioxide concentration, chlorine dioxide treatment temperature, pH, etc., but the operability is different. . Specifically, the first tower 13 is a facility for permeating chlorine dioxide into the chip, and the second tower 14 for producing holocellulose is formed. Includes at least a two-liquid circulation zone, and the second column includes at least a three-liquid circulation zone, and the total residence time of the first and second towers is at least 12 hours or more. The chip goes from the chute 10 to the circulation pump P1 and is fed to the permeation tower 13 with chlorine dioxide water as a carrier liquid. The top separator of the permeation tower 13 separates the chip from the chlorine dioxide liquid, Entering the permeation tower, the chlorine dioxide solution for transportation returns to the circulation pump P1, and when there is no residual chlorine dioxide, the new chlorine dioxide solution is replaced. The liquid in the tower is extracted and discharged from the upper circulation pump P2 of the osmosis tower 13, new chlorine dioxide is added, and the mixture is superheated by the heater H1 and put into the tower. Similarly, the liquid in the tower is extracted and discharged from the lower circulation pump P3, new chlorine dioxide is injected, heated by the heater H2, and put into the tower. The partially delignified chip is sent to the reaction tower 14, the liquid in the reaction tower is extracted and discharged from the pump P4 in the upper circulation zone, is replaced with new chlorine dioxide liquid, is heated with the heater H3, and is put into the upper circulation zone. . Next, the liquid in the column is extracted from the pump P5 in the intermediate circulation zone, a new chlorine dioxide solution is injected, and the mixture is superheated with the heater H4 and then put into the intermediate circulation zone. Similarly, the liquid in the tower is extracted with the pump P6 in the lower circulation zone, a new chlorine dioxide solution is added, and the mixture is superheated with the heater H5, put into the lower circulation zone, and delignification is performed. Holocellulose is blown with a scraper and a blow device in the bottom of the reaction tower 14 and placed in a blow tank 15. As with the batch production formula, the holocellulose kappa number from the continuous production formula is 10 or less, and as will be described later, the kappa number 10 is a total of 6% of the clason (sulfuric acid) lignin and sulfuric acid-dissolved lignin (of the holocellulose. %) And the sum of hemicellulose and cellulose is 94% of the produced holocellulose.
The present invention is not limited to the two-column system for continuously producing the holocellulose, and a system having two or more towers can also be applied.

(2-3) Reuse of lignin in chlorine dioxide waste liquid by holocellulose production process Lignin in woody biomass (referred to as protolignin) is mainly formed from a phenol structure and a non-phenol structure, and reacts with chlorine dioxide. Reactions such as demethoxy group and benzene ring cleavage are carried out to produce water-soluble methanol, o-benzoquinone, p-benzoquinone, muconic acid and the like. (Dence, CW, In “Pulp Bleaching-Principles and Practice”, Eds. Dence, CW, Reeve, DW, Tappi Press, Atlanta, GA, 1996, pp. 132-138). That is, the decomposition lignin in the chlorine dioxide waste liquid from the chlorine dioxide treatment step mainly becomes a low molecular weight compound and methanol. Chlorine dioxide is 10 g. Since the volume of chlorine dioxide used in the holocellulose production reactor is large because it is produced at a concentration of L- ¹ or less, the generated chlorine dioxide waste liquid has a low TS, and the TS is 55 to burn in the boiler. % Concentration process is required, and black liquor concentration measures of alkaline pulp (eg kraft pulp) can be used, the name of the nuclear concentration measure is called an evaporator, and generally a multi-stage evaporator is used, The number of stages can be up to 7 and each stage can have one or more towers (one tower has a heat exchanger and a vapor / liquid separator). : 80 ° C. → 95 ° C. → 105 ° C. → 115 ° C. → 130 ° C. → 145 ° C. → 145 ° C.) and the temperature of the lignin solution also increases (eg 65 ° C. → 80 ° C. → 95 ° C. → 105 ° C. → 115 ° C. → 125 ° C.) → 125 ℃ , Resulting TS lignin solution is increased (eg: 3.5% → 7% → 14.5% → 30% → 45% → 60% → 65%). Concentrated chlorine dioxide waste liquid is burned in a boiler and heat is recovered as steam, and nuclear steam is used in a holocellulose manufacturing process, a purification process of 2,3-butanediol, methyl ethyl ketone, and the like to save energy.

(3) Monosaccharide conversion step and 2,3-butanediol production step The produced holocellulose includes hemicellulose and cellulose, and hemicellulose is a pentose and hexose polysaccharide (pentose: xylan, Arabinan, rhamnan; hexose: mannan, galactan, glucan), cellulose is a refractory polysaccharide called polysaccharide of hexose (glucan). It is necessary to hydrolyze the polysaccharide of sugar and to monosaccharideize it.
In the present invention, the polysaccharide of holocellulose is hydrolyzed by two methods such as an inorganic acid (sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.) or an enzyme to produce a monosaccharide.

(3-1) Monosaccharideization of holocellulose with an inorganic acid The present invention uses a sulfuric acid as the inorganic acid and monosaccharides the polysaccharide of holocellulose based on the well-known Krason (also referred to as sulfuric acid) lignin measurement method, Fermentation is performed in the subsequent steps of 2,3-butanediol, bioethanol, and acetic acid. Specifically, the holocellulose slurry is dehydrated with a filter from the blow tank 15 to a medium concentration (7-15%), and then goes to the first reactor 16, where the sulfuric acid is 100-140% (wv- ¹ ). The holocellulose material is decomposed and oligosed under the conditions of preferably 100 to 125%, temperature of 10 to 70 ° C., desirably 20 to 50 ° C., residence time of 30 to 180 minutes, desirably 35 to 90 minutes. Saccharification is performed, and then the nuclear oligosaccharide solution is sent to the second reactor 17, where the sulfuric acid is 2-6% (w.v ^-1 ), preferably 3-4%. Dilute with waste liquid obtained from within the manufacturing process of the invention, conditions of 100-140 ° C, preferably 110 ° C-120 ° C, and 30-90 minutes, preferably 45-60 minutes residence time, etc. Completely mono-saccharify with The saccharification rate is 100%, and there is no residue of holocellulose. This is a method of effectively using biomass. In order to increase the efficiency of the subsequent 2,3-butanediol production process, it is necessary to increase the concentration of monosaccharides, and the membrane concentration / distillation technology (eg, 4 kg · m ⁻² water flow at 35 ° C.) Pore polytetrafluoroethylene membrane) (Qureshi, N., Meagher, MM, Hutkins, RW, Recovery of 2,3-butanediol by vacuum membrane distillation. Separation Science and Technology 29 (13): 1733-1748 (1994) ), The sugar concentration of the nuclear monosaccharide solution is 20-30 g. L- ¹ to 100-150 g. L- ¹ and then passed through a bed of mixed bed ion resin 18 (example: AG-501-X8- (D) manufactured by Bio-Rad) and adjusted to pH 5.3-5.5 with quick lime. To do.

(3-2) Production of 2,3-butanediol of a monosaccharide solution by hydrolysis of sulfuric acid The fermenter 19 having a residence time of four days by a pump is used for the monosaccharide solution neutralized by treatment with the mixed bed ion resin 18 To the pump inlet, the medium for Klebsiella pneumoniae belonging to the genus Klebsiella of the bacterium, the inoculum for Klebsiella pneumoniae at the outlet of the pump, and the yeast extract 1-6 g. L- ¹ is added daily to the pump inlet to ferment 2,3-butanediol, bioethanol, and acetic acid. Depending on the residence time of the fermenter 19, the frequency of addition of medium and inoculation was once every four days, and the concentration of 2,3-butanediol obtained was 25-55 g. The concentration of L ⁻¹ and bioethanol was 10-25 g. L- ¹ . In addition, 2,3-butanediol fermentation is a continuous operation, and the medium for Klebsiella pneumoniae is ammonium chloride (1-3 g · L ⁻¹ ), sodium chloride (0.5-1.5 g · L ⁻¹ ), sulfuric acid. Glucose (6-10 g · L ⁻¹ ), xylose (1-5 g · L) formed from magnesium heptahydrate (0.1-0.5 g · L ⁻¹ ) and further incubated at 120 ° C. for 15 minutes. ^-1 ), and a mixture of phenol red soup (8-15 g · L ⁻¹ ), aseptically add a microbe of platinum ears, grow at 35-40 ° C. for 24 hours, and centrifuge to inoculate Klebsiella pneumoniae can get.

(3-3) Simultaneous saccharification by enzyme and 2,3-butanediol fermentation by bacteria In the produced holocellulose, hemicellulose and cellulose coexist, so that xylanase that degrades hemicellulose and cellulase that degrades cellulose, Fermentation of 2,3-butanediol, bioethanol, and acetic acid by the Klebsiella pneumoniae is performed while monosaccharide of the holocellulose polysaccharide is combined with β-glucosidase. In the present invention, Pentopan Mono BG as a xylanase, Celluclast as a cellulase, Novozyme 188 (all manufactured by Novozyme) as a β-glucosidase, or Pentopan Mono BG (available from Novozyme) as a xylanase, and β-glucosidase Hydrolysis of holocellulose by combining two enzymes Accellerase 100 (Genencor) as cellulase containing sesame, and the resulting pentose sugar (xylose, arabinose, etc.) and hexose sugar (glucose, mannose, galactose, etc.) 2,3-butanediol, bioethanol, and acetic acid are produced by metabolism of the Klebsiella pneumoniae in the same fermentor. Incidentally, the amount of enzyme added was 0.20 g. Holocellulose g ⁻¹ , manufactured by Genencor, 0.30 g. It is holocellulose g- ¹ .
Specifically, the holocellulose slurry in the blow tank 15 is passed through a heat exchanger to obtain a temperature of 50 ° C. for the next fermentation process, and is dehydrated with a filter to a concentration of 7-15%, preferably 10-12%. Then, sterilization is performed in a sterilization tower 20 at 120 ° C. for about 15 minutes, and the pH of the caustic soda solution at the inlet of the pump for feeding to the fermenter 21 having a residence time of 4 days with a pump is adjusted to pH 5. After adjusting 0-5.2, yeast extract and the medium of Klebsiella pneumoniae are added to the same inlet. Further, at the outlet of the pump, the combination of the three enzymes or the two enzymes and the inoculation of the Klebsiella pneumoniae are sequentially added to ferment 2,3-butanediol, bioethanol, and acetic acid while mono-staining holocellulose. Yeast extract 1-6 g. L- ¹ is added daily, with the Klebsiella pneumoniae medium and inoculation once every four days. The saccharification rate by the enzyme is 70-90%, the saccharification slurry is sent to the filter 37, and the residual holocellulose is recovered and reused in the sterilization tower 20. The filtrate containing 2,3-butanediol is sent to the purification process. Compared to 100% monosaccharide conversion with sulfuric acid, the monosaccharide ratio obtained from enzymatic hydrolysis is low, and the production of 2,3-butanediol and bioethanol is small due to low monosaccharide production. The concentration of monosaccharide is low, and in order to obtain the next high efficiency of 2,3-butanediol production, a concentration step for improving the concentration of monosaccharide in the sulfuric acid solution is necessary, and a large amount of energy is applied.

(4) Purification process of 2,3-butanediol, bioethanol and acetic acid Since the chemicals produced in the fermenters 19 and 21 are mixed substances of 2,3-butanediol, ethanol and acetic acid, each chemical is purified. There is a need. This chemical solution is sent to the multi-distillation tower system 22 and has different boiling points of ethanol (boiling point: 78.3 ° C), acetic acid (boiling point: 118.1 ° C), and 2,3-butanediol (boiling point: 183-184 ° C). Then, distill and collect at a boiling point that gradually increases. Nuclear distilled bioethanol is 95% (v.v ^-1 ) and the remaining 5% water is removed with a bed of molecular sieve beads to make absolute ethanol, which can be used as an alternative fuel for transportation and traffic or as an organic solvent. Distilled acetic acid can be sold as an organic solvent because of its small production. The fermented 2,3-butanediol has the highest boiling point and takes a large amount of energy when recovered as a high-quality chemical in a plurality of distillation towers. Therefore, it is used in the next methyl ethyl ketone production process.

(5) Methyl ethyl ketone production process The 2,3-butanediol solution after obtaining the above-mentioned distilled acetic acid was treated with a two-layered column 23 of activated carbon / sand (ratio = 90-99: 1-10), and then 150- The solid acid catalyst bed 24 at 220 ° C. is entered and subjected to a dehydration reaction to produce methyl ethyl ketone. Since the conversion rate from 2,3-butanediol to methyl ethyl ketone by the solid acid catalyst of the present invention is 80%, 20% becomes residual 2,3-butanediol. Since the boiling point of methyl ethyl ketone (79.6 ° C.) is lower than that of 2,3-butanediol (183-184 ° C.), the methyl ethyl ketone is purified by the multiple distillation tower system 25 to recover the residual 2,3-butane diol and multiple distillation It is mixed with 2,3-butanediol from the tower system 22 and reused again for the production of methyl ethyl ketone. Similar to the distilled ethanol, the purified methyl ethyl ketone removes residual water in the bed of molecular sieve beads, obtains high-quality chemicals, stores them in the storage tank 26, and can be used as an alternative fuel for transportation and traffic.
In the present invention, a sulfhydryl group is covalently bonded to powdered silica / alumina (40-60 mesh, manufactured by American Cyanamid) through a silane intermediate, and the core sulfhydryl group is converted to a sulfone group at 90 ° C. to form a solid acid catalyst (sulfone group). = 1.5-2.5 meq. Solid catalyst g- ¹ ) is produced and used.

In addition to the woody biomass, other usable raw materials include cardboard, newspapers, magazines, and ledgers collected from homes and offices. The pulping flow of these raw materials will be described in detail with reference to FIG.
In the waste paper, newspaper, magazine, ledger, sticky problems occur due to glue, plastic, etc. contained in the raw materials, and in order to avoid nuclear problems, first, caustic soda, sodium silicate, peroxide which is a mixture of pH 9-10 The raw material is disaggregated with a pulper 27 containing hydrogen, a fatty acid-based deinking agent or a deinking enzyme, then subjected to primary selection with a coarse screen 28 having a diameter of 1.4 mm, and then deinked with a front flotator 29. Secondary selection is performed with a pressure type fine screen 30 having a 0.2 mm hole, and the pulp concentration is increased to 30% by a dehydrator 31. Further, the press 32 is used to increase the pulp concentration to 40% or more. In order to disperse the residual ink in a fine and uniform manner, the waste paper pulp is treated in a disperser process 33, and then deinked again by a flotator 34. In order to obtain a medium concentration, dehydration is performed by a dehydrator 31, and then the production of holocellulose, monosaccharification, 2,3-butanediol fermentation, and the final product by the batch (A) method or continuous (B) method of FIG. Methyl ethyl ketone is produced.
For the recovered corrugated cardboard (also referred to as OCC: old corrugated containers), the pulping flow is simpler than that of the used paper, newspaper, magazine, and ledger. Specifically, after the pulper 27 disaggregates the pulp, Sand, glue, impurities, etc. are removed with a screen 28, a fine screen 30, and a lightweight cleaner 35. Waste paper pulp is dehydrated with a dehydrator 31 in order to obtain a medium concentration, and then the batch (A) system shown in FIG. (B) Production of holocellulose, monosaccharification, 2,3-butanediol fermentation, and methyl ethyl ketone as the final product are produced by the method (B).

    Hereinafter, although the effect of the present invention is explained using an example, the present invention is not limited to these examples.

A mixed eucalyptus hardwood chip that passed through a 45 mm diameter square chip screen and remained on a 5 mm diameter round hole chip screen was used. The average chip size was 2.8 mm thick, 19.8 mm wide, 28.2 mm long, chip moisture Was 48.5%. The tip of 340 g of absolutely dry (OD) is put in a polyethylene bag, tap water (5 L) is introduced, immersed under the pressure of an aspirator overnight, and dehydrated until the tip moisture is 45% by centrifugation. It was. Next, after adding chlorine dioxide water (concentration: 6.5 to 7.8 g · L ⁻¹ ) and placing it in a constant temperature bath at 85 ° C. for a certain reaction time, cool it with tap water and wash it with a 200 mesh screen. went. Caustic soda (2.7% vs. OD chip) was added to the chlorine dioxide / chip mixture to maintain a pH range of 1.5-1.8 after the reaction. When the reaction time exceeds 15 hours, the chip becomes soft and partially becomes holocellulose, so it is processed with a British standard disaggregator, and the holocellulose and the chip are separated on a laboratory 6-cut flat screen. Stored at 5 ° C., the chip was also treated with chlorine dioxide. This chlorine dioxide treatment / washing / flat screen treatment separation cycle was repeated, and the chlorine dioxide treatment was completed in a total of 87 hours. The reject obtained from the final treatment of the chlorine dioxide treatment was dried at 105 ° C., the holocellulose was dehydrated in a centrifuge, kappa number (10.2), clathon lignin (acid soluble: 2.28%; Acid insoluble: 3.98%) and yield (55.14%) were measured. The results are shown in Table 1.

    Using the chip of Example 1, chlorine dioxide treatment was performed at room temperature to prepare holocellulose. Compared with the holocellulose produced at 85 ° C. in Example 1, the holocellulose obtained at room temperature had a reaction time of 8.5 times longer and a chlorine dioxide addition rate of 1.6 times higher. The result was about 10 points higher, and it was found that decomposition by woody chlorine dioxide was low at low temperatures. The results are shown in Table 2.

    Using sawdust, holocellulose was produced. The pretreatment for chemical penetration into sawdust (300g absolutely dry) was the same as in Example 1, but the chlorine dioxide treatment was performed in a constant temperature bath at 75 ° C. Compared to Example 1 above, holocellulose from sawdust was smaller in size, so the reaction time was less than half, but the chlorine dioxide addition rate was 1.3 times higher. The results are shown in Table 3.

The holocellulose of Example 1 was saccharified by the following two hydrolysis methods. The first method is a general method for isolating clason lignin (also referred to as sulfate lignin). First, wood or pulp is decomposed into oligosaccharides with 72% sulfuric acid (wv ^-1 ), then diluted to 3% sulfuric acid, and then mono-saccharified while heating and boiling. It becomes. In the present invention, as a result of oligosaccharification at various sulfuric acid concentrations, sulfuric acid capacity, reaction time, and reaction temperature for 1 g of holocellulose, the sulfuric acid concentration is 65% for dissolving holocellulose in sulfuric acid (oligosaccharification). %, The sulfuric acid capacity was 25 ml or less per 1 g raw material, the reaction time was 3 hours or less, and the reaction temperature was 50 ° C. or less.
In Example 4, 72% sulfuric acid (20 ml) was added to holocellulose (1 g absolutely dry), reacted under conditions of 30 ° C. and 40 minutes, distilled water (761 ml) was added, and the autoclave at 120 ° C. Monosaccharification was performed in 60 minutes. It is filtered through a 1G3 glass filter, the residue is acid-insoluble clathon lignin, and the filtrate contains completely monosaccharideized pentose, hexose and acid-soluble lignin. Measured at 205 nm. As a result, the acid-insoluble lignin is 3.98%, the acid-soluble lignin is 2.28% (vs. holocellulose), that is, the total lignin is 6.3%, and the monosaccharide is 93.7%. The results are shown in Table 4.

The second method hydrolyzes holocellulose with a combination of various enzymes. In Example 4, Holocellulose (10 g absolutely dry) was adjusted to a concentration of 10%, adjusted to pH 5 with dilute sulfuric acid solution, Celluclast (Novazyme product number C2730), Novozyme 188 (Sigma Aldrich product number C6105) , Pentopan Mono BG (Sigma Aldrich product number X2753) 0.06 g. g < ^-1 >, 0.12 g. g < ^-1 >, 0.18 g. After adding g ⁻¹ (to holocellulose), hydrolysis was performed at 45 ° C. for 120 hours while stirring (200 rpm). The produced reducing sugar was measured by the Somogyi method (Browning, BL, Methods of Wood Chemistry, 1967, Vol. 1, Interscience Publishers, New York, p. 592). As a result, the larger the amount of enzyme added, the more reducing sugar was produced, 0.18 g. With an enzyme addition amount of g- ¹ , 0.806 g. A reducing sugar of g ^-1 is obtained, resulting in a monosaccharification rate of 85.7% relative to the sugar content in holocellulose. Therefore, it was found that the enzyme was inferior in monosaccharification rate than sulfuric acid. The results are shown in Table 5.

Comparative example

    The said patent documents 1-5 were used as a comparative example with respect to the monosaccharification method of this invention. As shown in Table 6, the size of the wood lignocellulosic biomass is a weak store where only JP-A-2005-229822 is the same as the present invention, and other patent documents include a step of pulverizing raw materials and high energy consumption. There is. In terms of the rate of saccharification of wood, JP 2005-229822 is less than or equal to Example 1-3 of the present invention, and JP 2008-43328 and 2008-54608 are lower, so the present invention is superior. understood. In Japanese Patent Application Laid-Open No. 2007-301472, saccharification rate from hemicellulose and cellulose is 73.0%, lignin and extract are 23.5%, and residue is 1.5%. The wood shows no loss and is completely decomposed. However, it is well known that hot water extraction decomposes at least the acetyl group of hemicellulose to produce acetic acid, formic acid, and the like, so the saccharification rate of 73.0% in JP 2007-301472 is questionable.

When holocellulose is monosaccharified by the sulfuric acid hydrolysis method, the use weight (1 g) of holocellulose is small compared to the final 3% sulfuric acid solution (780 ml), the concentration of monosaccharide is low, and the following 2,3-butane Since the efficiency of the diol fermentation process deteriorates, an enzyme monosaccharification method was selected. In Example 5, the holocellulose (60 g absolute dry) of Example 1 was made into a 10% slurry, pH 5 was adjusted with dilute sulfuric acid solution, 10.8 g of each of Celluclast, Novozyme 188, and Pentopan Mono BG were added and stirred. Hydrolysis was carried out at 45 ° C. for 96 hours with (200 rpm), filtered through a 17G3 glass filter, and 2,3-butanediol was fermented using a monosaccharide concentration of 9.2% in the filtrate (553 ml). . The bacterium used was Klebsiella pneumoniae (ATCC 8724). Microorganisms were introduced into a brain heart injection agar slope (Difco), placed in a 37 ° C. incubator, cultivated for 2 days, and stored in a 2 ° C. refrigerator. As a preparation for inoculation, a mixture of glucose (10 g · L ⁻¹ ), xylose (2.5 g · L ⁻¹ ) and phenol red soup (10 g · L ⁻¹ ) incubated at 120 ° C. for 15 minutes One microbe of microorganism was aseptically added, cultivated at 37 ° C. for 24 hours, and centrifuged (1 × 10 ⁴ rpm, 10 minutes, 2 ° C.) to obtain a bacterial inoculum. A 100 ml inoculum was prepared. In the 9.2% monosaccharide solution, ammonium chloride (2 g · L ⁻¹ ), sodium chloride (1.0 g · L ⁻¹ ), magnesium sulfate heptahydrate (0.2 g · L ⁻¹ ), yeast Extract (2.0 g · L ⁻¹ ) was added, sterilized at 120 ° C. for 15 minutes, and transferred to the fermenter together with the inoculation of Klebsiella pneumoniae. The fermenter controlled pH 5.4 with 5N caustic soda solution while stirring at 32 ° C. and 350 ppm, and air 150 ml. Min- ¹ was fed and 2,3-butanediol was fermented in 120 hours. In order to investigate the effect on fermentation efficiency, yeast extract (2.0 g · L ⁻¹ ) was added once a day during the fermentation period. As a result, the daily addition of yeast extract improved the production efficiency of 2,3-butanediol by about 18%. The fermentation products 2,3-butanediol, bioethanol and acetic acid were quantified in a Varian Gas Chromatograph 3700 form having a 1 m glass column packed with Chromosorb 101. The accessories were FID (Flame Ionization Detector), Varian Autosampler 5000, Varian CDS-111c Integrator. The results are shown in Table 7.

Dehydration reaction was carried out with a solid acid catalyst using 2,1-butanediol (28.3 g · L ⁻¹ ) fermentation mash that was added once to the yeast extract to produce methyl ethyl ketone. A sulfhydryl group is covalently bonded to powdered silica / alumina (40-60 mesh, American Cyanamid) through a silane intermediate (Chambers, RP, Swan, GA, Walle, EM, Cohen, W., Baricos, WH, In Immobilized). Enzyme Technology, Eds., Weetall, HH, Suzuki, S., 1975, Plenum, New York, pp. 199-223), and the nuclear sulfhydryl group was converted to a sulfone group at 90 ° C (Backer, HJ Recueil des Travaux Chimiques 54 215 (1935)), a solid acid catalyst (sulfone group = 1.81 meq. Solid catalyst g ⁻¹ ) was produced. 35.2 g of solid acid catalyst was filled in SS pipe (inner diameter: 1.8 cm; length: 25 cm), placed in a 190 ° C. oil bath, passed through the fermentation mash treated with activated carbon, -Butanediol was dehydrated to produce methyl ethyl ketone. The activated carbon treatment was performed at 60 ° C. for 40 minutes under the condition of activated carbon: fermented mash liquid ratio 50 g: 1 L, filtered through filter paper, and then centrifuged (12 × 10 ³ × 10 minutes, 4 ° C.). The fermented mash that had been treated with activated charcoal produced 1.3 times more methyl ethyl ketone than the fermented mash that had not been treated with activated charcoal. In addition, methyl ethyl ketone (MEK) was quantified with the gas chromatograph apparatus which measures the said 2, 3- butanediol. The results are shown in Table 8.

    The present invention separates the chip-shaped composition of non-edible lignocellulosic biomass by chlorine dioxide treatment, that is, lignin, hemicellulose, holocellulose composed of cellulose, and recovers and reuses energy from dissolved lignin-degrading substances. , Providing a highly efficient and industrially available biomass utilization method in which holocellulose is monosaccharified by hydrolysis of sulfuric acid or enzyme, and the production equipment and equipment are paper pulp industry, petroleum refining industry, bioethanol production Since it is used in a company, production of holocellulose, monosaccharification, 2,3-butanediol, bioethanol, fermentation of acetic acid, and production of methyl ethyl ketone can be carried out industrially. Bioethanol can be used as an alternative fuel or organic solvent for transportation and traffic, and acetic acid can be used as an organic solvent. Methyl ethyl ketone is an alternative transportation and transportation fuel that is more effective than bioethanol, that is, the non-edible lignocellulosic biomass of the present invention. The monosaccharide production method and the alternative fuel production method are environmentally friendly and effective for resource reuse.

It is the schematic which shows an example of the continuous manufacturing apparatus of the monosaccharide manufacturing method and alternative fuel manufacturing method of the non-edible woody lignocellulosic biomass which concerns on this embodiment. The outline which shows an example of the continuous manufacturing apparatus of the monosaccharide manufacturing method of the non-edible lignocellulosic biomass which concerns on this embodiment, ie, the waste paper raw material from a household and an office, and (2) corrugated used paper, and an alternative fuel manufacturing method FIG.

Explanation of symbols

1: Wood log 2: Chipper 3: Chip pile 4: Chip silo
5: Chip thickness selector 6: Chip screen
7: tip bin 8: rotary tip meter 9: steaming vessel 10: tip chute 11: tip pump 12: batch type chlorine dioxide treatment reactor 13: first tower chlorine dioxide treatment continuous reactor 14: second tower chlorine dioxide treatment Continuous reactor 15: Holocellulose blow tank 16: First reaction tower 17 for two-stage sulfuric acid monosaccharification 17: Second reaction tower 18 for two-stage sulfuric acid monosaccharification 18: Mixed bed ion resin 19: 2,3-butanediol fermenter 20: Sterilization tower 21: Simultaneous saccharification by microorganisms / enzymes and 2,3-butanediol fermenter 22: Distillation tower 23 of 2,3-butanediol and bioethanol 23: Bed of activated carbon / sand 24: Solid acid catalyst 25: Methyl ethyl ketone and 2,3-butanediol distillation column 26: methyl ethyl ketone receiving tank 37: filter 38: activated carbon 39: Sand A: Batch method B: Continuous method C: Monosaccharification method D with sulfuric acid D: Method of simultaneous monosaccharification with microorganisms and enzymes and 2,3-butanediol fermentation H: Heater P: Pump 27: Pulper 28: Coarse screen 29: Front rotator 30: Fine screen 31: Dehydrator 32: Press 33: Disperser 34: Rear rotator 35: Light weight cleaner 36: High concentration cleaner

Claims (8)

A non-edible lignocellulosic biomass monosaccharide production method and alternative fuel production method,
When the biomass is woody, there is no need for a pulverization process, and a chip forming process for forming chips with a conventional chipper is formed,
In the case of recovered waste paper such as newspapers, magazines, ledgers, cardboard, etc., the biomass forms a pulping process comprising a pulper process, a screen cleaner selection process, and a flotator deinking process,
The chip or the deinked recovered pulp is treated with chlorine dioxide alone to form a holocellulose manufacturing process composed of dissolved lignin, hemicellulose, and cellulose.
The dissolved lignin waste liquid is concentrated to 55% or more of the total solids (total solid), burned in a boiler, recovers energy,
The holocellulose is hydrolyzed with sulfuric acid or microorganisms / enzymes to form a process of producing pentose and hexose monosaccharides,
The produced monosaccharide is fermented with 2,3-butanediol, bioethanol and acetic acid, nuclear bioethanol and acetic acid are distilled and purified, and the fermented 2,3-butanediol is produced by a solid acid catalyst. Performing the dehydration reaction to produce an alternative fuel, methyl ethyl ketone. The monosaccharide production method and alternative fuel production method of non-edible lignocellulosic biomass according to claim 1, wherein the holocellulose obtained from the chlorine dioxide treatment is formed under the following treatment conditions.
1) Set the pH to 1.0-2.5.
2) The temperature is set to room temperature-100 ° C.
3) The pressure is 150 kPa or less.
4) For the production of holocellulose, a batch method or a continuous method can be used. In the nuclear batch production method, one or more reactors are used, and in the nuclear continuous production method, two or more reactors are used. The non-edible product according to any one of claims 1 and 2, wherein the mono-saccharification process of holocellulose by sulfuric acid hydrolysis is performed under the following first-stage oligosaccharification and second-stage monosaccharification treatment conditions. Monosaccharide production method and alternative fuel production method of lignocellulosic biomass.
1) Treatment conditions for the first stage oligosaccharification,
(1) The amount of sulfuric acid added is 100-140% (wv- ¹ ).
(2) The temperature is 10-60 ° C.
(3) The reaction time is 30 to 180 minutes.
2) Treatment conditions for the second stage monosaccharification,
(1) The amount of sulfuric acid added is 2-6% (w.v ⁻¹ ).
(2) The temperature is 100-140 ° C.
(3) The reaction time is 30 to 90 minutes. The method for producing monosaccharides of non-edible lignocellulosic biomass and the alternative fuel production method according to any one of claims 1 and 2, wherein the monosaccharification step of holocellulose by enzymatic hydrolysis is performed under the following processing conditions. .
1) A combination of xylanase that degrades hemicellulose and cellulase that degrades cellulose, β-glucosidase or a combination of xylanase that degrades hemicellulose and cellulase containing β-glucosidase that degrades cellulose. Monosaccharides are converted into monosaccharides.
2) Set the pH to 4-6.
3) The temperature is 30-55 ° C. The process for producing 2,3-butanediol, bioethanol, and acetic acid by fermentation reaction by microorganisms is performed under the following processing conditions for the monosaccharide obtained from sulfuric acid of holocellulose or enzymatic hydrolysis. The monosaccharide manufacturing method and alternative fuel manufacturing method of nonedible lignocellulosic biomass of any one of Claims 1-4.
1) The fermenting microorganism is Klebsiella pneumoniae belonging to the genus Klebsiella.
2) Set the pH to 4-6.
3) The temperature is 30-55 ° C.   The saccharification process of pentose and hexose produced from the enzymatic hydrolysis of holocellulose and the subsequent fermentation process of 2,3-butanediol, bioethanol, and acetic acid may be performed in the same fermentor. The monosaccharide production method and alternative fuel production method of non-edible lignocellulosic biomass according to any one of claims 1, 2, 4, and 5, which is possible and simplifies the equipment.   The non-edible ligno of any one of claims 1 to 6, wherein the fermented 2,3-butanediol undergoes a dehydration reaction with a solid acid catalyst at 150 to 250 ° C to produce methyl ethyl ketone as an alternative fuel. Cellulose biomass monosaccharide production method and alternative fuel production method. The solid acid catalyst support is made of at least one of silica, alumina, platinum, and nickel, and the core support is 1.0 to 2.5 meq. The monosaccharide production method and alternative fuel production method of non-edible lignocellulosic biomass according to any one of claims 1 to 7, wherein a sulfone group of g ^-1 is covalently bonded.