WO2010146243A1 - Process and apparatus for manufacturing a product from lignocellulose-based raw stock - Google Patents

Process and apparatus for manufacturing a product from lignocellulose-based raw stock Download PDF

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Publication number
WO2010146243A1
WO2010146243A1 PCT/FI2010/050519 FI2010050519W WO2010146243A1 WO 2010146243 A1 WO2010146243 A1 WO 2010146243A1 FI 2010050519 W FI2010050519 W FI 2010050519W WO 2010146243 A1 WO2010146243 A1 WO 2010146243A1
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WO
WIPO (PCT)
Prior art keywords
fraction
raw stock
sugar
fiber suspension
residual
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PCT/FI2010/050519
Other languages
French (fr)
Inventor
Markku Karlsson
Esa SIPILÄ
Kai SIPILÄ
Anders ÖSTMAN
Original Assignee
Valtion Teknillinen Tutkimuskeskus
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Application filed by Valtion Teknillinen Tutkimuskeskus filed Critical Valtion Teknillinen Tutkimuskeskus
Priority to EP10789070A priority Critical patent/EP2443243A1/en
Publication of WO2010146243A1 publication Critical patent/WO2010146243A1/en

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Classifications

    • 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
    • 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
    • C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00—Bioreactors or fermenters specially adapted for specific uses
    • C12M21/12—Bioreactors or fermenters specially adapted for specific uses for producing fuels or solvents
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M43/00—Combinations of bioreactors or fermenters with other apparatus
    • C12M43/02—Bioreactors or fermenters combined with devices for liquid fuel extraction; Biorefineries
    • 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
    • C12M43/08—Bioreactors or fermenters combined with devices or plants for production of electricity
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M45/00—Means for pre-treatment of biological substances
    • C12M45/02—Means for pre-treatment of biological substances by mechanical forces; Stirring; Trituration; Comminuting
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M45/00—Means for pre-treatment of biological substances
    • C12M45/06—Means for pre-treatment of biological substances by chemical means or hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
    • C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
    • C12P5/023—Methane
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/02—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of bagasse, megasse or the like
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
    • 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
    • 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
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the invention relates to the process as defined in the preamble of claim 1 and to the apparatus as defined in the preamble of claim 11 for manufacturing a product from lignocellulose-based raw stock.
  • An objective of the invention is to disclose a new type of a process and apparatus for manufacturing a product from lignocellulose-based raw stock.
  • the invention is based on a process for manufacturing a product from lignocellulose-based raw stock.
  • cellulose fibers are separated from the raw stock in a water suspension to provide a fiber suspension
  • water is removed from the fiber suspension so as to have in the fiber suspension a percentage of solids of between 10 and 50 w-%, more preferably between 10 and 45 w-% and even more preferably between 10 and 40 w-%, in which case the fiber suspension is pumpable
  • the fiber suspension is treated by enzymatic hydrolysis to form at least one sugar-based fraction
  • the sugar-based fraction is fermented to form predetermined product fractions and at least one product fraction
  • at least one selected product fraction is separated from a residual fraction
  • the residual fraction is led to anaerobic treatment to form biogas .
  • Lignocellulose means in this connection a material formed from cellulose, hemicellulose and lig- nin.
  • Lignocellulose-based raw stock means in this connection any raw stock containing cellulose and/or hemicellulose, which may also contain, in addition to cellulose and hemicellulose, lignin and/or other substances.
  • cellulose fibers mean cellulose fibers and, if contained in the raw stock, hemicellulose fibers.
  • the lignocellulose-based raw stock is rich in cellulose fibers, e.g. it is fiber- rich waste material.
  • the lignocellulose-based raw stock contains waste-based raw stock and/or mixed and separately collected industrial and community waste and/or minor flows generated in industrial processes, which cannot be utilized in other ways, e.g. a fiber suspension, reclaimed fiber, residual flows, residual products, residual material, minor flows, reject products, reject flows or reject material, e.g. reject flows from a chemical pulp or paper mill, and/or packaging waste and/or separately collected energy waste and/or fiber waste from the paper or chemical pulp industry, which contain cellulose and/or hemicellulose.
  • the lignocellulose-based raw stock may contain wood-based material, plant- based material or the respective further-processed products, such as paper, which contain cellulose and/or hemicellulose.
  • the lignocellulose-based raw stock may contain other suitable components which contain cellulose and/or hemicellulose.
  • a sugar-based fraction means in this connection any fraction mainly based on monosaccharides and/or disaccharides .
  • the sugar-based fraction may contain sugar-based oligosaccharides.
  • the sugar-based fraction contains glucose, fructose, mannose, galactose, saccharose, cellobiose and/or lac- tose and/or other sugars known per se.
  • the disaccharides and oligosaccharides are mainly disintegrated to monosaccharides in the process according to the invention.
  • cellulose fibers are separated from the raw stock by any manner known per se, e.g. chemically or mechanically or by their different combinations.
  • cellulose fibers are separated from the raw stock by any defibration method known per se, e.g. a defibration method known in chemical pulp production, or by other suitable separation process.
  • cellulose fibers are separated from lignin and other material contained in the raw stock.
  • the other material in the raw stock, apart from the cellulose-rich material is led to recycling, energy production and/or other utilization process.
  • a fiber suspension means in this connection a suspension which is formed from cellulose fibers separated from the raw stock and which comprises cellulose fibers and water.
  • the fiber suspension may also contain hemicellulose fibers and small amounts of lignin and other substances.
  • water is removed from the fiber suspension before hydrolysis so as to have in the fiber suspension a percentage of solids of approximately 30 to 40%, in one embodiment approximately 30 to 35%, after removal of water.
  • the fiber suspension has a predetermined viscosity.
  • the dried fiber suspension to be led to production of ethanol contains more than 30 w-% of cellulose fibers, in one embodiment more than 50 w-% of cellulose fibers, and preferably less than 50 w-% of inorganic material and/or plastic material .
  • the selected product frac ⁇ tions are separated from the residual fraction by dis- tillating, fractionating, by their combination or by other suitable separating method known per se. The separated product fraction can be concentrated or absoluteized, if desired.
  • the selected and separated product fraction formed by fermenting is used as such to have a desired product or is processed further to have a desired product.
  • At least two selected product fractions are separated and recovered from the residual fraction after fermentation.
  • product fractions selected from the group of an enriched sugar fraction, ethanol, butanol, polymer fraction, precursor of a polymer fraction and their combinations are formed from the sugar-based fraction.
  • bio- plastics e.g. polylactide (PLA)
  • PLA polylactide
  • other suitable material components or compounds can be produced from the sugar-based fraction.
  • ethanol is formed from the sugar-based fraction in the fermentation step.
  • carbon dioxide is produced as a by-product.
  • the ethanol fraction is separated and recovered by distil- lating.
  • distillation the ethanol is concentrated.
  • solid matter and light and heavy hydrocarbons are formed as by-product fractions of distillation.
  • the by-product fractions considered as residual fractions are utilized and/or processed further mainly in anaerobic treatment to form biogas.
  • the determined by-product fraction or the determined by-product fractions are utilized in the production of energy, e.g. in a combustion boiler, to form energy, or in a desired further-processing process.
  • the preferred thickness in the feeding of raw stock to hydrolysis is approximately 10 to 45 w-%.
  • the selected product fraction is processed further to a desired product, e.g. ethanol is processed to fuel.
  • a desired product e.g. ethanol is processed to fuel.
  • the fiber suspension is pretreated before hydrolysis.
  • the fiber suspension is treated with heat before hydrolysis.
  • the heat treatment can be made with steam, preferably, e.g. steam from an integrated combustion boiler.
  • the fiber suspension is treated with heat at a temperature of 80 to 140°C.
  • a strong thermochemical steam treatment i.e. a so-called steam explosion, can be used.
  • the fiber suspension is treated before hydrolysis by grinding the fibers to a desired size class and by forming the fiber suspension. The aim of a pretreatment is to open the fibers so that, in the hydrolysis, the enzymes can be made better to penetrate in the fibers, and this way to accelerate the reaction.
  • a pretreatment particularly a heat treatment, the amount of waste-derived microbes and other detrimental elements and thereby their adverse effects in the hydrolysis can be reduced.
  • the fiber suspension is treated by one-step enzymatic hydrolysis.
  • the fiber suspension is fed to the hydrolysis step, and the enzymes are mixed with the fiber suspension at a temperature of 40 to 90°C, in one embodiment at a temperature of 40 to 75°C.
  • the duration of the hydrolysis step is 1 to 10 hours.
  • the fiber suspension is treated by at least two-step enzymatic hydrolysis.
  • two-step hydrolysis and a two-step hydrolysis device are used to treat the fiber suspension.
  • hydrolysis with more than two steps is used.
  • the fiber suspension is fed to two-step hydrolysis where, in the first hydrolysis step, the enzymes are mixed with the fiber suspension at a temperature of 40 to 90 0 C, the duration of the first step being 1 to 3 hours, and where, in the second hydrolysis step, the enzymes are mixed and the fiber suspension is treated at a temperature of 45 to 70°C, the duration of the second hydrolysis step being 4 to 12 hours.
  • the feeding of enzymes is phased so that the required amount of enzymes to achieve optimal hydrolysis is fed in a phased manner to each hydrolysis step.
  • the properties of different enzyme components are taken into account so that preferably different enzyme mixtures are fed to each hydrolysis step. Phasing of the enzymes can also be continued in connection with fermentation to achieve higher yield of a desired product fraction.
  • the enzymes as well as the enzyme mixtures formed from them are selected to hydrolysis and fermentation depending on the product fractions to be obtained.
  • the enzyme mixtures may contain enzymes of one or more groups. Any enzymes known per se and suitable for the purpose can be used as the enzymes.
  • enzymes which aid in the conversion of cellulose fibers and hemicellulose fibers to oligomeric, dimeric and/or monomeric saccharides and preferably further to monosaccharides are added in connection with hydrolysis to the fiber suspension for fermentation.
  • the fiber suspension is pretreated by a heat treatment if enzymes which do not withstand a high temperature are used in the hydrolysis .
  • the pH of the fiber suspension is set between 3.5 and 6, and the temperature is set between 30 and 70°C before addition of enzymes in the hydrolysis.
  • yeast, bacteria, microbes, nutrients or their mixtures are fed to the fiber suspension in connection with fermentation to promote the fermentation.
  • at least one enzyme is added to the fiber suspension in connection with fermentation.
  • the fermentation is continuous.
  • batch fermentation is used.
  • the duration of fermentation is 15 to 50 hours, preferably 15 to 30 hours.
  • the temperature of the fiber suspension is adjusted to the optimum temperature of yeast, preferably to a temperature of 30 to 40°C.
  • carbon dioxide (CO 2 ) which may be led to further processing and used e.g. as an industrial gas or in the food industry is produced as a by-product of fermentation.
  • the product flow formed in fermentation is treated by evaporating before separation of selected product fractions from the residual fraction.
  • the residual fraction from fermentation is treated by evaporating.
  • the selected product fraction is treated by evaporating.
  • the residual fraction from fermentation led to anaerobic treatment is solid matter, i.e. draff.
  • the draff and the nutrients are fed at a high thickness, preferably at a thickness of 15 to 30%, to mixing reactors in which the dwell time is 15 to 25 days and the temperature is 30 to 55°C depending on a microbial strain used.
  • biogas is formed by anaerobic treatment from the residual fraction from fermentation.
  • biogas which contains more than 50 vol-% of methane is formed by anaerobic treatment.
  • the biogas produced in anaerobic treatment is purified and, if necessary, pressurized.
  • the biogas may be used in energy production, such as fuel in a combustion boiler or a distinct power plant.
  • the biogas is processed further to be used as biofuel in transportation.
  • the biogas is used as a substituent for natural gas or liquid gas.
  • the residue generated in the production of biogas i.e.
  • solid matter is dried to a dry content of preferably 20 to 50% and is used in energy production, e.g. in a combustion boiler.
  • the solid matter is mixed with surplus fractions produced from the separation of a selected product fraction which was formed in fermentation, e.g. from the distillation of ethanol, and the obtained mixture can be used in energy production, e.g. in a combustion boiler.
  • any anaerobic process or apparatus known per se and suitable for the purpose can be used as the anaerobic treatment step.
  • the raw stock is sorted before separation of cellulose fibers, and the desired substance of the raw stock is led to production of a sugar-based fraction, the sugar-based fraction is produced and fermented, the residual frac- tion from fermentation is led to anaerobic treatment, and the residual material from sorting of the raw stock, separation of cellulose fibers and/or anaerobic , treatment is led to production of energy, and energy fractions are fed from energy production to the separation of cellulose fibers, production of a sugar-based fraction, fermentation and/or to be used as energy products .
  • substantially all the substances of the raw stock are utilized in the integrated process which includes the sorting of raw stock, production and fermentation of a sugar-based fraction, production of energy, e.g. a combustion boiler, and anaerobic treatment, to provide products preferably selected from the group of an enriched sugar-based product, ethanol, butanol, biogas, electricity, heat, steam and their combinations.
  • the raw stock is sorted before separation of cellulose fibers, and the desired sorted substance of the raw stock is led to production of a sugar-based fraction.
  • the residual material from sorting of the raw stock is led to energy production such as a combustion boiler which is preferably integrated in connection with production of a sugar-based fraction and anaerobic treatment.
  • the raw stock is subjected to evaporation before sorting.
  • the raw stock is crushed and sorted before separation of cellulose fibers.
  • the sorting is made mechanically.
  • heat treatment is used in the sorting.
  • the sorting is made mechanically and thermally.
  • the sorting is made in a water suspension at a temperature of less than 100 0 C.
  • An objective of the sorting is to provide fractions useful for production of a sugar-based fraction and preferably also for production of energy.
  • the raw stock, preferably rich in cellulose fibers, to be led to production of a sugar-based fraction contains lignin in an amount of less than 25 w-%, more preferably less than 10 w-%, of the dry content.
  • the low lignin content facilitates carrying out the hydrolysis process and improves efficiency of the hydrolysis.
  • residual and minor flows are led from production of a sugar- based fraction, fermentation, separation of a product fraction and/or anaerobic treatment to energy production.
  • residual fractions and minor flows are fed to a combustion boiler, preferably a combustion boiler integrated in connection with production of a sugar-based fraction, from production and fermentation of a sugar-based fraction, distillation of etha- nol, sorting of the raw stock, separation of cellulose fibers and/or anaerobic treatment.
  • the fractions fed to a combustion boiler are burned, and energy fractions such as electricity and district heat are produced.
  • the combustion is carried out as flu- idized bed combustion.
  • the waste-based raw stock is sorted in multiple phases so that the best substances are recycled as materials, after which the substances from which e.g. ethanol and biogas is produced are selected, and the residual fractions, e.g. wood and plastic, are utilized in production of energy, such as biofuel, electricity and heat.
  • fractions to be utilized directly, such as metal, and combustible fractions, such as wood and plastic are separated from other waste-based material, and are utilized as materials.
  • fuel is produced from the selected fractions.
  • at least one energy product is formed from the ligno- cellulose-based raw stock.
  • An energy product means in this connection any energy fraction or energy product such as biofuel, biooil, ethanol, butanol, biogas, electricity, heat and/or steam.
  • more than one energy product is formed simultaneously in the integrated apparatus.
  • the energy product is used as energy in separation of cellulose fibers, hydrolysis, fermentation, separation of a product fraction and/or concentration of a product fraction to carry out the process according to the invention, or as an energy product fraction in any other application.
  • the obtained ethanol product is used as fuel, e.g. transportation fuel.
  • the invention is based on an apparatus corresponding to the process for manufacturing a product from lignocellulose-based raw stock.
  • the apparatus includes raw stock feeding means, a cellulose fiber separating device for separating cellulose fibers from the raw stock in a water suspension to provide a fiber suspension, a dewa- terer for removing water from the fiber suspension so as to have in the fiber suspension a percentage of solids of between 10 and 50 w-%, a hydrolysis apparatus for treating the fiber suspension by enzymatic hydrolysis to form at least one sugar-based fraction, fermentation means for fermenting the sugar-based fraction and for forming at least one product fraction, separating means for separating at least one selected product fraction from a residual fraction, and an anaerobic treatment device to which the residual fraction is led and in which it is treated to form biogas.
  • the apparatus includes a defibration device as the cellulose fiber separating device.
  • the apparatus includes a distillation apparatus for separating a selected product fraction, e.g. ethanol.
  • the apparatus includes raw stock sorting means.
  • the apparatus includes a combustion boiler for burning residual and minor flows and for producing energy fractions.
  • the apparatus includes raw stock sorting means, raw stock feeding means, a cellulose fiber separating device, a dewaterer, a hydrolysis apparatus, fermentation means, separating means for separating at least one selected product fraction from the residual fraction, an anaerobic treatment device for treating the residual fraction, and a combustion boiler to form a substantially integrated configuration.
  • a sugar-based product, ethanol, butanol and their derivatives, and additionally biogas, other biofuel, electricity and/or heat can be produced from the raw stock, e.g. waste-based raw stock.
  • the process according to the invention it is possible to utilize different kinds of raw stock and raw stock components which could not be utilized cost-effectively before.
  • different product fractions can be formed in one process.
  • a good product yield is provided, preferably due to several simultaneously obtained products and product groups .
  • energy products such as energy fractions and fuel fractions are provided cost- effectively and with low production costs.
  • different added-value products are provided simultaneously with the main products, which further increases cost-effectiveness of the process.
  • lower-guality raw stock materials can be utilized in providing valuable main products.
  • Fig. 1 presents one process according to the invention as a schematic plan.
  • Waste-based raw stock which contained paper was used.
  • the waste-based raw stock was crushed and sorted into raw stock components.
  • the paper-based raw stock component was led to production of ethanol, and the other raw stock components were recycled directly as materials or were led to energy production.
  • a paper-based raw stock component is raw stock which is rich in cellulose.
  • an advantage of paper- based raw stock is that the cellulose fibers have been separated already in connection with papermaking, in which case the use of paper-based raw stock in the process according to the invention makes separation of cellulose fibers easier.
  • the raw stock to be used in production of ethanol was led to defibration where the cellulose and hemicellulose fibers were separated from the raw stock in a water suspension, and a fiber suspension was formed from the separated cellulose and hemicellulose fibers. Water was removed from the fiber suspension to provide in the fiber suspension a high percentage of solids, preferably a percentage of solids of 30% to 35%.
  • the obtained fiber suspension was fed to a first hydrolysis step.
  • the enzymes were mixed with the fiber suspension by powerful mixing in a blade reactor at a temperature of 40 to 75°C.
  • the duration of the first step was preferably approximately 2 hours.
  • the enzymes of the second step were mixed with the fiber suspension by powerful mixing in a mixing reactor at a temperature of 40 to 75°C.
  • the second hydrolysis step lasted approximately 4 hours. Mono- and oligosaccharides were formed in the hydrolysis.
  • the fiber suspension was moved to fermentation where the temperature was preferably approximately 35°C, and the duration was approximately 24 hours.
  • ethanol was formed from the mono- and oligosaccharide fraction.
  • the ethanol was separated from the residual fraction such as solid matter and other hydrocarbon fractions by distillating.
  • the distilled ethanol was utilized as a fuel component.
  • the solid-matter- containing residual fraction from distillation of ethanol was led to anaerobic treatment to form biogas.
  • the solid matter and the nutrients were fed to a mixing reactor where the dwell time was preferably 15 to 25 days and the temperature was between 30 and 55°C.
  • the integrated process and apparatus presented in this example and in Fig. 1 are used to produce etha- nol, biogas, carbon dioxide, steam and heat.
  • the integrated process of Fig. 1 includes a sorting step 2 for raw stock 1 and a separating step 4 for cellulose fibers to separate them from selected raw stock 3 to form a fiber suspension 5a. If desired, water 28 may be removed from the fiber suspension 5a in a dewaterer 27 to adjust the percentage of solids in the fiber suspension 5b. Furthermore, the process includes a hydrolysis step 6 for the fiber suspension 5b to form sugar-based fractions 7, and a fermentation step 8 for the sugar-based fractions 7 to form products 11 which contain ethanol . In fermentation, carbon dioxide 9 is produced as a by-product, which can be led to be utilized in other processes, e.g. as an industrial gas or in the food industry.
  • the process includes a distillation step 12 for ethanol, where the ethanol 13 and the other desired product fractions are separated from a residual fraction 10.
  • the solid-matter- containing residual fraction 10 is led to an anaerobic treatment step 22 to form biogas 21.
  • the process includes a combustion boiler 23 for producing energy fractions. Residual and minor flows of the process such as the residue 14 from sorting 2 of the raw stock, residual flow 15 from separation of the cellulose fibers, residual flow 18 from fermentation 8, possible residual flow 20 from distillation 12 and residue 17 from anaerobic treatment 22 may be fed to the combustion boiler 23 to produce energy.
  • other desired fuel can be fed to the combustion boiler.
  • the energy fractions formed in the combustion boiler 23 can be utilized as heat or steam in the process in question, or they can be led e.g. as heat 24 or steam 25 out of the process to be utilized elsewhere. Energy flows, e.g., can be led from the combustion boiler 23 to hydrolysis 16, fermentation 19 and separation of the cellulose fibers 26.
  • lignocellulose-based material From approximately two tons of industrial waste, 1000kg of lignocellulose-based material was separated.
  • the industrial waste contained, in addition to lignocellulose material, metals, plastics and wood waste.
  • the separation was made mechanically, magnetically and by air.
  • the separation was made by defibration in which the lignocellulose, especially the cellulose fibers, was separated to a suspension to have a percentage of solids of 3%.
  • the suspension was dried by a two-wire press to have a percentage of solids of 40%.
  • the suspension contained 65% of cellulose and hemicellulose, 5% of lignin, 10% of plastics and 20% of other organic and inorganic materials.
  • the suspension containing lignocellulose was diluted to have a percentage of solids of 20%. It was fed with 4kg of solid matter / h to enzymatic hydrolysis in a continuous manner. The dwell time in hydrolysis was six hours and the temperature was 55°C. In the hydrolysis step, the viscosity of the suspension was reduced owing to hydrolyzation of the cellulose and to the visible thixotropic property of the material, which was changed by powerful mixing.
  • the cellulose was hydrolyzed partially to mo- nomeric glucose and partially to oligomeric glucose, in which case the pumpability of the suspension was maintained.
  • the suspension was pumped continuously to a fermenting reactor where the dwell time was 48 hours.
  • the fermenting temperature was 35°C, and conventional yeast was added to the suspension.
  • the fermenting reactor operated as an SSF (Simultaneous Saccharification and Fermentation) reactor, thanks to the enzymes brought with the suspension. Fermentation of the produced glucose to ethanol was followed by conventional batch-type further process operations.
  • SSF Simultaneous Saccharification and Fermentation
  • the ethanol was led through evaporation, and the distillation waste was fed to anaerobic treatment where 350 to 500 liters of biogas was produced from one kilogram of solid matter.
  • the biogas contained on an average 72% of methane/dry-gas.
  • lactic acid and ethanol were produced by the process according to the invention.
  • test conditions according to Example 3 were used, except that the dwell time in fermentation was reduced to 24 hours.
  • the feed material was fed to hydrolysis at a temperature of 80 0 C to reduce the amount of lactobacilli and other harmful microorganisms.
  • bisulphite was added in a suitable amount, which does not cause problems to the yeast activity.
  • Ethanol was produced according to Examples 3 and 4.
  • the percentage of solids in the suspension was raised in the hydrolysis step to 25, 30 and 35% alternately. With a percentage of solids of 35%, it was more difficult to pump the suspension.
  • the reaction rate in the fermenting reactor was reduced a bit.
  • lactic acid and ethanol were produced by the process according to the invention.
  • Ethanol was produced according to Examples 3 and 4.
  • a waste fiber fraction from production of chemical pulp was used as raw stock.
  • the waste fiber fraction contained a very small amount of harmful microorganisms .
  • the waste fiber fraction was dried to have a percentage of solids of 50%.
  • the suspension was fed to hydrolysis with a percentage of solids of 20%.
  • the dwell time in fermentation was 40 hours.
  • the lactic acid bacilli did not increase substantially in fermentation, and the yield of ethanol was approximately 85% of the theoretical yield.
  • Partially sterilized lignocellulose was used as raw stock, and ethanol was produced according to Examples 3 and 4.
  • the percentage of solids in the feed was kept between 25 and 30%, and bisulphite was added as in Example 4.
  • the pH of fermentation was reduced to a value of approximately 4.
  • the yield of ethanol reduced to below 80% of the theoretical yield.
  • biogas was produced by the process according to the invention from distillation residual fractions.
  • the process and the apparatus according to the invention are suitable as different embodiments to be used in the manufacture of most different lignocellu- lose-based products.

Abstract

The invention relates to a process and apparatus for manufacturing a product from lignocellulose-based raw stock. According to the invention, cellulose fibers are separated from the raw stock in a water suspension to provide a fiber suspension (5a), water (27,28) is removed from the fiber suspension so as to have in the fiber suspension a percentage of solids (5b) of between 10 and 50 w-%, the fiber suspension (5b) is treated by enzymatic hydrolysis (6) to form at least one sugar-based fraction (7), the sugar-based fraction is fermented (8) to form at least one product fraction (11), at least one selected product fraction (13) is separated from a residual fraction (10), and the residual fraction is led to anaerobic treatment (22) to form biogas (21).

Description

PROCESS AND APPARATUS FOR MANUFACTURING A PRODUCT FROM LIGNOCELLULOSE-BASED RAW STOCK
FIELD OF THE INVENTION
The invention relates to the process as defined in the preamble of claim 1 and to the apparatus as defined in the preamble of claim 11 for manufacturing a product from lignocellulose-based raw stock.
BACKGROUND OF THE INVENTION
Known from the prior art are different processes and apparatuses for manufacturing energy products from different kinds of raw stock and waste materials e.g. by combustion technology.
Furthermore, known from the prior art is the disposal of waste materials by burning, anaerobically or by recycling. In addition, known from the prior art is the production of methane from different waste materials. A problem in the manufacture of energy products is often low efficiency and yield of the product fraction, as well as the residual flows which are generated in the manufacture and which may be difficult to be utilized.
Known from the prior art are processes for sorting waste to have fiber, plastic, metal and glass waste. In addition, known from the prior art are different processes for sorting waste at the site of its origin, after which large part of the waste remains nonetheless as unsorted mixed waste. In addition, the recycling of paper fibers is known. In addition, a problem with the known processes is that they are often based on the treatment of one or a few raw stock fractions at a time, in which case residual material is produced in the treatment of the waste material. Furthermore, known from the prior art are processes for producing ethanol from different kinds of raw stock.
Known from publications WO 00/35588 and WO 01/89730 is the sorting of waste material, its recycling, and energy production in connection with recycling. Especially known from the publications is the recycling of fiber-based waste materials into recycled products such as paper, board or chipboard.
OBJECTIVE OF THE INVENTION
An objective of the invention is to disclose a new type of a process and apparatus for manufacturing a product from lignocellulose-based raw stock.
SUMMARY OF THE INVENTION
The process and apparatus according to the invention for manufacturing a product are characterized by what is presented in the claims.
The invention is based on a process for manufacturing a product from lignocellulose-based raw stock. According to the invention, cellulose fibers are separated from the raw stock in a water suspension to provide a fiber suspension, water is removed from the fiber suspension so as to have in the fiber suspension a percentage of solids of between 10 and 50 w-%, more preferably between 10 and 45 w-% and even more preferably between 10 and 40 w-%, in which case the fiber suspension is pumpable, the fiber suspension is treated by enzymatic hydrolysis to form at least one sugar-based fraction, the sugar-based fraction is fermented to form predetermined product fractions and at least one product fraction, at least one selected product fraction is separated from a residual fraction, and the residual fraction is led to anaerobic treatment to form biogas . Lignocellulose means in this connection a material formed from cellulose, hemicellulose and lig- nin. Lignocellulose-based raw stock means in this connection any raw stock containing cellulose and/or hemicellulose, which may also contain, in addition to cellulose and hemicellulose, lignin and/or other substances. In this connection, cellulose fibers mean cellulose fibers and, if contained in the raw stock, hemicellulose fibers.
Preferably, the lignocellulose-based raw stock is rich in cellulose fibers, e.g. it is fiber- rich waste material. In one embodiment, the lignocellulose-based raw stock contains waste-based raw stock and/or mixed and separately collected industrial and community waste and/or minor flows generated in industrial processes, which cannot be utilized in other ways, e.g. a fiber suspension, reclaimed fiber, residual flows, residual products, residual material, minor flows, reject products, reject flows or reject material, e.g. reject flows from a chemical pulp or paper mill, and/or packaging waste and/or separately collected energy waste and/or fiber waste from the paper or chemical pulp industry, which contain cellulose and/or hemicellulose. Furthermore, the lignocellulose- based raw stock may contain wood-based material, plant- based material or the respective further-processed products, such as paper, which contain cellulose and/or hemicellulose. In addition, the lignocellulose-based raw stock may contain other suitable components which contain cellulose and/or hemicellulose.
A sugar-based fraction means in this connection any fraction mainly based on monosaccharides and/or disaccharides . The sugar-based fraction may contain sugar-based oligosaccharides. In one embodiment, the sugar-based fraction contains glucose, fructose, mannose, galactose, saccharose, cellobiose and/or lac- tose and/or other sugars known per se. In one preferred embodiment, the disaccharides and oligosaccharides are mainly disintegrated to monosaccharides in the process according to the invention.
Preferably, cellulose fibers are separated from the raw stock by any manner known per se, e.g. chemically or mechanically or by their different combinations. In one embodiment, cellulose fibers are separated from the raw stock by any defibration method known per se, e.g. a defibration method known in chemical pulp production, or by other suitable separation process. Preferably, cellulose fibers are separated from lignin and other material contained in the raw stock. In one embodiment, the other material in the raw stock, apart from the cellulose-rich material, is led to recycling, energy production and/or other utilization process.
A fiber suspension means in this connection a suspension which is formed from cellulose fibers separated from the raw stock and which comprises cellulose fibers and water. The fiber suspension may also contain hemicellulose fibers and small amounts of lignin and other substances.
In one embodiment, water is removed from the fiber suspension before hydrolysis so as to have in the fiber suspension a percentage of solids of approximately 30 to 40%, in one embodiment approximately 30 to 35%, after removal of water. In one embodiment, the fiber suspension has a predetermined viscosity.
In one embodiment, the dried fiber suspension to be led to production of ethanol contains more than 30 w-% of cellulose fibers, in one embodiment more than 50 w-% of cellulose fibers, and preferably less than 50 w-% of inorganic material and/or plastic material . In one embodiment, the selected product frac¬ tions are separated from the residual fraction by dis- tillating, fractionating, by their combination or by other suitable separating method known per se. The separated product fraction can be concentrated or absolutized, if desired.
In one embodiment, the selected and separated product fraction formed by fermenting is used as such to have a desired product or is processed further to have a desired product.
In one embodiment, at least two selected product fractions are separated and recovered from the residual fraction after fermentation.
In one embodiment of the invention, product fractions selected from the group of an enriched sugar fraction, ethanol, butanol, polymer fraction, precursor of a polymer fraction and their combinations are formed from the sugar-based fraction. In one embodiment, bio- plastics, e.g. polylactide (PLA), can be formed from polymer fractions and precursors of polymer fractions. In one embodiment, other suitable material components or compounds can be produced from the sugar-based fraction.
In one embodiment of the invention, ethanol is formed from the sugar-based fraction in the fermentation step. In the manufacture of ethanol, carbon dioxide is produced as a by-product. In one embodiment, the ethanol fraction is separated and recovered by distil- lating. In distillation, the ethanol is concentrated. In one embodiment, solid matter and light and heavy hydrocarbons are formed as by-product fractions of distillation. Preferably, the by-product fractions considered as residual fractions are utilized and/or processed further mainly in anaerobic treatment to form biogas. If desired, the determined by-product fraction or the determined by-product fractions are utilized in the production of energy, e.g. in a combustion boiler, to form energy, or in a desired further-processing process. When an ethanol concentration of at least 4 vol-% is desired for the ethanol fraction, the preferred thickness in the feeding of raw stock to hydrolysis is approximately 10 to 45 w-%.
In one embodiment, the selected product fraction is processed further to a desired product, e.g. ethanol is processed to fuel.
In one embodiment, the fiber suspension is pretreated before hydrolysis. In one embodiment of the invention, the fiber suspension is treated with heat before hydrolysis. In one embodiment, the heat treatment can be made with steam, preferably, e.g. steam from an integrated combustion boiler. In one embodiment, the fiber suspension is treated with heat at a temperature of 80 to 140°C. In one embodiment, a strong thermochemical steam treatment, i.e. a so-called steam explosion, can be used. In one embodiment, the fiber suspension is treated before hydrolysis by grinding the fibers to a desired size class and by forming the fiber suspension. The aim of a pretreatment is to open the fibers so that, in the hydrolysis, the enzymes can be made better to penetrate in the fibers, and this way to accelerate the reaction. In addition, by a pretreatment, particularly a heat treatment, the amount of waste-derived microbes and other detrimental elements and thereby their adverse effects in the hydrolysis can be reduced.
In one embodiment, the fiber suspension is treated by one-step enzymatic hydrolysis. In one embodiment, the fiber suspension is fed to the hydrolysis step, and the enzymes are mixed with the fiber suspension at a temperature of 40 to 90°C, in one embodiment at a temperature of 40 to 75°C. In one embodiment, the duration of the hydrolysis step is 1 to 10 hours. In one embodiment, the fiber suspension is treated by at least two-step enzymatic hydrolysis. In one embodiment, two-step hydrolysis and a two-step hydrolysis device are used to treat the fiber suspension. In an alternative embodiment, hydrolysis with more than two steps is used.
In one embodiment, the fiber suspension is fed to two-step hydrolysis where, in the first hydrolysis step, the enzymes are mixed with the fiber suspension at a temperature of 40 to 900C, the duration of the first step being 1 to 3 hours, and where, in the second hydrolysis step, the enzymes are mixed and the fiber suspension is treated at a temperature of 45 to 70°C, the duration of the second hydrolysis step being 4 to 12 hours.
In one embodiment, the feeding of enzymes is phased so that the required amount of enzymes to achieve optimal hydrolysis is fed in a phased manner to each hydrolysis step. In the phasing, the properties of different enzyme components are taken into account so that preferably different enzyme mixtures are fed to each hydrolysis step. Phasing of the enzymes can also be continued in connection with fermentation to achieve higher yield of a desired product fraction.
In a preferred embodiment, the enzymes as well as the enzyme mixtures formed from them are selected to hydrolysis and fermentation depending on the product fractions to be obtained. The enzyme mixtures may contain enzymes of one or more groups. Any enzymes known per se and suitable for the purpose can be used as the enzymes. In one embodiment, enzymes which aid in the conversion of cellulose fibers and hemicellulose fibers to oligomeric, dimeric and/or monomeric saccharides and preferably further to monosaccharides are added in connection with hydrolysis to the fiber suspension for fermentation. In one embodiment, the fiber suspension is pretreated by a heat treatment if enzymes which do not withstand a high temperature are used in the hydrolysis .
In one embodiment, the pH of the fiber suspension is set between 3.5 and 6, and the temperature is set between 30 and 70°C before addition of enzymes in the hydrolysis.
In one embodiment, yeast, bacteria, microbes, nutrients or their mixtures are fed to the fiber suspension in connection with fermentation to promote the fermentation. In one embodiment of the invention, at least one enzyme is added to the fiber suspension in connection with fermentation. In one embodiment, the fermentation is continuous. In one embodiment, batch fermentation is used. In one embodiment, the duration of fermentation is 15 to 50 hours, preferably 15 to 30 hours. In one embodiment, in connection with fermentation, the temperature of the fiber suspension is adjusted to the optimum temperature of yeast, preferably to a temperature of 30 to 40°C. In one embodiment, carbon dioxide (CO2) which may be led to further processing and used e.g. as an industrial gas or in the food industry is produced as a by-product of fermentation.
In one embodiment, the product flow formed in fermentation is treated by evaporating before separation of selected product fractions from the residual fraction. In one embodiment, the residual fraction from fermentation is treated by evaporating. In one embodiment, the selected product fraction is treated by evaporating.
In one embodiment, the residual fraction from fermentation led to anaerobic treatment is solid matter, i.e. draff. In one embodiment, in anaerobic treatment, the draff and the nutrients are fed at a high thickness, preferably at a thickness of 15 to 30%, to mixing reactors in which the dwell time is 15 to 25 days and the temperature is 30 to 55°C depending on a microbial strain used.
In the process according to the invention, biogas is formed by anaerobic treatment from the residual fraction from fermentation. In one embodiment, biogas which contains more than 50 vol-% of methane is formed by anaerobic treatment. In one embodiment, the biogas produced in anaerobic treatment is purified and, if necessary, pressurized. In one embodiment, the biogas may be used in energy production, such as fuel in a combustion boiler or a distinct power plant. In one embodiment, the biogas is processed further to be used as biofuel in transportation. In one embodiment, the biogas is used as a substituent for natural gas or liquid gas. In one embodiment, the residue generated in the production of biogas, i.e. solid matter, is dried to a dry content of preferably 20 to 50% and is used in energy production, e.g. in a combustion boiler. In one embodiment, the solid matter is mixed with surplus fractions produced from the separation of a selected product fraction which was formed in fermentation, e.g. from the distillation of ethanol, and the obtained mixture can be used in energy production, e.g. in a combustion boiler.
In one embodiment, in addition to the residual fractions formed in fermentation, other suitable feed material can be fed to the anaerobic treatment step as well.
In one embodiment, any anaerobic process or apparatus known per se and suitable for the purpose can be used as the anaerobic treatment step.
In one embodiment of the invention, the raw stock is sorted before separation of cellulose fibers, and the desired substance of the raw stock is led to production of a sugar-based fraction, the sugar-based fraction is produced and fermented, the residual frac- tion from fermentation is led to anaerobic treatment, and the residual material from sorting of the raw stock, separation of cellulose fibers and/or anaerobic , treatment is led to production of energy, and energy fractions are fed from energy production to the separation of cellulose fibers, production of a sugar-based fraction, fermentation and/or to be used as energy products .
In one embodiment, substantially all the substances of the raw stock are utilized in the integrated process which includes the sorting of raw stock, production and fermentation of a sugar-based fraction, production of energy, e.g. a combustion boiler, and anaerobic treatment, to provide products preferably selected from the group of an enriched sugar-based product, ethanol, butanol, biogas, electricity, heat, steam and their combinations.
In one embodiment of the invention, at least part of the raw stock is sorted before separation of cellulose fibers, and the desired sorted substance of the raw stock is led to production of a sugar-based fraction. In one embodiment, the residual material from sorting of the raw stock is led to energy production such as a combustion boiler which is preferably integrated in connection with production of a sugar-based fraction and anaerobic treatment. In one embodiment, the raw stock is subjected to evaporation before sorting. In one embodiment, the raw stock is crushed and sorted before separation of cellulose fibers. In one embodiment, the sorting is made mechanically. In one embodiment, heat treatment is used in the sorting. In one embodiment, the sorting is made mechanically and thermally. In one embodiment, the sorting is made in a water suspension at a temperature of less than 1000C. An objective of the sorting is to provide fractions useful for production of a sugar-based fraction and preferably also for production of energy.
In one embodiment, the raw stock, preferably rich in cellulose fibers, to be led to production of a sugar-based fraction contains lignin in an amount of less than 25 w-%, more preferably less than 10 w-%, of the dry content. The low lignin content facilitates carrying out the hydrolysis process and improves efficiency of the hydrolysis.
In one embodiment of the invention, residual and minor flows are led from production of a sugar- based fraction, fermentation, separation of a product fraction and/or anaerobic treatment to energy production. In one embodiment, residual fractions and minor flows are fed to a combustion boiler, preferably a combustion boiler integrated in connection with production of a sugar-based fraction, from production and fermentation of a sugar-based fraction, distillation of etha- nol, sorting of the raw stock, separation of cellulose fibers and/or anaerobic treatment. The fractions fed to a combustion boiler are burned, and energy fractions such as electricity and district heat are produced. In one embodiment, the combustion is carried out as flu- idized bed combustion.
In one embodiment, the waste-based raw stock is sorted in multiple phases so that the best substances are recycled as materials, after which the substances from which e.g. ethanol and biogas is produced are selected, and the residual fractions, e.g. wood and plastic, are utilized in production of energy, such as biofuel, electricity and heat. In one embodiment, fractions to be utilized directly, such as metal, and combustible fractions, such as wood and plastic, are separated from other waste-based material, and are utilized as materials. In one embodiment, fuel is produced from the selected fractions. In one preferred embodiment of the invention, at least one energy product is formed from the ligno- cellulose-based raw stock. An energy product means in this connection any energy fraction or energy product such as biofuel, biooil, ethanol, butanol, biogas, electricity, heat and/or steam. Preferably, more than one energy product is formed simultaneously in the integrated apparatus.
In one embodiment, the energy product is used as energy in separation of cellulose fibers, hydrolysis, fermentation, separation of a product fraction and/or concentration of a product fraction to carry out the process according to the invention, or as an energy product fraction in any other application.
In one embodiment, the obtained ethanol product is used as fuel, e.g. transportation fuel.
In addition, the invention is based on an apparatus corresponding to the process for manufacturing a product from lignocellulose-based raw stock. According to the invention, the apparatus includes raw stock feeding means, a cellulose fiber separating device for separating cellulose fibers from the raw stock in a water suspension to provide a fiber suspension, a dewa- terer for removing water from the fiber suspension so as to have in the fiber suspension a percentage of solids of between 10 and 50 w-%, a hydrolysis apparatus for treating the fiber suspension by enzymatic hydrolysis to form at least one sugar-based fraction, fermentation means for fermenting the sugar-based fraction and for forming at least one product fraction, separating means for separating at least one selected product fraction from a residual fraction, and an anaerobic treatment device to which the residual fraction is led and in which it is treated to form biogas. In one embodiment of the invention, the apparatus includes a defibration device as the cellulose fiber separating device.
In one embodiment of the invention, the apparatus includes a distillation apparatus for separating a selected product fraction, e.g. ethanol.
In one embodiment of the invention, the apparatus includes raw stock sorting means.
In one embodiment of the invention, the apparatus includes a combustion boiler for burning residual and minor flows and for producing energy fractions.
In one embodiment, the apparatus includes raw stock sorting means, raw stock feeding means, a cellulose fiber separating device, a dewaterer, a hydrolysis apparatus, fermentation means, separating means for separating at least one selected product fraction from the residual fraction, an anaerobic treatment device for treating the residual fraction, and a combustion boiler to form a substantially integrated configuration.
By the process and apparatus according to the invention, considerable advantages are achieved in comparison with the prior art. According to the invention, a sugar-based product, ethanol, butanol and their derivatives, and additionally biogas, other biofuel, electricity and/or heat can be produced from the raw stock, e.g. waste-based raw stock. By the process according to the invention, it is possible to utilize different kinds of raw stock and raw stock components which could not be utilized cost-effectively before. Furthermore, by the invention, different product fractions can be formed in one process. By the invention, a good product yield is provided, preferably due to several simultaneously obtained products and product groups . By the invention, energy products such as energy fractions and fuel fractions are provided cost- effectively and with low production costs. By the invention, different added-value products are provided simultaneously with the main products, which further increases cost-effectiveness of the process.
In addition, by the invention, lower-guality raw stock materials can be utilized in providing valuable main products.
LIST OF FIGURES
Fig. 1 presents one process according to the invention as a schematic plan.
DETAILED DESCRIPTION OF THE INVENTION
In the following, the invention will be described by means of detailed exemplary embodiments with reference to the accompanying figure.
Example 1
In this example, ethanol and biogas were produced by the process according to the invention.
Waste-based raw stock which contained paper was used. The waste-based raw stock was crushed and sorted into raw stock components. The paper-based raw stock component was led to production of ethanol, and the other raw stock components were recycled directly as materials or were led to energy production. A paper-based raw stock component is raw stock which is rich in cellulose. In addition, an advantage of paper- based raw stock is that the cellulose fibers have been separated already in connection with papermaking, in which case the use of paper-based raw stock in the process according to the invention makes separation of cellulose fibers easier. The raw stock to be used in production of ethanol was led to defibration where the cellulose and hemicellulose fibers were separated from the raw stock in a water suspension, and a fiber suspension was formed from the separated cellulose and hemicellulose fibers. Water was removed from the fiber suspension to provide in the fiber suspension a high percentage of solids, preferably a percentage of solids of 30% to 35%. The obtained fiber suspension was fed to a first hydrolysis step.
In the first hydrolysis step, the enzymes were mixed with the fiber suspension by powerful mixing in a blade reactor at a temperature of 40 to 75°C. The duration of the first step was preferably approximately 2 hours. In a second hydrolysis step following the first hydrolysis step, the enzymes of the second step were mixed with the fiber suspension by powerful mixing in a mixing reactor at a temperature of 40 to 75°C. The second hydrolysis step lasted approximately 4 hours. Mono- and oligosaccharides were formed in the hydrolysis.
After the hydrolysis steps, the fiber suspension was moved to fermentation where the temperature was preferably approximately 35°C, and the duration was approximately 24 hours. In fermentation, ethanol was formed from the mono- and oligosaccharide fraction. After fermentation, the ethanol was separated from the residual fraction such as solid matter and other hydrocarbon fractions by distillating. The distilled ethanol was utilized as a fuel component. The solid-matter- containing residual fraction from distillation of ethanol was led to anaerobic treatment to form biogas. In the anaerobic treatment, the solid matter and the nutrients were fed to a mixing reactor where the dwell time was preferably 15 to 25 days and the temperature was between 30 and 55°C. Example 2
The integrated process and apparatus presented in this example and in Fig. 1 are used to produce etha- nol, biogas, carbon dioxide, steam and heat.
The integrated process of Fig. 1 includes a sorting step 2 for raw stock 1 and a separating step 4 for cellulose fibers to separate them from selected raw stock 3 to form a fiber suspension 5a. If desired, water 28 may be removed from the fiber suspension 5a in a dewaterer 27 to adjust the percentage of solids in the fiber suspension 5b. Furthermore, the process includes a hydrolysis step 6 for the fiber suspension 5b to form sugar-based fractions 7, and a fermentation step 8 for the sugar-based fractions 7 to form products 11 which contain ethanol . In fermentation, carbon dioxide 9 is produced as a by-product, which can be led to be utilized in other processes, e.g. as an industrial gas or in the food industry. Furthermore, the process includes a distillation step 12 for ethanol, where the ethanol 13 and the other desired product fractions are separated from a residual fraction 10. The solid-matter- containing residual fraction 10 is led to an anaerobic treatment step 22 to form biogas 21. In addition, the process includes a combustion boiler 23 for producing energy fractions. Residual and minor flows of the process such as the residue 14 from sorting 2 of the raw stock, residual flow 15 from separation of the cellulose fibers, residual flow 18 from fermentation 8, possible residual flow 20 from distillation 12 and residue 17 from anaerobic treatment 22 may be fed to the combustion boiler 23 to produce energy. In addition, other desired fuel can be fed to the combustion boiler. The energy fractions formed in the combustion boiler 23 can be utilized as heat or steam in the process in question, or they can be led e.g. as heat 24 or steam 25 out of the process to be utilized elsewhere. Energy flows, e.g., can be led from the combustion boiler 23 to hydrolysis 16, fermentation 19 and separation of the cellulose fibers 26.
Example 3
In this example, ethanol was produced by the process according to the invention.
From approximately two tons of industrial waste, 1000kg of lignocellulose-based material was separated. The industrial waste contained, in addition to lignocellulose material, metals, plastics and wood waste. In the first step, the separation was made mechanically, magnetically and by air. In the second step, the separation was made by defibration in which the lignocellulose, especially the cellulose fibers, was separated to a suspension to have a percentage of solids of 3%. The suspension was dried by a two-wire press to have a percentage of solids of 40%. The suspension contained 65% of cellulose and hemicellulose, 5% of lignin, 10% of plastics and 20% of other organic and inorganic materials.
The suspension containing lignocellulose was diluted to have a percentage of solids of 20%. It was fed with 4kg of solid matter / h to enzymatic hydrolysis in a continuous manner. The dwell time in hydrolysis was six hours and the temperature was 55°C. In the hydrolysis step, the viscosity of the suspension was reduced owing to hydrolyzation of the cellulose and to the visible thixotropic property of the material, which was changed by powerful mixing.
The cellulose was hydrolyzed partially to mo- nomeric glucose and partially to oligomeric glucose, in which case the pumpability of the suspension was maintained.
From the hydrolysis container, the suspension was pumped continuously to a fermenting reactor where the dwell time was 48 hours. The fermenting temperature was 35°C, and conventional yeast was added to the suspension. The fermenting reactor operated as an SSF (Simultaneous Saccharification and Fermentation) reactor, thanks to the enzymes brought with the suspension. Fermentation of the produced glucose to ethanol was followed by conventional batch-type further process operations.
After running for 25 hours, the production of lactic acid increased. After running for 30 to 40 hours, the formation of ethanol became constant and started to decrease. After running for 90 to 100 hours, predominantly lactic acid was formed.
The ethanol was led through evaporation, and the distillation waste was fed to anaerobic treatment where 350 to 500 liters of biogas was produced from one kilogram of solid matter. The biogas contained on an average 72% of methane/dry-gas.
Example 4
In this example, lactic acid and ethanol were produced by the process according to the invention.
The test conditions according to Example 3 were used, except that the dwell time in fermentation was reduced to 24 hours. The feed material was fed to hydrolysis at a temperature of 800C to reduce the amount of lactobacilli and other harmful microorganisms. In addition, bisulphite was added in a suitable amount, which does not cause problems to the yeast activity.
The raising of temperature did not destroy- all lactobacilli, and in an attempt to improve the situation of yeast, pH was reduced by sulfuric acid. This did not, however, reduce the pH because the mixture contained inorganic carbonate compounds. Despite the increase in the amount of lactic acid, the yield of ethanol was increased to 80% of the theoretical yield.
Example 5
In this example, pumpability of the suspension was tested in production of ethanol.
Ethanol was produced according to Examples 3 and 4. The percentage of solids in the suspension was raised in the hydrolysis step to 25, 30 and 35% alternately. With a percentage of solids of 35%, it was more difficult to pump the suspension. The reaction rate in the fermenting reactor was reduced a bit.
Example 6
In this example, lactic acid and ethanol were produced by the process according to the invention.
Ethanol was produced according to Examples 3 and 4. A waste fiber fraction from production of chemical pulp was used as raw stock. The waste fiber fraction contained a very small amount of harmful microorganisms .
The waste fiber fraction was dried to have a percentage of solids of 50%. The suspension was fed to hydrolysis with a percentage of solids of 20%. In an 80 hour run, the dwell time in fermentation was 40 hours. The lactic acid bacilli did not increase substantially in fermentation, and the yield of ethanol was approximately 85% of the theoretical yield.
Example 7
In this example, ethanol was produced by the process according to the invention.
Partially sterilized lignocellulose was used as raw stock, and ethanol was produced according to Examples 3 and 4. The percentage of solids in the feed was kept between 25 and 30%, and bisulphite was added as in Example 4. The pH of fermentation was reduced to a value of approximately 4. The yield of ethanol reduced to below 80% of the theoretical yield.
Most of the yeast cells were destroyed after a run of approximately 30 to 40 hours. Fresh yeast was added at specific time intervals.
Example 8
In this example, biogas was produced by the process according to the invention from distillation residual fractions.
In all of the Examples 3 to 7, the distillation waste was fed to anaerobic treatment in a biogas reactor in which biogas was produced from the distillation waste. Significant differences in production of biogas were not discovered between different examples.
The process and the apparatus according to the invention are suitable as different embodiments to be used in the manufacture of most different lignocellu- lose-based products.
The invention is not limited merely to the examples referred to above; instead, many variations are possible within the scope of the inventive idea defined by the claims.

Claims

1. A process for manufacturing a product from lignocellulose-based raw stock, c h a r a c t e r i z e d in that cellulose fibers are separated from the raw stock in a water suspension to provide a fiber suspension, water is removed from the fiber suspension so as to have in the fiber suspension a percentage of solids of between 10 and 50 w-%, the fiber suspension is treated by enzymatic hydrolysis to form at least one sugar-based fraction, the sugar-based fraction is fermented to form at least one product fraction, at least one selected product fraction is separated from a residual fraction, and the residual fraction is led to anaerobic treatment to form biogas.
2. The process according to claim 1, c h a r a c t e r i z e d in that ethanol is formed from the sugar-based fraction.
3. The process according to any one of claims 1 to 2, c h a r a c t e r i z e d in that the ethanol is separated by distillating.
4. The process according to any one of claims 1 to 3, c h a r a c t e r i z e d in that product fractions selected from the group of an enriched sugar fraction, ethanol, butanol, polymer fraction, precursor of a polymer fraction and their combinations are formed from the sugar-based fraction.
5. The process according to any one of claims 1 to 4, c h a r a c t e r i z e d in that the fiber suspension is treated with heat before hydrolysis.
6. The process according to any one of claims 1 to 5, c h a r a c t e r i z e d in that an enzyme is added to the fiber suspension in connection with fermentation.
7. The process according to any one of claims 1 to 6, c h a r a c t e r i z e d in that at least part of the raw stock is sorted before separation of cellu- lose fibers, and the desired substance of the raw stock is led to production of a sugar-based fraction.
8. The process according to any one of claims 1 to 7, c h a r a c t e r i z e d in that the raw stock to be led to production of a sugar-based fraction contains lignin in an amount of less than 25 w-% of the dry content.
9. The process according to any one of claims 1 to 8, c h a r a c t e r i z e d in that residual and minor flows are led from production of a sugar-based fraction, fermentation and/or anaerobic treatment to energy production.
10. The process according to any one of claims 1 to 9, c h a r a c t e r i z e d in that the raw stock is sorted before separation of cellulose fibers, and the desired substance of the raw stock is led to production of a sugar-based fraction, the sugar-based fraction is produced and fermented, the residual fraction from fermentation is led to anaerobic treatment, and the residual material from sorting of the raw stock, separation of cellulose fibers and/or anaerobic treatment is led to production of energy, and energy fractions are fed from energy production to separation of cellulose fibers, production of a sugar-based fraction, fermentation and/or used as energy products.
11. An apparatus for manufacturing a product from lignocellulose-based raw stock, c h a r a c t e r i z e d in that the apparatus includes raw stock feeding means, a cellulose fiber separating device (4) for separating cellulose fibers from the raw stock (3) in a water suspension to provide a fiber suspension (5a), a dewaterer (27) for removing water (28) from the fiber suspension so as to have in the fiber suspension (5b) a percentage of solids of between 10 and 50 w-%, a hydrolysis apparatus (6) for treating the fiber suspension (5b) by enzymatic hydrolysis to form at least one sugar-based fraction (7), fermentation means (8) for fermenting the sugar-based fraction and for forming at least one product fraction (11), separating means (12) for separating at least one selected product fraction (13) from a residual fraction (10), and an anaerobic treatment device (22) to which the residual fraction (10) is led and in which it is treated to form biogas (21) .
12. The apparatus according to claim 11, c h a r a c t e r i z e d in that the apparatus includes a defibration device (4) as the cellulose fiber separating device.
13. The apparatus according to claim 11 or 12, c h a r a c t e r i z e d in that the apparatus includes a distillation apparatus (12) for separating a selected product fraction.
14. The apparatus according to any one of claims 11 to 13, c h a r a c t e r i z e d in that the apparatus includes raw stock sorting means (2) .
15. The apparatus according to any one of claims 11 to 14, c h a r a c t e r i z e d in that the apparatus includes a combustion boiler (23) for burning residual and minor flows and for producing energy fractions .
16. The apparatus according to any one of claims 11 to 15, c h a r a c t e r i z e d in that the apparatus includes raw stock sorting means (2), raw stock feeding means, a cellulose fiber separating device (4), a dewaterer (27), a hydrolysis apparatus (6), fermentation means (8), separating means (12) for separating at least one selected product fraction (13) from a residual fraction (10), an anaerobic treatment device (22) for treating the residual fraction, and a combustion boiler (23) to form a substantially integrated configuration.
PCT/FI2010/050519 2009-06-18 2010-06-18 Process and apparatus for manufacturing a product from lignocellulose-based raw stock WO2010146243A1 (en)

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