WO2024204270A1 - バイオマス固体燃料、及びバイオマス固体燃料の製造方法 - Google Patents

バイオマス固体燃料、及びバイオマス固体燃料の製造方法 Download PDF

Info

Publication number
WO2024204270A1
WO2024204270A1 PCT/JP2024/012086 JP2024012086W WO2024204270A1 WO 2024204270 A1 WO2024204270 A1 WO 2024204270A1 JP 2024012086 W JP2024012086 W JP 2024012086W WO 2024204270 A1 WO2024204270 A1 WO 2024204270A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid fuel
biomass
mass
biomass solid
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2024/012086
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
浩 小林
友祐 平岩
茂也 林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Ube Cement Corp
Original Assignee
Mitsubishi Ube Cement Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Ube Cement Corp filed Critical Mitsubishi Ube Cement Corp
Priority to AU2024249204A priority Critical patent/AU2024249204A1/en
Priority to JP2025510974A priority patent/JPWO2024204270A1/ja
Publication of WO2024204270A1 publication Critical patent/WO2024204270A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • 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

  • This disclosure relates to biomass solid fuel and a method for producing biomass solid fuel.
  • Biomass solid fuels using biomass have been known in the past. Biomass solid fuels are expected to be an alternative to fossil fuels.
  • Patent Document 1 discloses a biomass solid fuel that reduces the chemical oxygen demand (COD) of wastewater.
  • Patent Document 2 discloses a method for producing a biomass solid fuel that suppresses disintegration during production while reducing self-heating.
  • Non-Patent Documents 1 and 2 describe methods for analyzing the constituent sugars of biomass.
  • Biomass solid fuel is produced by molding raw biomass and heating the biomass molded body to carbonize it.
  • the biomass solid fuel may be pulverized during the carbonization process. By suppressing such pulverization during production, dust can be reduced and work efficiency can be improved.
  • the present disclosure provides a biomass solid fuel that can sufficiently reduce the pulverization rate during biomass solid fuel production, and a method for producing biomass solid fuel.
  • One aspect of the present disclosure provides a biomass solid fuel that includes a carbonized product of biomass containing polysaccharides, and has a mannose content of 7.0 mass% or less as a constituent sugar.
  • the biomass solid fuel has a mannose content of 7.0% by mass or less as a constituent sugar. Since such a biomass solid fuel has a low content of mannose, which is difficult to decompose in biomass carbonized material, decomposition of polysaccharides and constituent sugars in the biomass is sufficiently advanced. Since the carbonized materials constituting the biomass solid fuel are firmly bonded to each other, the powdering rate during the production of the biomass solid fuel can be sufficiently reduced.
  • One aspect of the present disclosure provides a method for producing biomass solid fuel, which includes a heating step of heating a biomass molded body that contains polysaccharides, has xylose as a constituent sugar, and has a mannose content of 9.0% by mass or less to obtain a biomass solid fuel, and in the heating step, the reduction rate of the xylose when obtaining the biomass solid fuel from the biomass molded body is 45.0% or more.
  • the above-mentioned production method includes a heating step in which the content of mannose as a constituent sugar is 9.0% by mass or less, and the reduction rate of xylose when obtaining biomass solid fuel from the biomass molded body is 45.0% or more.
  • the xylose in the biomass molded body is sufficiently decomposed, so that the particles of the biomass solid fuel are firmly adhered to each other, and it is possible to obtain biomass solid fuel with a sufficiently reduced powdering rate during the production of the biomass solid fuel.
  • the present disclosure can provide a biomass solid fuel that can sufficiently reduce the powdering rate during biomass solid fuel production, and a method for producing biomass solid fuel.
  • 1 is a photograph of the biomass solid fuel of Example 1, in which bagasse was used as a raw material.
  • 1 is a photograph of the biomass solid fuel of Example 5, which uses acacia as a raw material.
  • 1 is a photograph of the biomass solid fuel of Comparative Example 1, which uses coniferous wood as a raw material.
  • 1 is a photograph showing an image of a powdered portion of the biomass solid fuel of Comparative Example 1, which used coniferous wood as a raw material, observed with an optical microscope.
  • 1 is a photograph showing an SEM image of small pieces obtained from the biomass solid fuel of Example 1 observed with an SEM.
  • 1 is a photograph showing an SEM image of small pieces obtained from the biomass solid fuel of Example 5 observed with an SEM.
  • FIG. 1 is a photograph showing an SEM image of small pieces obtained from the biomass solid fuel of Comparative Example 1 observed with an SEM.
  • FIG. 1 is a diagram showing a flow of component analysis of biomass solid fuel and WP.
  • FIG. 1 shows a chromatogram obtained by measuring the acid-insoluble residue of a biomass molded body using bagasse as a raw material by pyrolysis GC-MS.
  • FIG. 13 is a chromatogram obtained by measuring the acid-insoluble residue of the biomass solid fuel of Example 3, in which bagasse was used as the raw material, by pyrolysis GC-MS.
  • FIG. 1 shows a chromatogram obtained by measuring the acid-insoluble residue of a biomass molded body using acacia as a raw material by pyrolysis GC-MS.
  • FIG. 13 is a chromatogram obtained by measuring the acid-insoluble residue of the biomass solid fuel of Example 5, in which acacia was used as the raw material, by pyrolysis GC-MS.
  • FIG. 2 is a diagram showing a chromatogram obtained by measuring the acid-insoluble residue of a biomass molded body using coniferous wood as a raw material by pyrolysis GC-MS.
  • FIG. 1 is a diagram showing a chromatogram obtained by measuring, by pyrolysis GC-MS, the acid-insoluble residue of the biomass solid fuel of Comparative Example 1, in which coniferous wood was used as the raw material.
  • FIG. 1 is a diagram showing a chromatogram obtained by measuring the acetone extract of a biomass molded body using bagasse as a raw material by GC-MS.
  • FIG. 13 is a chromatogram obtained by measuring, by GC-MS, an acetone extract of the biomass solid fuel of Example 3 in which bagasse was used as the raw material.
  • FIG. 1 is a diagram showing a chromatogram obtained by measuring the acetone extract of a biomass molded body using acacia as a raw material by GC-MS.
  • FIG. 13 is a chromatogram obtained by measuring, by GC-MS, the acetone extract of the biomass solid fuel of Example 5, in which acacia was used as the raw material.
  • FIG. 1 is a diagram showing a chromatogram obtained by measuring the acid-insoluble content of a biomass molded body using coniferous wood as a raw material by GC-MS.
  • FIG. 2 is a diagram showing a chromatogram obtained by measuring the acid-insoluble matter of the biomass solid fuel of Comparative Example 1, in which coniferous wood was used as the raw material, by GC-MS.
  • FIG. 2 is a diagram showing the mannose content (converted content) in each of a biomass molded body and a biomass solid fuel based on the biomass before heating.
  • FIG. 1 is a diagram showing the xylose content (converted content) in each of a biomass molded body and a biomass solid fuel based on the biomass before heating.
  • FIG. 1 is a diagram showing the xylose content (converted content) in each of a biomass molded body and a biomass solid fuel based on the biomass before heating.
  • FIG. 1 is a diagram showing the relative concentrations of linear hydrocarbons in biomass molded bodies and biomass solid fuel before heating in Examples 3 and 5, and Comparative Example 1.
  • FIG. 1 is a diagram showing the relative concentrations of higher alcohols in the biomass molded bodies and biomass solid fuel before heating in Examples 3 and 5, and Comparative Example 1.
  • the biomass solid fuel has a mannose content of 7.0% by mass or less as a constituent sugar. Since such a biomass solid fuel has a low content of persistent mannose, the decomposition of polysaccharides and constituent sugars by heating during production has progressed sufficiently. As the polysaccharides and constituent sugars are decomposed, a substance that inhibits powdering is produced, so that the powdering rate can be reduced. From the viewpoint of further reducing the powdering rate, the mannose content of the biomass solid fuel as a constituent sugar may be, for example, 5.0% by mass or less, 3.5% by mass or less, 2.0% by mass or less, 1.0% by mass or less, or 0.5% by mass or less.
  • Mannose may not be contained in the biomass solid fuel, but may be contained to such an extent that, for example, a trace amount of mannose as a constituent sugar is detected, may be more than 0% by mass, or may be 0.1% by mass or more.
  • An example of the mannose content of the solid fuel as a constituent sugar is more than 0% by mass and 7.0% by mass or less.
  • one example of the biomass solid fuel may have mannose detected as a constituent sugar, and the mannose content may be 7.0% by mass or less.
  • the biomass solid fuel may contain xylose as a constituent sugar, and the xylose content may be 15.0% by mass or less.
  • an example of the biomass solid fuel may further contain xylose as a constituent sugar, and the xylose content may be 15.0% by mass or less.
  • the xylose is sufficiently decomposed by heating during production, and the xylose is converted into a substance that suppresses powdering.
  • the xylose content may be 10.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, or 6.0% by mass or less.
  • the xylose content is preferably present at a moderate level from the viewpoint of yield, and may be greater than 0% by mass, 0.1% by mass or more, 1.0% by mass or more, 2.0% by mass or more, greater than 3.1% by mass, 3.5% by mass or more, 4.0% by mass or more, or 5.0% by mass or more.
  • the xylose content is preferably low from the viewpoints of reducing COD, improving fuel characteristics (fixed carbon, fuel ratio, calorific value), improving BMI2, increasing soaking water content, and reducing chlorine content. On the other hand, from the viewpoint of DU, the higher the content, the more preferable.
  • the xylose content is, for example, 0.1 to 15.0% by mass, greater than 3.1% by mass and 15.0% by mass or less, 4.0 to 15.0% by mass, or 5.0 to 15.0% by mass.
  • Monosaccharides such as mannose and xylose constitute the polysaccharides contained in biomass solid fuel. Since polysaccharides have a large molecular weight, their content cannot be directly measured using analytical equipment. Therefore, in this disclosure, the polysaccharide content is determined, for example, by measuring the content of constituent sugars obtained by hydrolyzing polysaccharides in a sample with an acid using HPLC or GC, and multiplying the content by a polysaccharide conversion factor that takes into account overdecomposition of the constituent sugars.
  • the method for analyzing the constituent sugars of biomass can be measured, for example, by the method described in Non-Patent Document 1 or Non-Patent Document 2.
  • each monosaccharide as a constituent sugar means the content of each monosaccharide detected by the method described in Non-Patent Document 1 or Non-Patent Document 2, and does not necessarily specify that it is present as a monosaccharide in biomass solid fuel.
  • the content of biomass constituent sugars can be determined, for example, by adding 3 mL of 72% sulfuric acid to 0.3 g of biomass solid fuel, reacting at 30°C for 1 hour, filtering the reaction liquid, and analyzing the filtrate by HPLC or GC-MS.
  • GC-MS is preferably used because of its versatility and excellent selectivity.
  • the content of biomass constituent sugars can be determined by the method described in the Examples.
  • the above analysis method can measure the content of glucose, galactose, arabinose, xylose, mannose, and other constituent sugars that make up polysaccharides. By multiplying the measurement result by the polysaccharide conversion factor for each constituent sugar, the content of polysaccharides containing each constituent sugar can be considered.
  • polysaccharides include glucan, galactan, arabinan, xylan, and mannan.
  • the biomass solid fuel may contain at least one of these polysaccharides.
  • the biomass solid fuel may contain, for example, glucan, xylan, and arabinan.
  • the biomass solid fuel may not contain mannan. In this disclosure, not containing constituent sugars or polysaccharides means that it is below the detection limit.
  • the biomass which is the raw material for biomass solid fuel, is not particularly limited in terms of tree species or part, but may have a mannose content of 9.0% by mass or less, 7.0% by mass or less, or 5.0% by mass or less as a constituent sugar.
  • the biomass may not contain mannose as a constituent sugar.
  • the biomass may be broad-leaved woody trees, such as acacia, rubber trees, eucalyptus, meranti, or teak.
  • the biomass may also be herbaceous, such as oil palm trunks, palm empty fruit bunches (EFB), sorghum, bagasse, or napier grass.
  • the biomass may contain one of these types alone, or two or more types in combination.
  • the raw material biomass may contain the polysaccharides mentioned above. Furthermore, polysaccharides to which at least one selected from the above polysaccharides is bonded and which have a higher molecular weight are called cellulose or hemicellulose. Biomass may contain the above cellulose or hemicellulose. Cellulose is composed of multiple glucans bonded together. On the other hand, hemicellulose is composed of two or more types of polysaccharides bonded together, and examples of such polysaccharides include glucuronoxylan, arabinoxylan, and glucomannan.
  • the content of arabinose contained as a constituent sugar in the biomass solid fuel may be 1.0 mass% or less, 0.7 mass% or less, 0.5 mass% or less, or less than 0.5 mass%.
  • arabinose may not be contained, it is desirable that it is contained in a moderate amount from the viewpoint of yield, and taking both into consideration, the content of 0 to 1.0 mass% is desirable.
  • the content of arabinose is preferably low from the viewpoints of reducing COD, improving fuel characteristics (fixed carbon, fuel ratio, calorific value), improving BMI2, increasing soaking water content, and reducing chlorine content.
  • the content of arabinose is preferably high from the viewpoint of increasing DU. Examples of the content of arabinose contained as a constituent sugar are, for example, 0 to 1.0 mass%, 0 to 0.7 mass%, or 0 mass% or more and less than 0.5 mass%.
  • the content of glucose contained as a constituent sugar in the biomass solid fuel may be 43.0% by mass or less, or 42.0% by mass or less. Furthermore, since glucose forms the basic skeleton of the carbonized material, if there is too little glucose, it becomes impossible to maintain the skeleton, so it is preferable that it is present in an appropriate amount. From this viewpoint, it may be 25.0% by mass or more, 30.0% by mass or more, or 35.0% by mass or more.
  • An example of the content of glucose contained as a constituent sugar is, for example, 25.0 to 43.0% by mass, or 35.0 to 43.0% by mass.
  • the content of galactose contained as a constituent sugar of the biomass solid fuel may be 0.9% by mass or less, 0.7% by mass or less, 0.5% by mass or less, or less than 0.5% by mass.
  • Galactose may also not be contained. Examples of the content of galactose contained as a constituent sugar are, for example, 0 to 0.9% by mass, 0 to 0.7% by mass, or 0% by mass or more and less than 0.5% by mass.
  • the components of the acid insoluble matter can be evaluated by dissolving the biomass solid fuel in 72% by mass sulfuric acid, repeatedly filtering and washing to recover the residue that did not dissolve in the sulfuric acid, and subjecting the residue to pyrolysis GC-MS to measure the components. Specifically, the components of the acid insoluble matter are evaluated using the peak area of the peak detected by pyrolysis GC-MS measurement. Pyrolysis GC-MS can be performed by introducing the gas obtained by pyrolyzing the recovered residue in a helium gas atmosphere in a heating furnace set at 600°C into the GC-MS.
  • the amount of the detected components is slightly affected by the equipment conditions when comparing the peak areas directly, so from the perspective of improving accuracy, it is preferable to determine the relative amount (relative concentration) based on the peak area of the acacia biomass compact (acacia WP).
  • the amount of a component detected per mass of residue B of the biomass solid fuel relative to the amount of a component detected per mass of residue A of the acacia biomass molded body can be expressed as a relative concentration by the following formula (1).
  • Relative concentration (peak area of components detected by pyrolysis GC-MS / mass of residue B put into heating furnace) / (peak area of components detected by pyrolysis GC-MS of acacia WP / mass of residue A put into heating furnace) (1)
  • the biomass solid fuel may contain components that are insoluble in sulfuric acid (acid insoluble matter), and by containing such components, powdering during production is further suppressed.
  • the components that are insoluble in sulfuric acid may be those that produce specific gas components when heated. Examples of the specific gas components include pentatriacont-17-ene and 4-ethylphenol. Note that pentatriacont-17-ene is a component that is not contained in coniferous trees, and is also not observed in the heat decomposition gas of coniferous trees.
  • the amount of detection B per unit mass of the residue B of Pentatriacont-17-ene generated in the gas generated when the biomass solid fuel according to this embodiment is dissolved in 72% by mass sulfuric acid and the undissolved residue B is heated in a heating furnace under conditions of a helium gas atmosphere and 600°C the amount of detection B per unit mass of the residue B of Pentatriacont-17-ene generated in the gas generated when the biomass solid fuel according to this embodiment is dissolved in 72% by mass sulfuric acid and the undissolved residue B is heated in a heating furnace under conditions of a helium gas atmosphere and 600°C
  • the amount of detection B may be 0.1 to 2.0 times the amount of detection A.
  • the relative concentration of Pentatriacont-17-ene calculated by replacing “components detected by pyrolysis GC-MS" in the above formula (1) with “Pentatriacont-17-ene detected by pyrolysis GC-MS” may be 0.1 to 2.0.
  • the relative concentration of Pentatriacont-17-ene may be 0.2 to 1.5, 0.4 to 1.4, 0.6 to 1.2, or 0.9 to 1.1.
  • the relative concentration of linear hydrocarbons in residue B when biomass solid fuel is dissolved in 72% by mass sulfuric acid may be 0.20 to 1.50, 0.30 to 1.40, 0.50 to 1.20, or 0.60 to 0.90 in order to further suppress pulverization of biomass solid fuel.
  • Biomass solid fuel containing linear hydrocarbons in the above relative concentration ranges can further reduce the pulverization rate.
  • Linear hydrocarbons are represented by the sum of the areas of the peaks of linear hydrocarbons detected during retention times of 20 minutes or more under the pyrolysis GC-MS conditions used in the examples.
  • the relative concentration of higher alcohols in the residue when biomass solid fuel is dissolved in 72% by mass sulfuric acid may be 0.05 to 0.80, 0.10 to 0.50, or 0.20 to 0.40 in order to further suppress pulverization of the biomass solid fuel.
  • Biomass solid fuel containing higher alcohols in the above relative concentration ranges can further reduce the pulverization rate.
  • the higher alcohols are represented by the sum of the areas of the peaks of higher alcohols detected after a retention time of 20 minutes under the pyrolysis GC-MS conditions used in the examples.
  • the acetone extract of the biomass solid fuel obtained based on ISO 14453:2014 "Determination of acetone soluble matter in pulp” may contain 2,6-dimethoxyphenol, and the content of the 2,6-dimethoxyphenol may be 50 to 2000 mg/kg of the mass of the biomass solid fuel in an absolutely dry state. From the viewpoint of further reducing the dusting rate, the content of 2,6-dimethoxyphenol may be 60 to 1500 mg/kg, 70 to 1000 mg/kg, 70 to 500 mg/kg, or 80 to 200 mg/kg of the mass of the biomass solid fuel in an absolutely dry state. Since 2,6-dimethoxyphenol is a component not contained in coniferous trees, biomass solid fuel containing 2,6-dimethoxyphenol in the above range can further reduce the dusting rate.
  • bone-dry state refers to biomass solid fuel that has been heat-treated at 107°C for at least four hours and has reached a constant weight.
  • the acetone extract of the biomass solid fuel obtained based on ISO 14453:2014 "Determination of acetone soluble matter in pulp” may contain 4-ethylphenol, and the content of the 4-ethylphenol may be 10 to 100 mg/kg of the mass of the biomass solid fuel in an absolutely dry state. From the viewpoint of further suppressing pulverization, the content of 4-ethylphenol may be 30 to 90 mg/kg or 50 to 80 mg/kg of the mass of the biomass solid fuel in an absolutely dry state. Since 4-ethylphenol is a component not contained in conifers and acacia, biomass solid fuel containing 4-ethylphenol in the above range can further reduce the pulverization rate.
  • the fuel ratio (fixed carbon/volatile matter) of the biomass solid fuel may be 0.1 or more, or 0.2 or more, from the viewpoint of further improving combustibility.
  • the fuel ratio may be 0.5 or less, 0.4 or less, or 0.3 or less.
  • An example of the fuel ratio of the biomass solid fuel may be 0.1 to 0.5, 0.1 to 0.45, 0.1 to 0.4, 0.1 to 0.3, or 0.2 to 0.3. By having the fuel ratio in this range, the combustibility of the biomass solid fuel can be further improved.
  • the fixed carbon and volatile matter of the biomass solid fuel can be measured in accordance with JIS M 8812:2016.
  • the fixed carbon may be 10 to 30 mass%, 15 to 25 mass%, 10 to 25 mass%, 10 to 21 mass%, or 13 to 21 mass%.
  • the volatile content may be 60-80% by mass, or 65-75% by mass.
  • the higher heating value of the biomass solid fuel may be 15,000 to 25,000 kJ/kg, 17,000 to 22,000 kJ/kg, or 18,000 to 20,000 kJ/kg.
  • the higher heating value of the biomass solid fuel may be measured in accordance with JIS M 8814:2003.
  • the moisture content of the biomass solid fuel may be 4.0% by mass or more, or 5.0% by mass or more, from the viewpoint of increasing the binding property of the raw material of the solid fuel. Also, from the viewpoint of reducing the fluidity of the biomass solid fuel and improving its handleability, the moisture content of the biomass solid fuel may be 8.0% by mass or less, 7.0% by mass or less, or 6.0% by mass or less.
  • An example of the moisture content range of the biomass solid fuel may be 4.0 to 8.0% by mass, 5.0 to 7.0% by mass, or 5.0 to 6.0% by mass. When the moisture content of the biomass solid fuel is within the above range, the elasticity of the biomass solid fuel tends to improve and the powdering rate tends to decrease. When the moisture content of the biomass solid fuel is within the above range, the powdering rate of the biomass solid fuel can be further reduced.
  • the ash content of the biomass solid fuel may be 0.1 mass% or more, 1.0 mass% or more, 3.0 mass% or more, 4.0 mass% or more, or 4.6 mass% or more.
  • the ash content of the biomass solid fuel may be 10.0 mass% or less, 9.0 mass% or less, 8.0 mass% or less, 6.0 mass% or less, 5.7 mass% or less, or 5.4 mass% or less.
  • An example of the ash content of the biomass solid fuel may be 0.1 to 8.0 mass%, 0.5 to 7.0 mass%, 0.1 to 10.0 mass%, 0.5 to 9.5 mass%, 1.0 to 9.0 mass%, 2.0 to 8.5 mass%, 3.0 to 8.0 mass%, 3.0 to 6.0 mass%, 4.0 to 5.7 mass%, or 4.6 to 5.4 mass%.
  • the ash content in the biomass solid fuel increases, the hardness of the biomass solid fuel tends to increase and the pulverization rate tends to decrease.
  • the pulverization rate of the biomass solid fuel can be further reduced.
  • the moisture and ash content of biomass solid fuel can be measured in accordance with JIS M 8812:2016.
  • the maximum temperature reached by biomass solid fuel in the self-heating test may be less than 200°C.
  • the self-heating test is a test specified in the "United Nations: Recommendations on the Transport of Dangerous Goods: Manual of Tests and Criteria: 5th Edition: Self-heating test.”
  • the chemical oxygen demand (COD) of the biomass solid fuel may be 1500 ppm or less, 1000 ppm or less, or 700 ppm or less.
  • the COD may be 100 ppm or more, 200 ppm or more, 300 ppm or more, or 500 ppm or more.
  • An example of the range of COD may be 100 to 1500 ppm, or 500 to 1500 ppm.
  • the COD of the immersion water when the biomass solid fuel is immersed in water refers to the COD value of the immersion water sample for COD measurement prepared at room temperature under the following conditions in accordance with the Environment Agency Notification No.
  • sample: water 1:10 (mass ratio)
  • Shaking method 200 times/min in the horizontal direction
  • Dissolution time 6 hours
  • the COD value of the immersion water can be measured in accordance with JIS K 0102:2016-17 "Oxygen consumption by potassium permanganate at 100°C".
  • the room temperature is, for example, 20°C.
  • the room temperature may be 15 to 25°C, or 20 to 25°C.
  • the mechanical durability (DU) of biomass solid fuel can be determined in accordance with the American Agricultural and Industrial Standard ASAE S 269.4 and the German Industrial Standard DIN EN 15210-1.
  • the DU value may be 90.0 or more, 95.0 or more, 96.0 or more, or 97.0 or more.
  • the DU value may also be 100 or less. With the DU in this range, the biomass solid fuel can be made sufficiently easy to handle. In addition, the biomass solid fuel becomes appropriately hard, and powdering can be further suppressed.
  • An example of the DU range may be 90.0 to 100, or 97.0 to 100.
  • the bulk density of the biomass solid fuel based on JIS Z 8807:2012 may be 500 to 700 kg/m 3 , 550 to 650 kg/m 3 , 580 to 650 kg/m 3 , or 600 to 650 kg/m 3.
  • the powdering rate of the biomass solid fuel can be further reduced.
  • the biomass solid fuel may have a crushability index (HGI) based on JIS M 8801:2008 of 60 or less, 50 or less, or 40 or less.
  • the HGI may be 15 or more, 20 or more, or 25 or more.
  • the HGI may be, for example, 15 to 60, 20 to 60, or 20 to 40.
  • the crushing work index (BMI2) of biomass solid fuel may be 50.0 to 95.0, 65.0 to 90.0, 72.0 to 90.0, 73.0 to 90.0, or 72.0 to 85.0.
  • BMI2 is defined as the ratio of the mass of the sieve with a mesh size of 150 ⁇ m to the total mass of the sieve with a mesh size of 1000 ⁇ m for a sample crushed for 20 minutes according to a procedure based on JIS M 4002:2000 "Test method for crushing work index".
  • the chlorine content in the biomass solid fuel may be 0.001 to 0.04 mass%, or 0.002 to 0.035 mass%.
  • the chlorine content can be measured by elemental analysis based on JIS M 8813:2006.
  • the shape of the biomass solid fuel may be cylindrical.
  • the diameter may be 6.0 to 10.0 mm, 6.0 to 8.5 mm, or 7.0 to 8.5 mm.
  • the length of the central axis may be 40 mm or less, or 30 mm or less.
  • the length of the central axis may be 15 mm or more.
  • the shape of the biomass solid fuel is not limited to a cylindrical shape.
  • the volume of the biomass solid fuel may be 1000 to 2500 mm 3 , or 1200 to 2000 mm 3. When the volume of the biomass solid fuel is within this range, the production efficiency and handling of the biomass solid fuel can be improved.
  • the biomass solid fuel may, for example, contain a carbonized product of biomass containing polysaccharides, and may have a mannose content of 7.0 mass% or less as a constituent sugar, an ash content of 3.0 to 8.0 mass%, a fixed carbon content of 10.0 to 21.0 mass%, and an HGI of 40.0 or less.
  • a biomass solid fuel has an even lower powdering rate.
  • the method for producing biomass includes a heating step of heating a biomass molded body that contains polysaccharides, has xylose as a constituent sugar, and has a mannose content of 9.0% by mass or less as a constituent sugar to obtain a biomass solid fuel, and in the heating step, when obtaining the biomass solid fuel from the biomass molded body, the reduction rate of the xylose is 45.0% or more.
  • the biomass solid fuel obtained by the above production method has a low powdering rate.
  • the biomass as the raw material of the biomass molded body can be one or more selected from acacia, rubber tree, eucalyptus, meranti, teak, oil palm trunk, palm empty fruit bunch (EFB), sorghum, bagasse, and napier grass.
  • One or more of these biomass raw materials may be used in combination.
  • the biomass contains xylose as a constituent sugar. Xylose is decomposed by the heating process and changes into a substance that reduces the powdering rate of the biomass solid fuel.
  • the content of xylose as a constituent sugar in the raw biomass may be 5.0% by mass or more, 10.0% by mass or more, 12.0% by mass or more, 15.0% by mass or more, or 20.0% by mass or more.
  • the content of xylose as a constituent sugar in the raw biomass may be 30.0% by mass or less, 25.0% by mass or less, or 23.0% by mass or less.
  • An example of the xylose content may be 5.0 to 30.0% by mass, 10.0 to 30.0% by mass, or 20.0 to 30.0% by mass.
  • polysaccharides containing xylose as a constituent sugar include glucuronoxylan and arabinoxylan.
  • acacia contains a lot of glucuronoxylan, so it is possible to further reduce the powdering rate when used as a biomass solid fuel.
  • bagasse and oil palm trunk contain a lot of arabinoxylan, so it is possible to further reduce the powdering rate when used as a biomass solid fuel.
  • the biomass which is the raw material for the biomass molded body, has a mannose content of 9.0% by mass or less as a constituent sugar. Since mannose is difficult to decompose, in biomass with a low mannose content, xylose and the like decompose during the heating process and change into a substance that reduces the powdering rate. This reduces the powdering rate of the biomass solid fuel. Therefore, the content of mannose as a constituent sugar in the raw biomass may be 7.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, or 2.0% by mass or less.
  • the raw biomass may not contain mannose, but may contain a trace amount of mannose as a constituent sugar, or may be more than 0% by mass, and the mannose content may be 0.1% by mass or more.
  • An example of the mannose content is more than 0% by mass and less than 7.0% by mass.
  • An example of a polysaccharide containing mannose as a constituent sugar is glucomannan.
  • the hemicellulose that makes up coniferous trees contains a lot of glucomannan as a polysaccharide, which is composed of glucose and mannose as monosaccharides. This mannose is not easily decomposed by heating and remains in the carbonized material, so it tends to suppress the change in xylose and increase the powdering rate of biomass solid fuel.
  • the biomass which is the raw material for the biomass molded body, may have an arabinose content of 1.5% by mass or more, which is a constituent sugar.
  • the arabinose is decomposed during the heating process and changes into a substance that reduces the powdering rate of the biomass solid fuel.
  • the arabinose content as a constituent sugar in the raw biomass may be 1.7% by mass or more, or 1.8% by mass or more.
  • the arabinose content may be 3.0% by mass or less, or 2.7% by mass or less.
  • An example of the arabinose content is 1.5 to 3.0% by mass.
  • Arabinoxylan is one example of a polysaccharide that contains arabinose and xylose as constituent sugars.
  • bagasse and oil palm trunk which are herbaceous plants, contain a lot of arabinoxylan, so the dusting rate can be further reduced when used as biomass solid fuel.
  • the biomass which is the raw material of the biomass molded body, may have a xylose content of 7.0% by mass or more as a constituent sugar.
  • the xylose is decomposed by the heating process and changes into a substance that reduces the powdering rate of the biomass solid fuel.
  • the content of xylose as a constituent sugar in the raw material biomass may be 10.0% by mass or more, 12.0% by mass or more, 14.0% by mass or more, or 20.0% by mass or more.
  • the content of xylose may be 50.0% by mass or less, 40.0% by mass or less, 30.0% by mass or less, or 25.0% by mass or less.
  • An example of the xylose content may be 7.0 to 50.0% by mass, 12.0 to 30.0% by mass, or 20.0 to 30.0% by mass.
  • the biomass which is the raw material for the biomass molded body, may have a galactose content of 3.0% by mass or less, which is a constituent sugar.
  • a low galactose content in the biomass makes it easier for xylose and the like to be converted into a substance that reduces the powdering rate.
  • the galactose content as a constituent sugar in the raw biomass may be 2.0% by mass or less, or 1.0% by mass or less.
  • the raw biomass may not contain galactose, but may contain, for example, a trace amount of galactose as a constituent sugar that is detectable, or may be greater than 0% by mass, and the galactose content may be 0.1% by mass or more.
  • An example of the galactose content may be greater than 0% by mass and less than 3.0% by mass, 0.1 to 3.0% by mass, or 0.1 to 1.0% by mass.
  • the biomass which is the raw material for the biomass molded body, may have a glucose content as a constituent sugar of 60.0% by mass or less, 55.0% by mass or less, or 50.0% by mass or less.
  • the glucose content as a constituent sugar in the raw material biomass may be 30.0% by mass or more, or 35.0% by mass or more.
  • An example of the glucose content may be 30% to 60.0% by mass.
  • a molding step may be performed before the heating step.
  • the molding step is a step of molding the biomass raw material to obtain a biomass molded body (White Pellets: hereinafter referred to as "WP").
  • the molding may be performed by a known method or by compression.
  • the shape of the WP may be a pellet.
  • the shape of the WP may be a cylinder, and the diameter may be 6.0 to 10.0 mm, or 7.0 to 8.5 mm.
  • the length of the central axis may be 40 mm or less, or 30 mm or less.
  • the length of the central axis may be 15 mm or more.
  • the volume of the WP may be 1000 to 2500 mm 3 , or 1200 to 2000 mm 3. It is not necessary to use a binder when obtaining a biomass molded body from biomass. By not using a binder, it is possible to reduce costs.
  • the forming step may include a step of crushing and pulverizing the biomass raw material. Crushing and pulverization may be performed by a known method.
  • the crushed powder may be used as the raw material for WP.
  • the size of the crushed powder may be 100 to 3000 ⁇ m, or 400 to 1000 ⁇ m, in terms of the arithmetic mean diameter of a circumscribed circle of the powder.
  • the biomass may be formed by the crushing and pulverizing step.
  • the biomass may be one or more selected from acacia, rubber tree, eucalyptus, meranti, teak, oil palm trunk, palm empty fruit bunch, sorghum, bagasse, and napier grass.
  • the heating process is a process in which the WP is heated to obtain a biomass solid fuel.
  • the xylose in the biomass solid fuel obtained by the heating process is reduced by 45.0% or more from the xylose in the WP.
  • the xylose in the WP is partially decomposed by the heating process and converted into another substance, which can reduce the powdering rate of the biomass solid fuel.
  • the reduction rate of xylose when obtaining a biomass solid fuel from the WP may be 55.0% or more, or 65.0% or more.
  • the reduction rate of xylose may be 100% or less, 95.0% or less, or 90.0% or less.
  • An example of the range of the reduction rate of xylose is 45.0 to 100%.
  • the reduction rate of xylose is based on mass. In this disclosure, the reduction rate means the conversion reduction rate based on the biomass molded body before heating.
  • the conversion reduction rate of xylose can be calculated using the xylose content in the biomass molded body (W0), the xylose content in the biomass solid fuel (W1), and the yield of the biomass solid fuel by the heating step (Y) according to the following formula (2).
  • Xylose conversion reduction rate (W0 - W1 x (Y / 100)) / W0 x 100 (2)
  • the converted xylose content in the biomass solid fuel may be 2.0 to 15.0% by mass, or 3.0 to 12.0% by mass.
  • the mannose content in the biomass solid fuel based on the biomass before heating may be 1.0% by mass or less, or 0.8% by mass or less.
  • the converted mannose content may be 0% by mass or more, or 0.1% by mass or more.
  • the reduction rate of Heptacosan-1-ol when obtaining biomass solid fuel from WP may be 70.0% or more.
  • Heptacosan-1-ol can be detected by measuring the residue that does not dissolve when the biomass solid fuel and WP are dissolved in 72% by mass sulfuric acid using pyrolysis GC-MS.
  • Heptacosan-1-ol is converted to Pentatriacont-17-ene by heating, which can suppress the powdering of the biomass solid fuel. Therefore, from the viewpoint of further suppressing the powdering of the biomass solid fuel, the reduction rate of Heptacosan-1-ol may be 80.0% or more, or may be 90.0% or more.
  • Heptacosan-1-ol can be detected by analyzing the residue of the WP and biomass solid fuel using pyrolysis GC-MS.
  • the heating step may include heating the biomass molded body in a temperature range of 150 to 400°C, 200 to 360°C, or 220 to 270°C.
  • the heating temperature range includes this range, the organic matter in the biomass solid fuel is reduced, and the COD of the wastewater containing the biomass solid fuel can be further reduced.
  • the heating time in the above temperature range may be 0.2 to 3 hours. Heating may be performed in a batch-type heating furnace or a continuous-type heating furnace.
  • the heating method may be an indirect resistance type electric furnace if it is a batch-type, or an indirect heating furnace using hot air if it is a continuous type.
  • the biomass molded body may be heated in an atmosphere with an oxygen concentration of 10.0% by mass or less, or 8.0% by mass or less.
  • the oxygen concentration may be adjusted by maintaining the inside of the heating furnace at atmospheric pressure, or by introducing nitrogen into the heating furnace. By keeping the oxygen concentration in this range, the production efficiency of biomass solid fuel can be sufficiently improved.
  • the yield (Y) of the biomass solid fuel in the heating step may be 70.0% by mass or more, 75.0% by mass or more, or 80.0% by mass or more.
  • the yield (Y) may be 100% by mass or less, or 95.0% by mass or less.
  • the yield (Y) may be adjusted to, for example, 70.0 to 100% by mass. This yield is the ratio of the mass of the biomass solid fuel to the mass of the biomass molded body. With the yield in this range, the production efficiency of the biomass solid fuel can be sufficiently improved.
  • the powdering rate of the biomass solid fuel obtained in this manner is sufficiently reduced.
  • the powdering rate can be determined by sieving the biomass solid fuel obtained by the heating step and calculating the mass fraction of the fuel that falls through a sieve with a mesh size of 3.35 mm.
  • the powdering rate may be, for example, 2.5 mass% or less, or 2.0 mass% or less.
  • the powdering rate may also be 0.1 mass% or more. The lower the powdering rate, the more the generation of dust during production is suppressed, improving the production efficiency of the biomass solid fuel and reducing the environmental load.
  • the sieve may be used based on a procedure in accordance with JIS M 8801:2008.
  • the biomass solid fuel may be obtained by heating the biomass molded body.
  • the heating conditions may be as described in the heating process above.
  • the biomass solid fuel may not contain a binder. Not containing a binder can further reduce the manufacturing cost.
  • a biomass solid fuel comprising a carbonized product of biomass containing polysaccharides, the carbonized product having a mannose content of 7.0 mass% or less as a constituent sugar.
  • the biomass solid fuel according to [1] which contains xylose as a constituent sugar and has a xylose content of 15.0 mass% or less.
  • the acetone extractable fraction contains 2,6-dimethoxyphenol;
  • the acetone extractables according to ISO 14453:2014 contain 4-ethylphenol.
  • biomass solid fuel according to any one of [1] to [6], wherein the content of 4-ethylphenol is 10 to 100 mg/kg based on the mass of the biomass solid fuel in an absolute dry state.
  • a biomass molded body made of acacia is dissolved in 72% by mass of sulfuric acid, and the undissolved residue A is heated in a heating furnace under a helium gas atmosphere at 600° C.
  • the amount of Pentatriacont-17-ene generated in the gas generated when the residue A is heated is defined as the amount of Pentatriacont-17-ene detected per unit mass of the residue A
  • the biomass solid fuel is dissolved in 72% by mass of sulfuric acid, and the undissolved residue B is heated in a heating furnace under a helium gas atmosphere at 600° C., and the amount of the pentatriacont-17-ene residue B detected per unit mass in the generated gas is defined as the detection amount B.
  • the biomass solid fuel according to any one of [1] to [7], wherein the detection amount B is 0.1 to 2.0 times the detection amount A.
  • the biomass solid fuel according to any one of [1] to [10] comprising a cylindrical molded body having a diameter of 6.0 to 10.0 mm and a length in a central axis direction of 40 mm or less.
  • a method for producing a biomass solid fuel by heating a biomass molded body containing polysaccharides, xylose as a constituent sugar, and having a mannose content of 9.0% by mass or less A method for producing a biomass solid fuel, wherein in the heating step, a reduction rate of the xylose when obtaining the biomass solid fuel from the biomass molded body is 45.0% or more.
  • the biomass molded body is molded by a process of crushing a raw material biomass, The method for producing a biomass solid fuel according to any one of [16] to [20], wherein the biomass is one or more selected from acacia, rubber tree, eucalyptus, meranti, teak, oil palm trunk, palm empty fruit bunch, sorghum, bagasse, and napier grass.
  • Example 1 The bagasse prepared as a raw material was crushed and then pulverized. A molding process was carried out to mold the crushed bagasse to 3000 ⁇ m or less. In the molding process, the crushed bagasse was uniaxially pressurized to obtain a cylindrical biomass molded body (hereinafter referred to as "WP") with a diameter (pellet diameter) of 8.3 mm and a length of 25 mm. The WP was obtained using only the raw biomass without adding a binder to the raw biomass. 4 kg of the obtained WP was put into a batch-type small electric rotary kiln (manufactured by Takasago Industrial Co., Ltd.) having a heating chamber with an inner diameter of 600 mm, and heated to 230 ° C.
  • WP cylindrical biomass molded body
  • Example 2 Biomass solid fuel was obtained in the same manner as in Example 1, except that the heating temperature in the rotary kiln was set to 240° C., 250° C., or 260° C., respectively.
  • the yield, bulk density, and powdering rate were calculated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 5 WP was produced in the same manner as in Example 1, except that acacia was used as the raw material for biomass, and the heating temperature during the heating step was set to 250°C to obtain a biomass solid fuel.
  • the yield, bulk density, and powdering rate were calculated in the same manner as in Example 1.
  • the pellet diameter of the WP was 8.1 mm. The results are shown in Table 1.
  • Example 6 WP was produced in the same manner as in Example 1, except that rubber trees were used as the biomass raw material, and the heating temperature in the heating step was set to 250°C to obtain a biomass solid fuel.
  • the yield, bulk density, and powdering rate were calculated in the same manner as in Example 1.
  • the pellet diameter of the WP was 7.7 mm. The results are shown in Table 2.
  • Example 7 WP was produced in the same manner as in Example 1, except that the raw material of biomass was a mixture of (70% by mass of acacia + 30% by mass of eucalyptus), and the heating temperature during the heating process was set to 250°C to obtain a biomass solid fuel. The yield, bulk density, and powdering rate were calculated in the same manner as in Example 1. The pellet diameter of the WP was 8.2 mm. The results are shown in Table 2.
  • Example 1 WP was produced in the same manner as in Example 1, except that the raw material for biomass was North American coniferous wood, and the heating temperature during the heating step was set to 250°C to obtain a biomass solid fuel. The yield, bulk density, and powdering rate were calculated in the same manner as in Example 1. The pellet diameter of the WP was 6.5 mm. The results are shown in Table 2.
  • Example 8 A WP was produced in the same manner as in Example 1, except that oil palm trunk (OPT) was used as the biomass raw material, and the heating temperature during the heating step was set to 250° C. to obtain a biomass solid fuel. The yield, bulk density, and powdering rate were calculated in the same manner as in Example 1. The results are shown in Table 3.
  • OPT oil palm trunk
  • Example 9 WP was produced using acacia as a biomass raw material in the same manner as in Example 5, and the heating temperature during the heating step was set to 290°C to obtain a biomass solid fuel.
  • the yield, bulk density, and powdering rate were calculated in the same manner as in Example 1.
  • the results are shown in Table 3.
  • the values of the WP in Table 3 are the same as the values of the WP in Table 1 using acacia as a raw material.
  • Example 10 WP was produced using acacia as a biomass raw material in the same manner as in Example 5, and the heating temperature in the heating step was set to 300° C. to obtain a biomass solid fuel.
  • the yield, bulk density, and powdering rate were calculated in the same manner as in Example 1. The results are shown in Table 3.
  • Example 1 ⁇ Physical property evaluation> [Visual Observation] The biomass solid fuels produced in Example 1, Example 5, and Comparative Example 1 were visually observed. Photographs of Example 1, Example 5, and Comparative Example 1 taken with a commercially available camera are shown in FIG. 1, FIG. 2, and FIG. 3. As shown in FIG. 1, FIG. 2, and FIG. 3, it was confirmed that the biomass solid fuels were black-brown cylindrical. On the other hand, in FIG. 3, more biomass solid fuels with distorted shapes were confirmed than in FIG. 1 and FIG. 2. Also, in FIG. 2, more biomass solid fuels with distorted shapes were confirmed than in FIG. 1.
  • the biomass solid fuels using coniferous trees as raw materials were most pulverized during production, and that the pulverization could be improved by using acacia and bagasse.
  • the bagasse maintained a clean cylindrical shape, had a smooth and glossy surface, and had few defects at the ends. It was shown that the color was the blackest brown, it was fully burned, and it could be most improved in pulverization.
  • Example and Comparative Example 1 the COD of the soaking water samples of the WP and each biomass solid fuel was measured by a method conforming to JIS K 0102:2016-17 "Oxygen consumption by potassium permanganate at 100°C".
  • the soaking water samples for COD measurement were prepared according to the Environment Agency Notification No. 13 (a) of 1973, which is a method for testing metals, etc. contained in industrial waste, by adding 10 times the amount of water by mass to the biomass solid fuel, and shaking the mixture at room temperature in a horizontal direction at a speed of 200 times per minute for 6 hours.
  • the results of Examples 1 to 5 are shown in Table 1, the results of Examples 6, 7 and Comparative Example 1 in Table 2, and the results of Examples 8 to 10 in Table 3.
  • HGI grindability index
  • Example and Comparative Example 1 the obtained WP and biomass solid fuel were pulverized for 20 minutes using a ball mill.
  • the ball mill used was one conforming to JIS M 4002:2000, and a cylindrical container with an inner diameter of 305 mm and an axial length of 305 mm was rotated at a speed of 70 rpm to accommodate standard ball bearings (diameter 36.5 mm x 43 pieces, diameter 30.2 mm x 67 pieces, diameter 24.4 mm x 10 pieces, diameter 19.1 mm x 71 pieces, diameter 15.9 mm x 94 pieces) as specified in JIS B 1501:2009.
  • Example and Comparative Example 1 the biomass solid fuel and WP were immersed in water for 100 hours to reach an equilibrium state, then removed from the water, the surface was wiped, and the mass was measured. The immersion moisture was calculated from the mass ratio before and after immersion.
  • Table 1 the results of Examples 6 and 7 and Comparative Example 1 in Table 2, and the results of Examples 8 to 10 in Table 3.
  • Non-Patent Document 2 uses GC-MS, which is highly versatile and has excellent selectivity, and GC-MS was used this time as well. Therefore, measurements were performed after the filtrate was derivatized using the aldonitrile-acetylation method.
  • the xylose content in the biomass solid fuel based on the biomass before heating was calculated (hereinafter referred to as "converted xylose content").
  • the "converted xylose content” was subtracted from the measured value (W0) of the xylose content in WP, and divided by W0 to calculate the converted xylose reduction rate as the xylose reduction rate.
  • the (W0-W1 x (Y/100)) part in formula (4) was calculated as the converted xylose reduction amount for each constituent sugar.
  • V1 x (Y/100) the mannose content in the biomass solid fuel based on the biomass before heating
  • Figure 21 shows the mannose content in the biomass molded body (WP) and the "equivalent mannose content” in the biomass solid fuel.
  • Figure 22 shows the xylose content in the biomass molded body (WP) and the "equivalent xylose content” in the biomass solid fuel.
  • the mannose and xylose contents in the biomass molded body (WP) are the measured values of the mannose content (V0) and the measured values of the xylose content (W0).
  • the recovered residue was introduced into a heating furnace set at 600°C under a helium atmosphere, and the generated gas was directly introduced into a GC-MS for pyrolysis GC-MS analysis to calculate the relative concentration.
  • the conditions for the heating furnace and GC-MS equipment were as follows:
  • Heating furnace Equipment: Frontier Labs "EGA/PY-3030D" Heating conditions: 600°C instantaneous heating atmosphere: He
  • FIG. 9 shows a chromatogram of the WP before heating in Example 3
  • Figure 10 shows the biomass solid fuel in Example 3
  • Figure 11 shows the WP before heating in Example 5
  • Figure 12 shows the biomass solid fuel in Example 5
  • Figure 13 shows the WP before heating in Comparative Example 1
  • Figure 14 shows the chromatogram of the biomass solid fuel in Comparative Example 1.
  • the relative concentration is a value calculated by the following formula (6).
  • Relative concentration (peak area of each component detected by pyrolysis GC-MS / sample mass put into heating furnace) ⁇ (peak area of each component detected by pyrolysis GC-MS of acacia WP / sample mass put into heating furnace) (6)
  • the peak area was calculated by taking the peak start position, which is the rising part of the peak, as the baseline start position, and the peak end position, which is the ending part of the peak, as the base end position, and the line connecting the baseline start and baseline end was taken as the baseline.
  • the peak area was calculated as the area enclosed by the curve passing through this baseline and the peak top.
  • Heptacosan-1-ol (CAS No. 2004-39-9, relative concentration 1.19) was detected at peak No. 17, retention time 30.183 minutes (position 30.183 minutes on the horizontal axis).
  • the relative concentration of Heptacosan-1-ol was determined based on Pentatriacont-17-ene in acacia WP as the standard.
  • Pentatriacont-17-ene (CAS No. 6971-10-0, relative concentration 1.08) was detected at peak No. 16, retention time 30.500 minutes.
  • Peak No. Pentatriacont-17-ene (CAS No. 2004-39-9, relative concentration 1.19) was detected at peak No. 17, retention time 30.183 minutes (position 30.183 minutes on the horizontal axis).
  • the relative concentration of Heptacosan-1-ol was determined based on Pentatriacont-17-ene in acacia WP as the standard.
  • Pentatriacont-17-ene (CAS No. 6971
  • GC-MS of acetone extract and pyrolysis compounds For the WP and biomass solid fuel of Example 3, Example 5, and Comparative Example 1, the acetone extract of about 10 g of the frozen and crushed sample was calculated in accordance with "ISO 14453: Pulpes-Determination of acetone-soluble matter". Qualitative analysis of the acetone extract was performed by appropriately diluting a part of the extract with acetone and then analyzing it with a gas chromatograph mass spectrometer (GC-MS) to identify the main detected components (peaks). The identification was estimated by matching the mass spectrum and GC retention index of the detected components with a library such as NIST.
  • a library such as NIST.
  • FIG. 15 shows the WP before heating in Example 3
  • Figure 16 shows the biomass solid fuel in Example 3
  • Figure 17 shows the WP before heating in Example 5
  • Figure 18 shows the biomass solid fuel in Example 5
  • Figure 19 shows the WP before heating in Comparative Example 1
  • Figure 20 shows the biomass solid fuel in Comparative Example 1.
  • Tables 1 to 5 are shown below. In Tables 1 to 5, items that do not need to be measured or cannot be calculated are indicated with “-”, and missing data is indicated with “N/A”. Additionally, “0.0" for the constituent sugars in Tables 1 to 3 indicates that they are below the detection limit.
  • Comparative Example 1 had a higher mannose content and a higher powdering rate than the other Examples. Therefore, it was confirmed that a biomass solid fuel with a low powdering rate can be obtained by using a biomass with a low mannose content as a raw material.
  • the reduction rate (converted reduction rate) of xylose when producing a biomass solid fuel from WP at a heating temperature of 250°C was 54.9% in Comparative Example 1, while it was 81.6% in Example 3, 77.2% in Example 5, 71.2% in Example 6, 67.1% in Example 7, and 82.4% in Example 8.
  • the powdering rate tends to decrease when xylose is decomposed a lot in the heating process. It is considered that this is because the decomposition of xylose produces a substance that functions as a binder that firmly bonds the carbonized materials that make up the biomass solid fuel together. Mannose tends to be difficult to decompose when heated, and in Comparative Example 1, which contains a large amount of mannose, it is believed that mannose inhibits the decomposition of xylose, making it difficult for xylose decomposition products to be produced.
  • the powdering rate was further reduced in the biomass solid fuels of Examples 1 to 4 and Example 8, which were obtained by heating WP made from bagasse and OPT containing 1.5% or more by mass of arabinose. Therefore, it was confirmed that by further containing arabinose in addition to the raw material xylose, a biomass solid fuel with an even lower powdering rate can be obtained. Also, as shown in Table 3, in Examples 9 and 10, which used acacia as the raw material and were heated at temperatures of 290°C and 300°C, the powdering rate was lower than in Comparative Example 1, which used coniferous wood as the raw material.
  • the components detected up to a retention time of 20 minutes are thought to be substances generated by the pyrolysis of cellulose and lignin through rapid pyrolysis at 600°C. Therefore, it is thought to be unrelated to substances generated through thermal production.
  • WP and biomass solid fuels made from bagasse and acacia as raw materials linear hydrocarbons and higher alcohols were detected after a retention time of 20 minutes.
  • no linear hydrocarbons or higher alcohols were detected in coniferous trees.
  • Pentatriacont-17-ene is preferable because it contributes to suppressing powdering during the production of biomass solid fuel. Therefore, among the linear hydrocarbons and higher alcohols, pentatriacont-17-ene in particular is thought to be the component that contributes to the pulverization of biomass solid fuel.
  • biomass solid fuel in which the powdering rate during the production of the biomass solid fuel is sufficiently reduced. It is also possible to provide a method for producing such a biomass solid fuel.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
PCT/JP2024/012086 2023-03-27 2024-03-26 バイオマス固体燃料、及びバイオマス固体燃料の製造方法 Ceased WO2024204270A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2024249204A AU2024249204A1 (en) 2023-03-27 2024-03-26 Biomass solid fuel and method for producing biomass solid fuel
JP2025510974A JPWO2024204270A1 (https=) 2023-03-27 2024-03-26

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023-050303 2023-03-27
JP2023050303 2023-03-27

Publications (1)

Publication Number Publication Date
WO2024204270A1 true WO2024204270A1 (ja) 2024-10-03

Family

ID=92905453

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/012086 Ceased WO2024204270A1 (ja) 2023-03-27 2024-03-26 バイオマス固体燃料、及びバイオマス固体燃料の製造方法

Country Status (3)

Country Link
JP (1) JPWO2024204270A1 (https=)
AU (1) AU2024249204A1 (https=)
WO (1) WO2024204270A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026074836A1 (ja) * 2024-10-02 2026-04-09 Ｕｂｅ三菱セメント株式会社 バイオマス固体燃料、及びバイオマス固体燃料の焼成方法、並びにバイオマス固体燃料の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020059737A1 (ja) * 2018-09-20 2020-03-26 日本製紙株式会社 固体燃料の製造方法
WO2022079427A1 (en) * 2020-10-12 2022-04-21 Hamer, Christopher Process for producing solid biomass fuel
US20220306958A1 (en) * 2020-02-06 2022-09-29 Hong Mei Bai Process for producing solid biomass fuel
WO2022209196A1 (ja) * 2021-03-29 2022-10-06 Ｕｂｅ三菱セメント株式会社 バイオマス炭化装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020059737A1 (ja) * 2018-09-20 2020-03-26 日本製紙株式会社 固体燃料の製造方法
US20220306958A1 (en) * 2020-02-06 2022-09-29 Hong Mei Bai Process for producing solid biomass fuel
WO2022079427A1 (en) * 2020-10-12 2022-04-21 Hamer, Christopher Process for producing solid biomass fuel
WO2022209196A1 (ja) * 2021-03-29 2022-10-06 Ｕｂｅ三菱セメント株式会社 バイオマス炭化装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026074836A1 (ja) * 2024-10-02 2026-04-09 Ｕｂｅ三菱セメント株式会社 バイオマス固体燃料、及びバイオマス固体燃料の焼成方法、並びにバイオマス固体燃料の製造方法

Also Published As

Publication number Publication date
JPWO2024204270A1 (https=) 2024-10-03
AU2024249204A1 (en) 2025-09-18

Similar Documents

Publication Publication Date Title
Liu et al. Comparison of biochar formation from various agricultural by-products using FTIR spectroscopy
Rehrah et al. Production and characterization of biochars from agricultural by-products for use in soil quality enhancement
Ilić et al. Surface functional groups and degree of carbonization of selected chars from different processes and feedstock
Santos et al. Application of orange peel waste in the production of solid biofuels and biosorbents
Tao et al. An integrated study on the pyrolysis mecanism of peanut shell based on the kinetic analysis and solid/gas characterization
Cao et al. Characterization of wood chars produced at different temperatures using advanced solid-state 13C NMR spectroscopic techniques
Eibisch et al. Properties and degradability of hydrothermal carbonization products
Nguyen et al. Properties of Biochars prepared from local biomass in the Mekong Delta, Vietnam
Rodríguez Correa et al. Investigation of the textural and adsorption properties of activated carbon from HTC and pyrolysis carbonizates
He et al. Production and characterization of biochar from agricultural by‐products: overview and use of cotton biomass residues
Wang et al. Evolution and correlation of the physiochemical properties of bamboo char under successive pyrolysis process
Saeed et al. Production and characterization of rice husk biochar and Kenaf biochar for value-added biochar replacement for potential materials adsorption
WO2024204270A1 (ja) バイオマス固体燃料、及びバイオマス固体燃料の製造方法
Yaacoubi et al. Synthesis of composites from activated carbon based on olive stones and sodium alginate for the removal of methylene blue
Yang et al. Physical and Chemical Characteristics of the Bamboo Culm and Wood Carbonized at Low Temperature.
Agweh et al. Production and characterization of waste nutshells derived biocarbon through slow pyrolysis: an investigation on the effects of pyrolysis temperature
Pasieczna-Patkowska et al. Comparison of photoacoustic, diffuse reflectance, attenuated total reflectance and transmission infrared spectroscopy for the study of biochars
Bakti et al. Characterization of active carbon from coconut shell using X-ray diffraction (X-RD) and SEM-EDX techniques
Hazourli et al. Characterization of activated carbon prepared from lignocellulosic natural residue:-Example of date stones
Hassen Effect of KOH ratio on the formation of activated carbon from pressed wood residues
Usha et al. Evaluation of loblolly pine wood biochar properties derived from the slow-pyrolysis process for the synergetic benefit of carbon sequestration and soil conditioning
Hernandez-Maglinao et al. Improving the Surface Areas and Pore Volumes of Biochar Produced from Pyrolysis of Cotton Gin Trash via Steam Activation Process
Dhifallah et al. Kinetic, thermodynamic, and reaction mechanism study of raw Phragmites australis pyrolysis using thermogravimetric analysis
Bardalai et al. Production and characterisation of teak tree saw dust and rice husk biochar
WO2026074836A1 (ja) バイオマス固体燃料、及びバイオマス固体燃料の焼成方法、並びにバイオマス固体燃料の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24780378

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: AU2024249204

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2025510974

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2025510974

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 2024249204

Country of ref document: AU

Date of ref document: 20240326

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2501006429

Country of ref document: TH

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 24780378

Country of ref document: EP

Kind code of ref document: A1