Biomass solid fuel

Abstract

To provide a biomass solid fuel that suppresses collapse due to rainwater and reduces COD of wastewater while suppressing increase in cost.SOLUTION: A biomass solid fuel obtained by molding biomass powder, which is characterized in that it has a fuel ratio (fixed carbon / volatile content) of 0.2-0.8, an anhydrous base high calorific value of 4,800-7,000 (kcal / kg), a molar ratio O / C of oxygen O to carbon C of 0.1-0.7, and a molar ratio H / C of hydrogen H to carbon C of 0.8-1.3.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a biomass solid fuel. [Background technology]

[0002] Conventionally, solid fuels made by molding woody biomass have been known, but they have problems such as being difficult to handle because they disintegrate when exposed to rainwater, etc. during outdoor storage, and also increasing the COD (chemical oxygen demand) of wastewater due to the elution of organic matter such as tar. Therefore, in Patent Document 1, plant-based raw materials are steam exploded, then molded and heated to obtain a solid fuel that does not disintegrate when exposed to rainwater, etc. during storage without using a binder, prevents the elution of tar components, and reduces the COD of wastewater. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Application No. 2012-266635 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the above-mentioned conventional technology requires a steam explosion process, which increases costs.

[0005] The present invention has been made to solve this problem, and its purpose is to provide a biomass solid fuel that is less susceptible to degradation due to rainwater and reduces the COD of wastewater, while suppressing increases in costs. [Means for solving the problem]

[0006] The biomass solid fuel of the present invention is It is characterized as a biomass solid fuel made by molding biomass powder, with a fuel ratio (fixed carbon / volatile matter) of 0.2 to 0.8, a higher heating value on an anhydrous basis of 4,800 to 7,000 (kcal / kg), a molar ratio of oxygen (O) to carbon (C) of O / C of 0.1 to 0.7, and a molar ratio of hydrogen (H) to carbon (C) of H / C of 0.8 to 1.3. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a biomass solid fuel that does not require a steam explosion process or binders, suppresses increases in costs, suppresses disintegration due to rainwater, and reduces COD in wastewater. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a graph showing the relationship between heating temperature and COD and pH of biomass solid fuel. [Figure 2] FIG. 10 is a graph showing the correlation between the heating temperature in the heating step and the pulverizability and pulverization speed of the obtained biomass solid fuel. [Figure 3] FIG. 1 is a diagram showing particle size distribution of biomass solid fuels subjected to a pulverization test. [Figure 4] FIG. 10 is a diagram showing the results of a water immersion test (solid moisture content) of a biomass solid fuel. [Figure 5] FIG. 1 is a graph showing the solid strength (rotational strength) before and after immersion in water. [Figure 6] FIG. 1 is a graph showing the solid strength (mechanical durability) before and after immersion in water. [Figure 7] FIG. 2 is a diagram showing the BET specific surface area of ​​a solid fuel. [Figure 8] FIG. 1 is a diagram showing the average pore diameter of the surface of a solid fuel. [Figure 9] FIG. 1 shows the total pore volume of the surface of a solid fuel. [Figure 10] FIG. 1 is a graph showing the yield of biomass solid fuel. [Figure 11] FIG. 1 is a diagram showing the spontaneous combustion index (SCI) of biomass solid fuel. [Figure 12] 1 is a cross-sectional photograph of Example A-2 before immersion in water. [Figure 13] 1 is a cross-sectional photograph of Example A-2 after immersion in water (2 seconds). [Figure 14] 1 is a cross-sectional photograph of Example A-2 after immersion in water (20 seconds). [Figure 15] 1 is a cross-sectional photograph of Comparative Example A before immersion in water. [Figure 16] 1 is a cross-sectional photograph of Comparative Example A after immersion in water (2 seconds). [Figure 17] 1 is a cross-sectional photograph of Comparative Example A after immersion in water (20 seconds). [Figure 18] FIG. 1 is a diagram showing a (presumed) mechanism of solid cross-linking development in PBT. [Figure 19] FIG. 1 is a diagram showing the results of FT-IR analysis of the outer surface of a pellet of a biomass solid fuel. [Figure 20] FIG. 1 is a diagram showing the results of FT-IR analysis of the center of a cross section of a pellet of a biomass solid fuel. [Figure 21] FIG. 10 is a diagram showing the results of FT-IR analysis of an acetone extract of a biomass solid fuel. [Figure 22] FIG. 10 is a diagram showing the results of FT-IR analysis of the solid after acetone extraction of the biomass solid fuel. [Figure 23] FIG. 1 shows the results of GC-MS analysis of an acetone extract of biomass solid fuel. [Figure 24] FIG. 10 shows the shape of the pellets after immersion in saline in Example B. [Figure 25] FIG. 10 shows the distribution of sodium before and after immersion in saline in Example B. DETAILED DESCRIPTION OF THE INVENTION

[0009] The biomass solid fuel of the present invention uses the molded solid obtained through a molding process in which biomass is crushed and pulverized, and the resulting chipped or powdered biomass is compressed and molded into lumps, followed by a heating process in which the lumps after the molding process are heated (this corresponds to PBT, described below). The biomass solid fuel of the present invention does not require a steam explosion process or a binder, and therefore can suppress cost increases. In this specification, the lumps obtained by the molding process and before the heating process are also referred to as "unheated lumps."

[0010] The biomass used as a raw material may be woody or plant-based, and the tree species and part thereof are not particularly limited. Examples include Douglas fir, American larch, cedar, Japanese cypress, Scots pine, old almond trees, almond shells, acacia wood, acacia bark, walnut shells, sago palm, EFB (empty fruit bunches left over from palm oil processing), meranti, rubber trees, and the like, and the biomass may be one of these or a mixture of two or more of them.

[0011] In the molding step, the mixture is formed into lumps using a known molding technique. The lumps are preferably pellets or briquettes and may be of any size. In the heating step, the molded lumps are heated.

[0012] The biomass solid fuel obtained after the heating step preferably has a COD (chemical oxygen demand) of 3000 ppm or less when soaked in water. Furthermore, the biomass solid fuel preferably has a COD ratio of 0.98 or less, expressed as (COD of biomass solid fuel after heating step / COD of unheated biomass solid fuel). Here, the COD (chemical oxygen demand) (also simply referred to as "COD") of the soaking water when the biomass solid fuel is soaked in water refers to the COD value obtained by preparing a soaking water sample for COD measurement in accordance with Environment Agency Notification No. 13 (A) of 1973, a method for testing metals, etc. contained in industrial waste, and analyzing the sample in accordance with JIS K0102 (2010)-17.

[0013] The biomass solid fuel obtained after the heating step preferably has a crushability index (HGI) based on JIS M 8801 of 15 or more and 60 or less, more preferably 20 or more and 60 or less. 2 / g, and 0.15 to 0.7m 2 / g. The equilibrium moisture content after immersion in water is preferably 15 to 65 wt%, more preferably 15 to 60 wt%.

[0014] The biomass solid fuel of the present invention has a fuel ratio (fixed carbon / volatile matter) of 0.2 to 0.8, a higher heating value on an anhydrous basis of 4,800 to 7,000 (kcal / kg), a molar ratio of oxygen (O) to carbon (C) of O / C of 0.1 to 0.7, and a molar ratio of hydrogen (H) to carbon (C) of H / C of 0.8 to 1.3. Having the physical property values ​​of the biomass solid fuel within these ranges reduces COD in wastewater during storage, reduces pulverization, and improves handleability during storage. The biomass solid fuel of the present invention can be obtained by, for example, adjusting the species and part of the biomass used as a raw material, the heating temperature in the heating step, etc. The proximate analysis values, elemental analysis values, and higher heating values ​​in this specification are based on JIS M 8812, 8813, and 8814.

[0015] The method for producing a biomass solid fuel of the present invention includes a molding step of molding biomass powder from crushed and pulverized biomass to obtain unheated aggregates, and a heating step of heating the unheated aggregates to obtain a heated solid. The heating temperature in the heating step is preferably 150°C to 400°C. By setting the temperature in this range, a biomass solid fuel having the above-mentioned properties can be obtained. The heating temperature is determined appropriately depending on the shape and size of the raw biomass and aggregates, but is preferably 150°C to 400°C, more preferably 200°C to 350°C, even more preferably 230°C to 300°C, and even more preferably 250°C to 290°C. The heating time in the heating step is not particularly limited, but is preferably 0.2 to 3 hours. The particle size of the biomass powder is not particularly limited, but is approximately 100 to 3000 μm on average, preferably 400 to 1000 μm on average. The particle size of the biomass powder may be measured using a known method. As described below, in the biomass solid fuel (PBT) of the present invention, the connection or adhesion between the biomass powders is maintained by solid cross-linking, so the particle size of the biomass powders is not particularly limited as long as it is within a moldable range. Furthermore, because fine pulverization increases costs, any known particle size range is acceptable as long as it is within a range that balances cost and moldability.

[0016] If the bulk density of the unheated aggregates before the heating step is A and the bulk density of the heated solid after the heating step is B, then it is preferable that B / A = 0.7 to 1. The value of bulk density A is not particularly limited as long as it is within a known range in which unheated aggregates can be obtained by molding biomass powder. Furthermore, since bulk density varies depending on the type of raw biomass, it may be set appropriately. Furthermore, if the HGI (Hardgrove Crushability Index according to JIS M8801) of the unheated aggregates is H1 and the HGI of the heated solid is H2, then it is preferable that H2 / H1 = 1.1 to 2.5. By performing heating so that either or both of the values ​​of B / A and H2 / H1 are within this range, it is possible to obtain a biomass solid fuel that reduces COD in wastewater during storage while also reducing pulverization, thereby improving handleability during storage.

[0017] The preferred ranges for the properties of biomass solid fuel may be determined depending on the species of biomass used as a raw material. Examples are given below, but the present invention is not limited to these species and their combinations. Below, preferred ranges are shown for the types of biomass raw materials used in the present invention, the properties of the resulting solid fuel (corresponding to PBT, described below), and its production method.

[0018] [Types of raw biomass and properties of solid fuel] (Dogwood, Japanese larch, Japanese cedar, and Japanese cypress: Solid fuel A) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel A) containing at least one species selected from Douglas fir, Douglas fir, Japanese cedar, and Japanese cypress as a raw material are as follows.

[0019] The COD is preferably 1000 ppm or less, more preferably 900 ppm or less, and even more preferably 800 ppm or less, and the COD ratio is preferably 0.80 or less, more preferably 0.70 or less, and even more preferably 0.68 or less.

[0020] The equilibrium moisture content (described later) after immersion in water is preferably 15 wt% to 45 wt%, more preferably 18 wt% to 35 wt%, and even more preferably 18 wt% to 32 wt%.

[0021] BET specific surface area is 0.25m 2 / g~0.8m 2 / g, and 0.28m 2 / g~0.6m 2 / g, more preferably 0.32m 2 / g~0.5m 2 / g is more preferred.

[0022] The HGI is preferably 20 to 60, more preferably 20 to 55, and even more preferably 22 to 55. Coal (bituminous coal) suitable as a boiler fuel for power generation has an HGI of around 50, and considering that it will be mixed and pulverized with other coal, the closer to around 50 the better. The HGI ratio (described below) is preferably 1.0 to 2.5.

[0023] The fuel ratio is preferably 0.2 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.2 to 0.65.

[0024] The higher heating value on an anhydrous basis is preferably 4800 to 7000 kcal / kg, more preferably 4900 to 7000 kcal / kg, and even more preferably 4950 to 7000 kcal / kg.

[0025] The molar ratio O / C of oxygen O to carbon C is preferably from 0.1 to 0.62, more preferably from 0.1 to 0.61, and even more preferably from 0.1 to 0.60.

[0026] The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and even more preferably 0.9 to 1.3.

[0027] The preferable ranges for the properties of solid fuel A have been described above.

[0028] When producing the solid fuel A, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 210 to 330°C, and even more preferably 220 to 300°C.

[0029] (Scots pine: solid fuel B) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel B) when the raw material is Scots pine are as follows.

[0030] The COD is preferably 900 ppm or less, more preferably 800 ppm or less, and even more preferably 700 ppm or less, and the COD ratio is preferably 0.75 or less, more preferably 0.68 or less, and even more preferably 0.64 or less.

[0031] The equilibrium moisture content after immersion in water is preferably 15 wt% to 45 wt%, more preferably 18 wt% to 40 wt%, and even more preferably 18 wt% to 31 wt%.

[0032] BET specific surface area is 0.30m 2 / g~0.7m 2 / g, and 0.30m 2 / g~0.6m 2 / g, more preferably 0.30m 2 / g~0.5m 2 / g is more preferred.

[0033] The HGI is preferably from 25 to 60, more preferably from 30 to 55, and even more preferably from 35 to 55. The HGI ratio (described later) is preferably from 1.0 to 2.5.

[0034] The fuel ratio is preferably 0.2 to 0.8, more preferably 0.2 to 0.7, and even more preferably 0.2 to 0.65.

[0035] The higher heating value on an anhydrous basis is preferably 4950 to 7000 kcal / kg, more preferably 5000 to 7000 kcal / kg, and even more preferably 5100 to 7000 kcal / kg.

[0036] The molar ratio O / C of oxygen O to carbon C is preferably from 0.1 to 0.60, more preferably from 0.2 to 0.60, and even more preferably from 0.3 to 0.60.

[0037] The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and even more preferably 0.9 to 1.3.

[0038] The preferable ranges for the properties of solid fuel B have been described above.

[0039] When producing solid fuel B, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 220 to 300°C, and even more preferably 240 to 290°C.

[0040] (Old Almond Tree: Solid Fuel C) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel C) when the raw material is old almond trees are as follows.

[0041] The COD is preferably 2100 ppm or less, more preferably 2000 ppm or less, and even more preferably 1500 ppm or less, and the COD ratio is preferably 0.80 or less, more preferably 0.75 or less, and even more preferably 0.55 or less.

[0042] The equilibrium moisture content after immersion in water is preferably 25 wt% to 60 wt%, more preferably 30 wt% to 50 wt%, and even more preferably 30 wt% to 45 wt%.

[0043] BET specific surface area is 0.20m 2 / g~0.70m 2 / g, and 0.22m 2 / g~0.65m 2 / g, more preferably 0.25m 2 / g~0.60m 2 / g is more preferred.

[0044] The HGI is preferably from 15 to 60, more preferably from 18 to 55, and even more preferably from 20 to 55. The HGI ratio (described later) is preferably from 1.0 to 2.0.

[0045] The fuel ratio is preferably 0.2 to 0.8, more preferably 0.25 to 0.7, and even more preferably 0.30 to 0.65.

[0046] The higher heating value on an anhydrous basis is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6500 kcal / kg, and even more preferably 4900 to 6500 kcal / kg.

[0047] The molar ratio O / C of oxygen O to carbon C is preferably 0.10 to 0.70, more preferably 0.20 to 0.60, and even more preferably 0.30 to 0.60.

[0048] The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and even more preferably 0.9 to 1.20.

[0049] The preferable ranges for the properties of the solid fuel C have been described above.

[0050] When producing the solid fuel C, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 220 to 300°C, and even more preferably 240 to 290°C.

[0051] (Mixture of almond shells and old almond trees: Solid fuel D) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel D) when the raw material is a mixture of almond shells and old almond trees are as follows.

[0052] The COD is preferably 2500 ppm or less, more preferably 2000 ppm or less, and even more preferably 1500 ppm or less, and the COD ratio is preferably 0.75 or less, more preferably 0.68 or less, and even more preferably 0.50 or less.

[0053] The equilibrium moisture content after immersion in water is preferably 15 wt% to 50 wt%, more preferably 20 wt% to 40 wt%, and even more preferably 20 wt% to 35 wt%.

[0054] BET specific surface area is 0.20m 2 / g~0.70m 2 / g, and 0.27m2 / g~0.70m 2 / g, more preferably 0.30m 2 / g~0.60m 2 / g is more preferred.

[0055] The HGI is preferably from 20 to 60, more preferably from 20 to 55, and even more preferably from 23 to 55. The HGI ratio (described later) is preferably from 1.0 to 2.0.

[0056] The fuel ratio is preferably 0.2 to 0.8, more preferably 0.30 to 0.7, and even more preferably 0.35 to 0.65.

[0057] The higher heating value on an anhydrous basis is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6500 kcal / kg, and even more preferably 4900 to 6300 kcal / kg.

[0058] The molar ratio O / C of oxygen O to carbon C is preferably from 0.10 to 0.70, more preferably from 0.20 to 0.60, and even more preferably from 0.30 to 0.55.

[0059] The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.8 to 1.25, and even more preferably 0.85 to 1.20.

[0060] The preferable ranges for the properties of solid fuel D have been described above.

[0061] When producing the solid fuel D, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 220 to 300°C, and even more preferably 240 to 290°C.

[0062] (Acacia wood: solid fuel E) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel E) when the raw material is acacia wood are as follows.

[0063] The COD is preferably 950 ppm or less, more preferably 850 ppm or less, and even more preferably 800 ppm or less, and the COD ratio is preferably 0.95 or less, more preferably 0.85 or less, and even more preferably 0.80 or less.

[0064] The equilibrium moisture content after immersion in water is preferably 20 wt% to 60 wt%, more preferably 20 wt% to 55 wt%, and even more preferably 23 wt% to 53 wt%.

[0065] BET specific surface area is 0.40m 2 / g~0.70m 2 / g, and 0.50m 2 / g~0.70m 2 / g, more preferably 0.55m 2 / g~0.70m 2 / g is more preferred.

[0066] The fuel ratio is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, and even more preferably 0.2 to 0.4.

[0067] The higher heating value on an anhydrous basis is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6000 kcal / kg, and even more preferably 4800 to 5500 kcal / kg.

[0068] The molar ratio O / C of oxygen O to carbon C is preferably from 0.40 to 0.70, more preferably from 0.45 to 0.70, and even more preferably from 0.48 to 0.65.

[0069] The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 1.0 to 1.3, and even more preferably 1.1 to 1.3.

[0070] The preferable ranges for the properties of the solid fuel E have been described above.

[0071] When producing the solid fuel E, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 220 to 300°C, and even more preferably 240 to 290°C.

[0072] (Acacia Bark: Solid Fuel F) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel F) when the raw material is acacia bark are as follows.

[0073] The COD is preferably 2500 ppm or less, more preferably 2000 ppm or less, and even more preferably 1200 ppm or less, and the COD ratio is preferably 0.30 or less, more preferably 0.20 or less, and even more preferably 0.15 or less.

[0074] The equilibrium moisture content after immersion in water is preferably 15 wt% to 50 wt%, more preferably 20 wt% to 45 wt%, and even more preferably 25 wt% to 40 wt%.

[0075] BET specific surface area is 0.35m 2 / g~0.55m 2 / g, and 0.40m 2 / g~0.55m 2 / g, more preferably 0.40m 2 / g~0.50m 2 / g is more preferred.

[0076] The fuel ratio is preferably 0.4 to 0.8, more preferably 0.42 to 0.75, and even more preferably 0.45 to 0.75.

[0077] The higher heating value on an anhydrous basis is preferably 4800 to 7000 kcal / kg, more preferably 5000 to 7000 kcal / kg, and even more preferably 5200 to 6500 kcal / kg.

[0078] The molar ratio O / C of oxygen O to carbon C is preferably from 0.25 to 0.60, more preferably from 0.30 to 0.60, and even more preferably from 0.30 to 0.55.

[0079] The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.2.

[0080] The preferable ranges for the properties of the solid fuel F have been described above.

[0081] When producing the solid fuel F, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 220 to 300°C, and even more preferably 240 to 290°C.

[0082] (Mixture of almond and walnut shells: Solid fuel G) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel G) when the raw material is a mixture of almond shells and walnut shells are as follows.

[0083] The COD is preferably 2500 ppm or less, more preferably 2100 ppm or less, and even more preferably 1500 ppm or less, and the COD ratio is preferably 0.65 or less, more preferably 0.55 or less, and even more preferably 0.45 or less.

[0084] The equilibrium moisture content after immersion in water is preferably 20 wt% to 45 wt%, more preferably 20 wt% to 40 wt%, and even more preferably 25 wt% to 35 wt%.

[0085] BET specific surface area is 0.15m 2 / g~0.35m 2 / g, and 0.19m 2 / g~0.33m 2 / g, more preferably 0.20m 2 / g~0.30m 2 / g is more preferred.

[0086] The HGI is preferably 18 to 60, and more preferably 20 to 60. The HGI ratio is preferably 1.0 or more.

[0087] The fuel ratio is preferably 0.2 to 0.7, more preferably 0.25 to 0.65, and even more preferably 0.28 to 0.60.

[0088] The higher heating value on an anhydrous basis is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6000 kcal / kg, and even more preferably 5000 to 6000 kcal / kg.

[0089] The molar ratio O / C of oxygen O to carbon C is preferably from 0.30 to 0.65, more preferably from 0.40 to 0.70, and even more preferably from 0.40 to 0.60.

[0090] The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.9 to 1.25, and even more preferably 0.9 to 1.2.

[0091] The preferable ranges for the properties of the solid fuel G have been described above.

[0092] When producing the solid fuel G, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 220 to 300°C, and even more preferably 240 to 290°C.

[0093] (Sago palm: solid fuel H) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel H) when the raw material is sago palm are as follows.

[0094] The COD is preferably 2000 ppm or less, more preferably 1600 ppm or less, and even more preferably 800 ppm or less, and the COD ratio is preferably 0.85 or less, more preferably 0.60 or less, and even more preferably 0.4 or less.

[0095] The equilibrium moisture content after immersion in water is preferably 20 wt% to 35 wt%, more preferably 20 wt% to 33 wt%, and even more preferably 22 wt% to 30 wt%.

[0096] BET specific surface area is 0.15m 2 / g~0.35m 2 / g, and 0.18m 2 / g~0.33m 2 / g, more preferably 0.18m 2 / g~0.30m 2 / g is more preferred.

[0097] The HGI is preferably from 20 to 60, more preferably from 25 to 55, and even more preferably from 30 to 55. The HGI ratio is preferably from 1.0 to 2.5, more preferably from 1.3 to 2.3, and even more preferably from 1.5 to 2.2.

[0098] The fuel ratio is preferably 0.2 to 0.8, more preferably 0.25 to 0.8, and even more preferably 0.5 to 0.8.

[0099] The higher heating value on an anhydrous basis is preferably 4800 to 7000 kcal / kg, more preferably 4900 to 6500 kcal / kg, and even more preferably 5000 to 6000 kcal / kg.

[0100] The molar ratio O / C of oxygen O to carbon C is preferably from 0.20 to 0.65, more preferably from 0.20 to 0.60, and even more preferably from 0.2 to 0.55.

[0101] The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and even more preferably 0.85 to 1.2.

[0102] The preferable ranges for the properties of the solid fuel H have been described above.

[0103] When producing the solid fuel H, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 220 to 300°C, and even more preferably 240 to 290°C.

[0104] (EFB: Solid fuel I) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel I) when the raw material is EFB (empty fruit bunches, a residue from palm oil processing) are as follows.

[0105] The COD is preferably 2350 ppm or less, more preferably 2300 ppm or less, and even more preferably 2000 ppm or less, and the COD ratio is preferably 0.98 or less, more preferably 0.96 or less, and even more preferably 0.85 or less.

[0106] The equilibrium moisture content after immersion in water is preferably 23 wt% to 45 wt%, more preferably 20 wt% to 40 wt%, and even more preferably 20 wt% to 35 wt%.

[0107] BET specific surface area is 0.25m 2 / g~0.65m 2 / g, and 0.30m 2 / g~0.60m 2 / g, more preferably 0.35m 2 / g~0.55m 2 / g is more preferred.

[0108] The fuel ratio is preferably 0.25 to 0.8, more preferably 0.30 to 0.8, and even more preferably 0.36 to 0.8.

[0109] The higher heating value on an anhydrous basis is preferably 4800 to 7000 kcal / kg, more preferably 4900 to 7000 kcal / kg, and even more preferably 5000 to 7000 kcal / kg.

[0110] The molar ratio O / C of oxygen O to carbon C is preferably from 0.15 to 0.65, more preferably from 0.15 to 0.60, and even more preferably from 0.15 to 0.55.

[0111] The molar ratio H / C of hydrogen H to carbon C is preferably 0.5 to 1.3, more preferably 0.55 to 1.3, and even more preferably 0.6 to 1.2.

[0112] The preferable ranges for the properties of solid fuel I have been described above.

[0113] When producing the solid fuel I, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 220 to 300°C, and even more preferably 240 to 260°C.

[0114] (Meranti: Solid Fuel J) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel J) when the raw material is meranti are as follows.

[0115] The COD is preferably 330 ppm or less, more preferably 320 ppm or less, and even more preferably 300 ppm or less, and the COD ratio is preferably 0.98 or less, more preferably 0.95 or less, and even more preferably 0.90 or less.

[0116] The equilibrium moisture content after immersion in water is preferably 15 wt% to 30 wt%, more preferably 15 wt% to 27 wt%, and even more preferably 18 wt% to 25 wt%.

[0117] The fuel ratio is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, and even more preferably 0.2 to 0.45.

[0118] The higher heating value on an anhydrous basis is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6500 kcal / kg, and even more preferably 4800 to 6000 kcal / kg.

[0119] The molar ratio O / C of oxygen O to carbon C is preferably from 0.3 to 0.60, more preferably from 0.35 to 0.60, and even more preferably from 0.40 to 0.60.

[0120] The molar ratio H / C of hydrogen H to carbon C is preferably 0.9 to 1.2, more preferably 0.95 to 1.2, and even more preferably 1.0 to 1.2.

[0121] The preferable ranges for the properties of the solid fuel J have been described above.

[0122] When producing the solid fuel J, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 220 to 300°C, and even more preferably 230 to 290°C.

[0123] (Rubber tree: solid fuel K) In one embodiment of the present invention, the properties of a biomass solid fuel (hereinafter sometimes referred to as solid fuel K) when the raw material is rubber wood are as follows.

[0124] The fuel ratio is preferably 0.2 to 0.8, more preferably 0.2 to 0.7. The higher heating value on an anhydrous basis is preferably 4800 to 7000 kcal / kg.

[0125] The molar ratio O / C of oxygen O to carbon C is preferably 0.1 to 0.7, and the molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3.

[0126] The preferable ranges for the properties of the solid fuel K have been described above.

[0127] When producing the solid fuel K, the heating temperature in the heating step is preferably 200 to 350°C, more preferably 220 to 300°C, and even more preferably 230 to 290°C.

[0128] The present inventors have speculated that in a method for producing a biomass solid fuel, by performing a molding step followed by a heating step in which the unheated aggregates are heated, the connection or adhesion between the biomass powder particles is maintained using components derived from the raw material biomass without using a binder, and a highly water-resistant biomass solid fuel that does not disintegrate even when immersed in water can be produced.The present inventors' analysis has led to the following findings regarding the mechanism by which biomass solid fuel acquires water resistance.

[0129] The present inventors have analyzed the mechanism of water resistance of three types of biomass solid fuels produced by different methods, specifically, an unheated solid fuel made by molding pulverized biomass (White Pellet: hereinafter sometimes referred to as WP), and a solid fuel obtained by molding pulverized biomass and then heating it (Pelletizing Before Torrefaction: hereinafter sometimes referred to as PBT), by performing FT-IR analysis, GC-MS analysis, SEM observation, etc. Note that neither WP nor PBT uses a binder.

[0130] First, the acetone extracts of each solid fuel were analyzed using FT-IR. The results showed that the PBT obtained through the heating process had a lower content of hydrophilic COOH groups compared to unheated WP, ​​but a higher content of C=C bonds, suggesting that heating changes the chemical structure of the components that make up the biomass, making them hydrophobic.

[0131] Furthermore, GC-MS analysis of the acetone-extracted components of each solid fuel suggested that the thermal decomposition of terpenes, such as abietic acid and its derivatives (hereinafter referred to as "abietic acid, etc."), upon heating is involved in the water resistance of biomass solid fuels. Abietic acid, etc., is the main component of rosin found in pine and other trees.

[0132] Figure 18 shows a hypothetical mechanism for the development of solid crosslinks in PBT. In the case of PBT, as the temperature rises during the heating process following the molding process, the liquid resulting from the melting of abietic acid dissolves into the gaps between the pulverized biomass (hereinafter sometimes referred to as biomass powder) (the gaps between adjacent biomass powder particles that are compacted by molding after pulverization). Further evaporation and thermal decomposition of the abietic acid occur, and hydrophobic substances adhere to the gaps between the biomass powder particles, developing crosslinks (solid crosslinks). This allows the biomass powder particles to maintain their connection or adhesion with the abietic acid and other components derived from the raw biomass, without the need for a binder. This connection or adhesion between the biomass powder particles is thought to prevent water penetration and improve water resistance.

[0133] On the other hand, in the case of WP, biomass powder is simply molded without being heated, so there is no solid cross-linking between the biomass powder particles as in the case of PBT. As mentioned above, the surface of the raw biomass powder that makes up WP contains many hydrophilic COOH groups, allowing water to easily penetrate, which greatly widens the gaps between the particles, making the molded pellets, etc., more susceptible to collapse.

[0134] Furthermore, in the case of solid fuels molded after heating biomass powder (Pelletizing After Torrefaction: hereafter sometimes referred to as PAT), the surface of each individual biomass powder becomes hydrophobic due to the elution of abietic acid and other substances when heated, but because the biomass powder is crushed and molded only after it has become hydrophobic through heating, it is thought that cross-linking between the biomass powder particles does not occur as in PBT. Therefore, with PAT, which is heated before molding, water easily penetrates into the gaps between the compacted biomass powder particles, and it is thought that its water resistance is inferior to that of PBT.

[0135] Abietic acid or its derivatives have a melting point of approximately 139 to 142° C. and a boiling point of approximately 250° C. Therefore, it is presumed that when heated, abietic acid or the like melts near the melting point, causing liquid crosslinking, and that abietic acid or the like thermally decomposes near the boiling point, causing solid crosslinking.

[0136] Terpenes, including abietic acid, are generally found in biomass (Hokkaido Forest Products Research Institute Monthly Report No. 171, April 1966; Japan Wood Preservation Association, "Wood Preservation," Vol. 34-2 (2008), etc.). Although the content varies slightly depending on the type of biomass ("Utilization of Essential Oils," by Ohira Tatsuro, Japan Wood Research Society, 6th Research Subcommittee Report, p. 72, Table 1, Japan Wood Research Society, 1999, etc.), in the following <Examples A> to <Example I>, water resistance is observed when heated above 230°C (they do not disintegrate even after immersion in water, see Table 6), so it is thought that water resistance is imparted to biomass in general when heated to at least 230°C to 250°C or higher.

[0137] Figures 19 to 22 show the results of FT-IR analysis of the biomass solid fuel of the present invention. The raw material was Scots pine (Example B below). After crushing, the solid fuel (PBT) was formed into pellets and heated at 250°C. The same raw material was crushed, molded, and then unheated (WP) was also shown. The amount of COOH groups on the outer surface of the pellets (Figure 19) and at the center of the cross section (Figure 20) was WP > PBT, and the amount of C=C bonds was PBT > WP. Furthermore, the amount of COOH groups eluted in the acetone extract (Figure 21) was WP > PBT, indicating that PBT has fewer hydrophilic COOH groups. Furthermore, in the solid after acetone extraction (Figure 22), PBT had more C=C bonds than WP. This indicates that PBT has superior water resistance.

[0138] Figure 23 shows the results of GC-MS analysis of the acetone extract. As in Figures 19 to 22 above, the raw material was Scots pine from Example B. The raw material was a solid fuel (PBT) made by crushing and molding the pellets into pellets and heating them at 250°C, and an unheated sample (WP) was also used. As shown in Figure 23, the amount of abietic acid, a type of terpene, eluted into acetone in PBT was less than in WP, which is thought to indicate that abietic acid melted upon heating to form liquid crosslinks, and then solid crosslinks were formed by the evaporation of abietic acid, etc.

[0139] Furthermore, with PBT, the development of solid cross-linking improves the strength of the solid fuel, and it is thought that, similar to water resistance, heating to at least 230°C to 250°C or higher will provide good crushability (HGI and crushing speed, described below) and good handleability (pulverization test, described below) without the addition of a binder. Furthermore, as mentioned above, PBT reduces COD, and this is thought to be because heating volatilizes the tar components of the biomass feedstock, while at the same time the surface of the PBT solid fuel is coated with solidified abietic acid, etc., which further makes the solid fuel surface hydrophobic and inhibits the elution of tar components remaining in the biomass feedstock. [Example]

[0140] <Example A> (Examples A-1 to A-6) Biomass solid fuel A (PBT) was obtained by crushing and pulverizing the biomass, followed by a molding process and subsequent heating process. No binder was used in either process. The raw biomass was a mixture of 40% by weight of Douglas-fir, 58% by weight of Japanese larch, 1% by weight of Japanese cedar, and 1% by weight of Japanese cypress. In the molding process for each example, the biomass was molded into pellets with a diameter of 8 mm. In the heating process for each example, 4 kg of each raw material was placed in a φ600 mm electric batch furnace and heated at a heating rate of 2°C / min to the target temperature for each example (heating temperature in Table 1). Hereinafter, the target temperature and heating temperature refer to the same thing. In Examples A-1 to A-6, the target temperature (heating temperature) was not maintained (the same applies to Examples B to K below). The heating temperatures in the heating processes for Examples A-1 to A-6 and the properties of the biomass solid fuel A obtained after the heating process are shown in Table 1.

[0141] (Comparative example A) Comparative Example A is an unheated biomass solid fuel (WP) that has only been crushed, pulverized, and then molded, without undergoing a heating process. Comparative Example A also does not use a binder. The raw biomass is the same as in Example A-1. The properties of the solid fuel of Comparative Example A are also shown in Table 1.

[0142] In Table 1, as mentioned above, the HGI is based on JIS M 8801, and the higher the value, the better the grindability. Table 1 also shows the higher heating value (anhydrous basis), the fuel ratio calculated based on the proximate analysis value (air-dry basis), and the results of elemental analysis (air-dry basis) and the molar ratios of oxygen (O), carbon (C), and hydrogen (H) obtained based on these.

[0143] [Table 1]

[0144] The biomass solid fuels obtained in the above Examples and Comparative Examples were further analyzed as follows.

[0145] [COD] Figure 1 shows the correlation between the heating temperature in the heating process and the COD (chemical oxygen demand) and pH of the soaking water when the obtained biomass solid fuel is soaked in water (pH will be discussed later). The soaking water sample for COD measurement was prepared in accordance with the Environment Agency Notification No. 13 (a) of 1973, which stipulates the testing method for metals and other substances contained in industrial waste, and COD was analyzed according to JIS K0102 (2010)-17.

[0146] As can be seen from FIG. 1, the COD of Comparative Example A (WP: biomass solid fuel that was only molded and not subjected to a heating process) was a high value of approximately 1200 ppm. In contrast, the COD of the biomass solid fuel heated at 230°C or higher was 800 ppm or less, indicating low tar elution. Therefore, the biomass solid fuels of Examples A-1 to A-6 are shown to be fuels with low tar elution and excellent handleability even when stored outdoors. The COD of the biomass solid fuels of Examples A-1 to A-6 heated at 230°C or higher decreased as the heating temperature increased. This is presumed to indicate that the COD value decreased due to the volatilization of tar and other components associated with heating. Therefore, it is presumed that when the heating temperature is less than 230°C, i.e., even when the heating temperature is 150°C or higher but less than 230°C, the COD value will be lower than that of Comparative Example A.

[0147] [pH] The solid fuels of Examples A-1 to A-6 and Comparative Example A were immersed in a solid-liquid ratio of 1:3, and the pH was measured. Figure 1 shows that although the values ​​were slightly lower for Examples A-2 and A-3, the pH was generally around 6 for all Examples A-1 to A-6, and there was no particular change compared to Comparative Example A before heating. This shows that there is no particular problem with the pH of the wastewater discharged when Examples A-1 to A-6 are stored outdoors.

[0148] [Crushability] FIG. 2 is a diagram showing the correlation between the heating temperature in the heating step and the pulverizability (HGI) and pulverization speed (described later) of the obtained biomass solid fuel A for the biomass solid fuels of Comparative Example A and Examples A-1 to A-6.

[0149] As is clear from Table 1 and Figure 2, the properties of Examples A-1 to A-6 change upon heating, and the HGI (based on JIS M 8801) values ​​are higher than those of Comparative Example A (WP: briquetting, unheated biomass solid fuel). The HGI of ordinary coal (bituminous coal) is around 50, and the crushing characteristics of Examples A-1 to A-6 can be said to be better and closer to those of coal than those of Comparative Example A.

[0150] The grinding rate in Figure 2 was measured by measuring the weight of ground material per unit time (g / min) after grinding a 700cc sample in a ball mill and passing it through a 150μm sieve. The ball mill conformed to JIS M4002 and contained standard-grade ball bearings (43 balls, 36.5mm diameter, 67 balls, 24.4mm diameter, 10 balls, 19.1mm diameter, 71 balls, and 15.9mm diameter, 94 balls) specified in JIS B1501. Heating improved the grinding rate, with a particularly rapid increase at temperatures above 230°C. The elution and solidification of organic components such as tar during heating enhanced the grindability of biomass solid fuel A, resulting in an increased grinding rate. Therefore, it is presumed that even if the heating temperature in the heating step is 150°C or higher and lower than 230°C, the HGI and grinding speed are improved compared to the unheated Comparative Example A.

[0151] [Powdering test] Table 2 shows the cumulative percentage of particles that undersieve for biomass solid fuel A subjected to the pulverization test, and Figure 3 shows the particle size distribution. A pulverization test was conducted to evaluate the handling characteristics of the pellets. A 1 kg sample was placed in a plastic bag and dropped 20 times from a height of 8.6 m. A rotational strength test was then conducted based on JIS Z 8841 to measure the particle size distribution. The resulting particle size distribution is shown in Figure 3. A sample with a particle size distribution of 30 wt% or less of particles undersieve 2 mm and 15 wt% or less of particles undersieve 0.5 mm is considered to have a particle size that allows handling during transportation, storage, etc. Table 2 and Figure 3 show that the particle size of the samples after the rotational strength test became finer as the solid temperature increased, but all samples met the above-mentioned evaluation criteria, suggesting that they could be handled without any problems.

[0152] [Table 2]

[0153] [Underwater immersion] Table 3 and Figure 4 show the results of the water immersion test for biomass solid fuel A. The solid fuels of each example and comparative example were immersed in water, and after the specified time shown in Table 3 and Figure 4, they were removed, wiped clean, and the solid moisture content was measured. The solid fuel of comparative example A (WP) disintegrated upon immersion in water, making it impossible to measure the solid moisture content. In contrast, the moisture content of the solid fuel of example A-1 reached equilibrium approximately 10 hours after immersion, with an equilibrium moisture content of approximately 27 wt%. The moisture content of the solid fuel of example A-2 reached equilibrium approximately 100 hours after immersion, with an equilibrium moisture content of approximately 25 wt%. Examples A-3 to A-5 also reached equilibrium at a moisture content of approximately 23 wt% after approximately 100 hours. Example A-6 also reached equilibrium approximately 100 hours after immersion, with an equilibrium moisture content of approximately 28 wt% (the fluctuation was larger than that of examples A-3 to A-5, but this is thought to be due to variations in the raw materials). These results are thought to be due to the surface of the biomass solid fuel becoming hydrophobic due to the elution and solidification of organic components such as tar during heating. Examples A-1 to A-6 (PBT) show advantageous properties as solid fuels that are often stored outdoors.

[0154] [Table 3]

[0155] [Solid strength before and after immersion in water] (Rotation strength) Figure 5 shows the results of measuring the solid strength (based on JIS Z 8841 rotational strength test method) for Examples A-1 to A-6 and Comparative Example A before and after immersion in water. As mentioned above, Comparative Example A (WP) collapsed after immersion in water, making it impossible to measure the rotational strength after immersion. For Examples A-1 to A-6 (PBT), the surface moisture of the solid fuel that had reached equilibrium moisture was wiped off, and then it was dried in a constant temperature dryer at 35°C for 22 hours. The strength of Examples A-1 to A-6 (PBT) that underwent the heating process showed almost no decrease, and it can be said that they were less likely to powder than Comparative Example A (WP) before immersion in water, and that they maintained their handleability.

[0156] (mechanical durability) 6 shows the results of measuring the mechanical durability before and after immersion in water. For the solid fuels of Examples A-1 to A-6 and Comparative Example A, the mechanical durability DU was measured according to the following formula in accordance with American Agricultural Standard ASAE S 269.4 and German Industrial Standard DIN EN 15210-1: where m0 is the sample weight before the tumbling process, m1 is the weight of the sample on the sieve after the tumbling process, and a plate sieve with a circular hole diameter of 3.15 mm was used as the sieve.

[0157] DU=(m1 / m0)×100 As with rotational strength, the mechanical durability of Examples A-1 to A-6 (PBT) that underwent the heating process showed almost no decrease in strength, and they were less likely to powder compared to Comparative Example A (WP) before immersion in water, demonstrating that they could maintain their handling properties.

[0158] [Spontaneous combustion] The evaluation was based on the "Spontaneous Combustion Test" in the "United Nations Manual of Tests and Criteria: Regulations for the Carriage and Storage of Dangerous Goods by Ship, 16th Edition." Example A-2 biomass solid fuel (heating temperature 250°C) 1-2 cm 3 was dropped onto an inorganic heat insulating board from a height of 1m, and measurements were made six times to see if it ignited during the drop or within 5 minutes after the drop. No ignition occurred in any of the six tests, and Example A-2 (PBT) was determined not to fall under Packing Group I in the above-mentioned UN Manual of Tests and Criteria.

[0159] [Self-heating] As with spontaneous combustion, the evaluation was based on the "self-ignition test" in the "Regulations for the Transportation and Storage of Dangerous Goods by Ship, 16th Edition." A sample container (a stainless steel cube with a side length of 10 cm) was filled with Example A-2 biomass solid fuel (heated to 250°C), suspended inside a thermostatic chamber, and the temperature of the substance was measured continuously for 24 hours at 140°C. Substances that ignited or showed a temperature rise exceeding 200°C were deemed to be self-heating substances. A similar test was then conducted using a sample container with a side length of 2.5 cm to confirm the presence or absence of ignition or a temperature rise exceeding 60°C. Based on the test results, Example A-2 (PBT) was determined not to be a self-heating substance.

[0160] [Pore size distribution] (BET specific surface area) Figure 7 shows the results of measuring the BET specific surface area of ​​solid fuel A. For the solid fuels of Examples A-1 to A-6 and Comparative Example A, the BET specific surface area was determined using an automatic specific surface area / pore size distribution analyzer (BELSORP-min II, manufactured by BEL Japan Co., Ltd.) by cutting the samples into 2-6 mm pieces as a pretreatment and placing them in a container. The samples were then vacuum degassed at 100°C for 2 hours. Nitrogen gas was used as the adsorption gas. Figure 7 shows that the BET specific surface area increases with increasing heating temperature, indicating that pores develop with heating (pyrolysis).

[0161] (average pore diameter, total pore volume) Figure 8 shows the average pore diameter on the surface of solid fuel A, and Figure 9 shows the total pore volume. Both the average pore diameter and the total pore volume were measured using the same equipment as for the BET specific surface area. Note that "pores" here refer to pores with diameters of 2 nm to 100 nm. The average pore diameter decreases as the heating temperature increases from Example A-2 onwards, indicating that many small pores are being generated. This is thought to be due to the decomposition of cellulose.

[0162] [yield] 10 shows the yields (solid yield and heat yield) of biomass solid fuel A after the heating process. The solid yield is the weight ratio before and after heating, and the heat yield is the ratio of the calorific value before and after heating. As mentioned above, the target temperature (heating temperature) was not maintained in each example (the same applies to Examples B to K below).

[0163] The results of Examples A-1 to A-6 above demonstrate that the present invention makes it possible to obtain biomass solid fuel A (PBT) at low cost, with reduced COD, improved crushability, reduced water absorption, improved solid strength, and improved yield.

[0164] [Spontaneous heating] The spontaneous heating property of the solid fuel of Example A-2 was measured using the following method. 1 kg of sample was placed in a container, and the reactor was placed in a thermostatic bath at 80°C. Air was passed through the sample, and the O2, CO, and CO2 concentrations of the resulting gas were measured. The amounts of O2 adsorption, CO generation, and CO2 generation due to heating of the sample were calculated from the concentrations before and after heating, and the spontaneous heating index (SCI) was calculated using the following formula (1).

[0165] Spontaneous heating index (SCI) = {O2 adsorption amount * O2 adsorption heat * (1 / 100)} + {CO generation amount * (CO formation heat + (1 / 2) * H2O formation heat * H / C) * (1 / 100)} + {CO2 generation amount * (CO2 formation heat + (1 / 2) * H2O formation heat * H / C) * (1 / 100)} Formula (1)

[0166] The adsorption amount, generation amount, and H / C ratio for the solid fuel of Example A-2 are as follows:

[0167] O2 adsorption amount 0.42[ml / kg min] CO generation rate: 0.03 [ml / kg·min] CO2 generation rate: 0.02 [ml / kg·min] H / C (hydrogen to carbon molar ratio in the solid fuel of Example A-2) 1.28 [mol / mol] (see Table 1) The heat of adsorption and heat of formation used in formula (1) are as follows:

[0168] O2 adsorption heat 253 [kJ / mol] (same value as O2 adsorption heat to coal) Heat of CO formation 110.5[kJ / mol] Heat of H2O formation 285.83[kJ / mol] Heat of CO2 formation 393.5[kJ / mol] Based on the above, the SCI of the solid fuel in Example A-2 was calculated to be SCI = 1.3. Note that since the properties of the biomass solid fuel A of the present invention are similar to those of coal, the heat of O2 adsorption used was the same as the heat of adsorption to coal.

[0169] Using the same method for calculating the SCI for Example A-2, the SCI was also calculated for Examples A-1 to A-3, A-6, and Example A-2 after the powdering test (see Table 2 and Figure 3). The calculation results are shown in Figure 11. For comparison, Figure 11 also shows the SCI for bituminous coal in Table 4. Note that the horizontal axis in Figure 11 represents moisture content on arrival, and the SCI for bituminous coal in Figure 11 was calculated by adding moisture to the bituminous coal shown in Table 4 to prepare four samples with different moisture contents.

[0170] As shown in formula (1), the lower the SCI value, the lower the spontaneous heating tendency. Therefore, when Examples A-1 to A-3, A-6, and Example A-2 after the pulverization test (see Table 2 and Figure 3) were compared with bituminous coal, if the moisture content was similar, the biomass solid fuel A (PBT) of the present invention had a lower SCI (spontaneous heating tendency) than bituminous coal, and was at the same level as high-moisture bituminous coal. This means that the biomass solid fuel A (PBT) of the present invention can be said to be a good fuel with a reduced risk of ignition during handling.

[0171] [Table 4]

[0172] [Front photo] Figures 12 to 14 are cross-sectional SEM photographs of the solid fuel (PBT) in Example A-2 before and after immersion in water. Figure 12 is before immersion, Figure 13 is after 2 seconds of immersion, and Figure 14 is after 20 seconds of immersion. Similarly, Figures 15 to 17 are cross-sectional SEM photographs of Comparative Example A (WP) before and after immersion in water, with Figure 15 being before immersion, Figure 16 being after 2 seconds of immersion, and Figure 17 being after 20 seconds of immersion. Note that in both Example A-2 and Comparative Example A, the cross section after immersion refers to a cross section of the solid fuel cut after immersion for 2 or 20 seconds. The magnification and scale are also shown below each photograph.

[0173] Comparing the photographs before and after immersion in water, the pores in Comparative Example A (Figures 15 to 17) were enlarged after immersion in water. As mentioned above, Comparative Example A (WP) is a compact of pulverized biomass, and it is presumed that this is because the biomass absorbed water when immersed in water, causing the pores (gaps between the biomass powder particles) to enlarge. Therefore, it is thought that as more water penetrates into the enlarged pores, the pulverized biomass particles separate, causing the solid fuel itself to collapse (see Figure 4).

[0174] In contrast, the pores on the surface of the solid fuel in Example A-2 (Figures 12 to 14) did not expand significantly even after immersion in water, and there was little change due to immersion. In Example A-2, solid cross-linking developed between the biomass powders due to heating, improving hydrophobicity and making them less susceptible to water absorption, presumably resulting in little change due to immersion. Therefore, even after immersion, the connection or adhesion between the pulverized biomass particles due to solid cross-linking is maintained, and there is little collapse as in Comparative Example A. Therefore, in the solid fuels of Examples A-1 to A-6 (PBT) that were heated, as shown in Figure 4, biomass solid fuels were obtained that were less susceptible to collapse due to rainwater, etc., and were easy to handle when stored outdoors.

[0175] <Example B> In Examples B-1 to B-4 (PBT), the raw biomass was heated to the target temperature (heating temperature listed in Table 5) in the same manner as in Example A, except that Scots pine was used as the raw biomass. The properties of the biomass solid fuel B (Examples B-1 to B-4) obtained after the heating process are shown in Tables 5 and 6. The same is true for Comparative Example B (WP). As in Example A, no binder was used in Examples B-1 to B-4 and Comparative Example B. Since the moisture content after immersion in water was measured after immersion for 100 hours or more (168 hours in Example B), it is considered that the moisture content in solid fuel B had essentially reached equilibrium. The methods for measuring each property of the biomass solid fuel were the same as in Example A. The ball mill grindability listed in Table 6 was measured as follows.

[0176] [Ball mill grindability] The grinding time for each biomass solid fuel B was 20 minutes, and the weight ratio of the material passing through a 150 μm sieve after 20 minutes was taken as the grinding point. A ball mill conforming to JIS M4002 was used, and a cylindrical container with an inner diameter of 305 mm and an axial length of 305 mm was filled with standard-grade ball bearings specified in JIS B1501 (43 balls of 36.5 mm diameter, 67 balls of 30.2 mm diameter, 10 balls of 24.4 mm diameter, 71 balls of 19.1 mm diameter, and 94 balls of 15.9 mm diameter) was rotated at 70 rpm for measurement. A higher value indicates improved grindability. It was confirmed that the grinding point increased with increasing heating temperature.

[0177] Comparative Example B disintegrated immediately after immersion in water. In contrast, in Examples B-1, B-3, and B-4, the biomass powder particles maintained their connection or adhesion even after immersion in water (168 hours), and did not disintegrate. As a result, the solid shape was maintained even after immersion, making it possible to measure the moisture content, and the development of water resistance was confirmed. Furthermore, compared to Comparative Example B, the crushability was improved and the COD was reduced. From the perspective of water resistance (moisture content after immersion), Example B-3 was particularly excellent, and from the perspective of yield, the biomass solid fuels of Examples B-2 and B-3 showed particularly excellent physical properties.

[0178] Also, it is estimated that Example B-2 is a fuel that has excellent water resistance and crushability due to the development of solid cross-links, and also has reduced COD.

[0179] <Example C> Except that old almond trees were used as the raw biomass, the temperature was raised to the target temperature (heating temperature listed in Table 5) and heated in the same manner as in Example A (Examples C-1 to C-4: PBT). Ball mill grindability was measured in the same manner as in Example B above. The properties of the biomass solid fuel C obtained after the heating step are shown in Tables 5 and 6. As in Example B, the moisture content after immersion in water is considered to be in equilibrium because it was immersed for more than 100 hours (168 hours in Example C). The same is shown for Comparative Example C (WP). Note that no binder was used in Examples C-1 to C-4 and Comparative Example C.

[0180] Comparative Example C disintegrated immediately after immersion in water. In contrast, in Examples C-1 to C-4, the biomass powder particles maintained their connection or adhesion even after immersion in water, and did not disintegrate, resulting in improved water resistance. Also shown are improved grindability and reduced COD. From the perspective of COD and water resistance (moisture content after immersion), Examples C-2, C-3, and C-4 are superior, while from the perspective of heat yield, Examples C-1, C-2, and C-3 are superior. The HGI of Example C-1 is lower than that of Comparative Example C, but this is thought to be due to variations in the raw materials and measurement errors. It is estimated that Example C-1 has an HGI at least equal to or higher than that of Comparative Example C.

[0181] <Example D> The raw biomass was (30 wt% almond shells + 70 wt% old almond wood), and the temperature was raised to the target temperature (heating temperature listed in Table 5) and heated in the same manner as in Example A (Examples D-1 to D-4: PBT). Ball mill grindability was measured in the same manner as in Example B above. The properties of biomass solid fuel D obtained after the heating process are shown in Tables 5 and 6. The moisture content after immersion in water was considered to be equilibrated after immersion for 100 hours or more (168 hours in the case of Example D). The same is shown for Comparative Example D (WP). Note that no binder was used in Examples D-1 to D-4 and Comparative Example D.

[0182] Comparative Example D disintegrated immediately after immersion in water. In contrast, in Examples D-1 to D-4, the biomass powder particles maintained their connection or adhesion even after immersion in water, so they did not disintegrate and exhibited improved water resistance. They also exhibited improved pulverizability and reduced COD. From the perspective of COD, Examples D-2, D-3, and D-4 were superior, and from the perspective of heat yield, Examples D-1, D-2, and D-3 exhibited particularly excellent physical properties.

[0183] <Example E> Acacia wood was used as the raw biomass, and the biomass was molded into tablets. The procedure for heating was the same as in Example A, except that a 70 mm diameter tubular furnace was used as the heating device. The temperature was raised to the target temperature (the heating temperature listed in Table 5) and heated (Examples E-1 to E-3: PBT). The properties of the biomass solid fuel E obtained after the heating process are shown in Tables 5 and 6. The moisture content after immersion in water was considered to be equilibrated after immersion for 100 hours or more (168 hours for Example E). The same is true for Comparative Example E (WP). Note that no binder was used in Examples E-1 to E-3 and Comparative Example E. In Example E, the pH was measured by immersing the solid fuel at a solid-liquid ratio of 1:13. The immersion time for Comparative Example E in Table 6 refers to the time at which the pH was measured, i.e., the pH was measured 96 hours after immersion for Comparative Example E.

[0184] Comparative Example E collapsed immediately after immersion in water, but Examples E-1 to E-3 maintained the connection or adhesion between the biomass powder particles and showed water resistance without collapse. From the viewpoint of water resistance (moisture content after immersion in water), Examples E-2 and E-3 are superior, while Examples E-1 and E-2 are superior from the viewpoint of thermal yield. It is estimated that the above-mentioned solid crosslinking was also formed in the PBT heated at 240 to 270°C in Example E, and it is considered that the water resistance, COD, pulverizability, etc. are excellent. Furthermore, although the thermal yield of Example E-1 exceeds 100%, this is due to variations in the raw materials and measurement errors.

[0185] <Example F> Except for using acacia bark as the raw biomass, the temperature was raised to the target temperature (heating temperature listed in Table 5) and heated in the same manner as in Example E (Examples F-1 to F-4: PBT). The properties of the biomass solid fuel F obtained after the heating process are shown in Tables 5 and 6. The moisture content after immersion in water was considered to be equilibrated after immersion for 100 hours or more (168 hours or more in Example F). The same is shown for Comparative Example F (WP). Note that no binder was used in any of Examples F-1 to F-4 and Comparative Example F. In Example F, the pH was measured by immersing the solid fuel at a solid-liquid ratio of 1:13. Here, the immersion time for Comparative Example F in Table 6 indicates the time at which the pH was measured, i.e., the pH was measured 96 hours after immersion of Comparative Example F.

[0186] Comparative Example F collapsed within 1 hour after immersion in water, but Examples F-1 to F-4 maintained the connection or adhesion between the biomass powder particles and exhibited water resistance without collapse. From the viewpoints of COD and water resistance (moisture content after immersion in water), Examples F-2, F-3, and F-4 are superior, and from the viewpoint of heat yield, Examples F-1, F-2, and F-3 are superior.

[0187] <Example G> The raw biomass was (70 wt% almond shells + 30 wt% walnut shells) and the heating device was a 70 mm diameter tubular furnace. The temperature was raised to the target temperature (heating temperature listed in Table 5) and heated in the same manner as in Example A (Examples G-1 to G-4: PBT). The properties of the biomass solid fuel G obtained after the heating process are shown in Tables 5 and 6. The moisture content after immersion in water was after immersion for 100 hours or more (144 hours or more in Example G), and was considered to be in equilibrium. The same is true for Comparative Example G (WP). Note that no binder was used in Examples G-1 to G-4 and Comparative Example G.

[0188] Comparative Example G collapsed immediately after immersion in water, but Examples G-1 to G-4 maintained the connection or adhesion between the biomass powder particles and showed water resistance without collapse. From the viewpoints of COD and water resistance (moisture content after immersion in water), Examples G-2, G-3, and G-4 are superior, while from the viewpoint of heat yield, Examples G-1, G-2, and G-3 are superior. Although the heat yield of Example G-2 exceeds 100%, this is due to variations in the raw materials and measurement errors.

[0189] <Example H> Except for using sago palm as the raw biomass, the temperature was raised to the target temperature (heating temperature listed in Table 5) and heated in the same manner as in Example A (Examples H-1 to H-4: PBT). Ball mill grindability was measured in the same manner as in Example B above. The properties of the biomass solid fuel H obtained after the heating step are shown in Tables 5 and 6. The moisture content after immersion in water was after immersion for 100 hours or more (168 hours in the case of Example H), and was considered to have reached equilibrium. The same is shown for Comparative Example H (WP). Note that no binder was used in any of Examples H-1 to H-4 and Comparative Example H. The immersion time for Comparative Example H in Table 6 indicates the time at which the pH was measured, i.e., the pH was measured 24 hours after immersion of Comparative Example H.

[0190] Comparative Example H collapsed after immersion in water for 3 hours, but Examples H-1 to H-4 maintained the connection or adhesion between the biomass powder particles and showed water resistance without collapse. From the viewpoints of COD, pH (slightly low), and water resistance (moisture content after immersion in water), Examples H-2, H-3, and H-4 are superior, and from the viewpoint of heat yield, Examples H-1, H-2, and H-3 are superior.

[0191] <Example I> Except for using EFB (empty fruit bunches, a residue from palm oil processing) as the raw biomass, the temperature was raised to the target temperature (heating temperature listed in Table 5) and heated in the same manner as in Example A (Examples I-1 to I-4: PBT). The properties of the biomass solid fuel I obtained after the heating step are shown in Tables 5 and 6. The moisture content after immersion in water is considered to be equilibrium after immersion for 100 hours or more (168 hours in Example I). The same is true for Comparative Example I (WP). Note that no binder was used in Examples I-1 to I-4 and Comparative Example I.

[0192] The mechanical durability of Example I-3 heated at 270°C and Example I-4 heated at 300°C before and after immersion in water was measured using the following method. 50 g of sample was placed in a 1,000 cc polypropylene container and rotated at 60 rpm for 30 minutes (1,800 rotations in total) using a MISUGI Mazemazeman SKH-15DT. After rotation, the sample was sieved using a sieve with a circular hole diameter of 3.15 mm, and the weight of the sample was measured using the following formula: DU=(m1 / m0)×100 The mechanical durability (DU) was calculated by the following formula: where m0 is the weight of the sample before the rotation treatment, and m1 is the weight of the sample on the sieve after the rotation treatment.

[0193] Comparative Example I collapsed immediately after immersion in water, but Examples I-1 to I-4 maintained the connection or adhesion between the biomass powder particles and exhibited water resistance without collapse. From the viewpoints of COD and water resistance (moisture content after immersion in water), Examples I-2, I-3, and I-4 are superior, and from the viewpoint of heat yield, Examples I-1, I-2, and I-3 are superior.

[0194] <Example J> Except for using Meranti as the raw biomass, the temperature was raised to the target temperature (heating temperature listed in Table 5) and heated in the same manner as in Example A (Examples J-1 and J-2: PBT). The properties of the biomass solid fuel J obtained after the heating process are shown in Tables 5 and 6. The moisture content after immersion in water is after immersion for more than 100 hours (168 hours in the case of Example J), ​​and is considered to be in equilibrium. The same is shown for Comparative Example J (WP). Note that no binder was used in Examples J-1, J-2, and Comparative Example J.

[0195] Comparative Example J disintegrated immediately after immersion in water, but Examples J-1 and J-2 maintained the connection or adhesion between the biomass powder particles and exhibited water resistance without disintegrating. Excellent results were also shown for COD.

[0196] <Example K> The raw material biomass was rubber wood, and a 70 mm diameter tubular furnace was used as the heating device. The temperature was raised to the target temperature (heating temperature listed in Table 5) in the same manner as in Example A (Example K-1). The properties of the biomass solid fuel K obtained after the heating process are shown in Table 5. The same is true for Comparative Example K (WP). No binder was used in either case.

[0197] Comparative Example K is also expected to disintegrate when immersed in water, as with the other examples. On the other hand, Example K-1 does not disintegrate when immersed in water due to the formation of the solid crosslinks, and is expected to have improved water resistance and crushability, reduced COD, etc. Example K-1 was heated at 270°C, but similar effects are expected for heating temperatures of 230 to 270°C, as described above.

[0198] [Table 5]

[0199] [Table 6]

[0200] <Water absorption distribution> To compare the water resistance of PAT and PBT, we examined the sodium distribution in these biomass solid fuels after water absorption using saline solution. The PAT sample was a solid fuel made by heating Scots pine (Scots pine) at 250°C and molding it into 6-mm-diameter pellets. The PBT sample was a solid fuel (solid fuel B) made by molding Scots pine (Scots pine) into 6-mm-diameter pellets and heating it at 250°C. PBT and PAT were immersed in 0.9 wt% saline for 5 days. As shown in Figure 24, the PBT pellets maintained their shape (left side of Figure 24), while the PAT pellets were significantly disintegrated (right side of Figure 24). Furthermore, cross-sections of the PAT and PBT samples were analyzed using an Electron Probe MicroAnalyzer (EPMA) before and after immersion in saline for 5 days to compare the sodium distribution. With regard to the distribution of sodium, with PBT it remained on the pellet surface and did not penetrate into the interior, whereas with PAT it was widely distributed throughout the interior (see Figure 25). This means that PBT allowed less saline to penetrate than PAT. From these results, it can be inferred that with PBT the gaps between adjacent biomass powder particles are solidified and cross-linked by the pyrolysis products of the extracted components, making them hydrophobic and preventing water from penetrating, whereas with PAT water is able to penetrate into the gaps between the biomass powder particles and penetrate into the pellet, widening the gaps between the biomass powder particles and resulting in collapse.

[0201] [Expansion rate before and after immersion in water] The pellet lengths of the solid fuels of Examples A-1 and A-3 were measured before and after immersion in water. Ten pellets were selected before immersion and measured with an electronic caliper (Mitutoyo CD-15CX, repeatability 0.01 mm, rounded to two decimal points). The same pellets were then immersed in water for 72 hours, after which their lengths were measured again with the electronic caliper. If the pellet end was angled before or after immersion, the length was measured from the very tip. The measurement results are shown in Table 7. As shown in Table 7, the pellet length of Example A-1 increased by an average of 4.6%, and that of Example A-3 increased by an average of 0.2%.

[0202] [Table 7]

[0203] Furthermore, for the solid fuels of Examples A-1 to A-6, the pellet diameters were measured before and after immersion using the same electronic calipers and measurement method as in Table 7. The measurement results are shown in Table 8. The measured pellet diameters are the average values ​​of 10 pellets randomly selected in each of Examples A-1 to A-6.

[0204] [Table 8]

[0205] Tables 7 and 8 show that the higher the temperature in the heating process, the lower the expansion rate. It is presumed that expansion is suppressed by the formation of solid crosslinks during heating. The diameter expansion rate in Table 8 is higher than the length expansion rate in Table 7. This is thought to be because the immersion time in Table 7 is longer and because Example A is in the form of pellets, it is primarily compacted in the radial direction, resulting in greater expansion in the radial direction. In Table 8, even Example A-1, which has the highest diameter expansion rate, only achieves an expansion rate of 10% or less. In Example A, the diameter and length expansion rates are preferably 10% or less, and more preferably 7% or less. The volume expansion rate is preferably 133% or less, and more preferably 123% or less.

[0206] The expansion coefficients of Example A are shown in Tables 7 and 8 above, but the expansion coefficients of Examples B to J are calculated based on Table 6. As in Example A, the expansion coefficients were calculated using the following formula (2).

[0207] Expansion rate = {(value after immersion - value before immersion) / value before immersion} × 100 (2)

[0208] Example B is a pellet, and the radial expansion rate calculated based on formula (2) using the pellet diameter before immersion (initial dimension in Table 6) and the pellet diameter after immersion (dimension after immersion in Table 6) was 15% or less (hereinafter, formula (2) will be used for the radial expansion rate in Examples B and later). As in Example A, it is estimated that the length expansion rate of pellets is less than the radial expansion rate. Therefore, assuming that the length expansion rate of Example B is also 15% or less at most, the volume expansion rate is calculated to be 152% or less (volume after immersion relative to 100% volume before immersion; the same applies to Examples C and later). In Example B, the radial expansion rate is preferably 20% or less, and more preferably 10% or less. The volume expansion rate is preferably 173% or less, and more preferably 133% or less.

[0209] Example C is also a pellet, and assuming that the radial expansion rate before and after immersion is 7.2% or less and the length expansion rate is also a maximum of 7.2%, the volume expansion rate is 123% or less (the volume expansion rate is calculated in the same way for the pellet examples below). The radial expansion rate in Example C is preferably 13% or less, more preferably 7% or less. The volume expansion rate is preferably 144% or less, more preferably 123% or less.

[0210] For Example D (pellets), the radial expansion rate before and after immersion is 8.8% or less, and the volume expansion rate based on this is 129% or less. The radial expansion rate in Example D is preferably 10% or less, more preferably 8% or less. The volume expansion rate is preferably 133% or less, more preferably 126% or less.

[0211] Example E is in the form of a tablet, and has a diameter (φ) expansion rate of 2.5% or less, a height (H) expansion rate of 40% or less, and a volume expansion rate of 147% or less. The diameter expansion rate is preferably 5% or less, more preferably 2.3% or less. The height expansion rate is preferably 50% or less, more preferably 20% or less. The volume expansion rate is preferably 165% or less, more preferably 126% or less.

[0212] For Example F (tablet), the diameter expansion rate is 4.0% or less, the height expansion rate is 15% or less, and the volume expansion rate is 124% or less. Note that the height after immersion in Example F-3 is considered to be due to measurement error or individual variation. The diameter expansion rate is preferably 5% or less, more preferably 3% or less. The height expansion rate is preferably 40% or less, more preferably 10% or less. The volume expansion rate is preferably 154% or less, more preferably 117% or less.

[0213] For Example G (pellets), the diameter expansion rate before and after immersion was 8.8% or less, and the volume expansion rate based on this was 129% or less. The diameter expansion rate is preferably 10% or less, more preferably 8% or less. The volume expansion rate is preferably 133% or less, more preferably 126% or less.

[0214] For Example H (pellets), the radial expansion rate before and after immersion was 6.9% or less, and the volume expansion rate based on this was 122% or less. The radial expansion rate is preferably 10% or less, and more preferably 7% or less. The volume expansion rate is preferably 133% or less, and more preferably 123% or less.

[0215] For Example I (pellets), the diameter expansion rate before and after immersion was 4.1% or less, and the volume expansion rate based on this was 113% or less. The diameter expansion rate is preferably 10% or less, more preferably 5% or less. The volume expansion rate is preferably 133% or less, more preferably 116% or less.

[0216] For Example J (pellets), the diameter expansion rate before and after immersion was 5.4% or less, and the volume expansion rate based on this was 117% or less. The diameter expansion rate is preferably 20% or less, more preferably 10% or less. The volume expansion rate is preferably 173% or less, more preferably 133% or less.

[0217] As described above, the solid fuel (PBT) of the present invention, which is made from biomass as a raw material, preferably has a length (including diameter and height) expansion rate of 40% or less before and after immersion, and a volume expansion rate of approximately 275% or less. It is more preferable that the diameter and length expansion rates are 30% or less, and the volume expansion rate is approximately 220% or less. It is even more preferable that the diameter and length expansion rates are 20% or less, and the volume expansion rate is approximately 173% or less. It is even more preferable that the diameter and length expansion rates are 10% or less, and the volume expansion rate is approximately 133% or less. Since the expansion rate after immersion in water is within a certain range, the biomass solid fuel (PBT) of the present invention does not collapse even when immersed, demonstrating that it is water resistant.

Claims

1. A biomass solid fuel obtained by molding biomass powder having a particle size of 100 to 3000 μm (however, this does not include biomass powder obtained by steam explosion of biomass) into unheated aggregates, and heating the unheated aggregates, After immersion in water for 24 hours, the biomass powders maintained their connections with each other, and Does not contain a binder, and A biomass solid fuel that satisfies any one of the following conditions (a2) to (j2): Condition (a2): The biomass powder is made from a mixture of Douglas-fir, Douglas-fir, Japanese cedar, and Japanese cypress, and when the biomass solid fuel is immersed in water, the COD (chemical oxygen demand) of the immersion water is 800 ppm or less, and the diameter expansion rate after immersion in water is 7.7% or less; Condition (b2): The biomass powder is made from Scots pine, and when the biomass solid fuel is immersed in water, the COD of the immersion water is 42 ppm or more and 710 ppm or less, and the diameter expansion rate after immersion in water is 15% or less; Condition (c2): The biomass powder is made from old almond trees, and when the biomass solid fuel is immersed in water, the COD of the immersion water is 210 ppm or more and 1900 ppm or less, and the radial expansion coefficient after immersion in water is 60 / 8.3 (%) or less; Condition (d2): The biomass powder is made from a mixture of almond shells and old almond trees, and when the biomass solid fuel is immersed in water, the COD of the immersion water is 150 ppm or more and 1900 ppm or less, and the radial expansion coefficient after immersion in water is 8.75% or less; Condition (e2): The biomass powder is made from acacia wood, and when the biomass solid fuel is immersed in water, the COD of the immersion water is 300 ppm or more and 810 ppm or less, and the radial expansion coefficient after immersion in water is 50 / 20.2 (%) or less; Condition (f2): The biomass powder is made from acacia bark as a raw material, and when the biomass solid fuel is immersed in water, the COD of the immersion water is 270 ppm or more and 1600 ppm or less, and the diameter expansion coefficient after immersion in water is 80 / 19.9 (%) or less; Condition (g2): The biomass powder is made from a mixture of almond shells and walnut shells, and when the biomass solid fuel is immersed in water, the COD of the immersion water is 510 ppm or more and 1800 ppm or less, and the diameter expansion coefficient after immersion in water is 8.75% or less; Condition (h2): The biomass powder is made from sago palm as a raw material, and when the biomass solid fuel is immersed in water, the COD of the immersion water is 130 ppm or more and 1,300 ppm or less, and the diameter expansion coefficient after immersion in water is 50 / 7.2 (%) or less; Condition (i2): The biomass powder is made from EFB (empty fruit bunches left over from palm oil processing) as a raw material, and the COD of the immersion water obtained when the biomass solid fuel is immersed in water is 200 ppm or more and 2300 ppm or less, and the diameter expansion rate after immersion in water is 30 / 7.4 (%) or less; Condition (j2): The biomass powder is made from Meranti, and when the biomass solid fuel is immersed in water, the COD of the immersion water is 170 ppm or more and 260 ppm or less, and the diameter expansion coefficient after immersion in water is 40 / 7.4 (%) or less.

2. The biomass solid fuel according to claim 1 , wherein the unheated aggregates have a bulk density of 0.47 kg / L or more.

3. BET specific surface area: 0.15 to 0.8 m ２ The biomass solid fuel according to claim 1 or 2, wherein the carbon content is 1 / g.

4. A biomass solid fuel obtained by heating the unheated aggregates, The biomass solid fuel according to any one of claims 1 to 3, which satisfies any one of the following conditions (b4) to (j4): Condition (b4): The condition (b2) is satisfied, and the COD of the immersion water after immersion in water is 560 ppm or more; Condition (c4): The condition (c2) is satisfied, and the COD of the immersion water after immersion in water is 630 ppm or more; Condition (d4): The condition (d2) is satisfied, and the COD of the immersion water after immersion in water is 480 ppm or more; Condition (e4): The condition (e2) is satisfied, and the COD of the immersion water after immersion in water is 540 ppm or more; Condition (f4): The condition (f2) is satisfied, and the COD of the immersion water when immersed in water is 480 ppm or more; Condition (g4): The condition (g2) is satisfied, and the COD of the immersion water when immersed in water is 1100 ppm or more; Condition (h4): The condition (h2) is satisfied, and the COD of the immersion water after immersion in water is 310 ppm or more; Condition (i4): The condition (i2) is satisfied, and the COD of the immersion water when immersed in water is 740 ppm or more; Condition (j4): The condition (j2) is satisfied, and the COD of the immersion water when immersed in water is 170 ppm or more.

5. The biomass solid fuel according to any one of claims 1 to 4, which satisfies any one of the following conditions (a5) to (i5): Condition (a5): The condition (a2) is satisfied and the BET specific surface area is 0.25 to 0.8 m ２ / g; Condition (b5): The condition (b2) is satisfied, and the BET specific surface area is 0.30 to 0.7 m ２ / g; Condition (c5): The condition (c2) is satisfied, and the BET specific surface area is 0.20 to 0.70 m ２ / g; Condition (d5): The condition (d2) is satisfied, and the BET specific surface area is 0.20 to 0.70 m ２ / g; Condition (e5): The condition (e2) is satisfied, and the BET specific surface area is 0.40 to 0.709 m ２ / g; Condition (f5): The condition (f2) is satisfied, and the BET specific surface area is 0.35 to 0.55 m ２ / g; Condition (g5): The condition (g2) is satisfied, and the BET specific surface area is 0.15 to 0.35 m ２ / g; Condition (h5): The condition (h2) is satisfied, and the BET specific surface area is 0.15 to 0.35 m ２ / g; Condition (i5): The condition (i2) is satisfied, and the BET specific surface area is 0.25 to 0.65 m ２ / g.

6. The biomass solid fuel according to any one of claims 1 to 5, which satisfies any one of the following conditions (a6) to (i6): Condition (a6): The biomass powder satisfies condition (a2) and has a BET specific surface area of ​​0.32 to 0.5 m ２ / g; Condition (b6): The biomass powder satisfies condition (b2) and has a BET specific surface area of ​​0.374 to 0.558 m ２ / g; Condition (c6): The biomass powder satisfies condition (c2) and has a BET specific surface area of ​​0.261 to 0.628 m ２ / g; Condition (d6): The biomass powder satisfies condition (d2) and has a BET specific surface area of ​​0.320 to 0.672 m ２ / g; Condition (e6): The biomass powder satisfies condition (e2) and has a BET specific surface area of ​​0.567 to 0.709 m ２ / g; Condition (f6): The biomass powder satisfies condition (f2) and has a BET specific surface area of ​​0.442 to 0.462 m ２ / g; Condition (g6): The biomass powder satisfies condition (g2) and has a BET specific surface area of ​​0.228 to 0.284 m ２ / g; Condition (h6): The biomass powder satisfies condition (h2) and has a BET specific surface area of ​​0.191 to 0.276 m ２ / g; Condition (i6): The biomass powder satisfies condition (i2) and has a BET specific surface area of ​​0.374 to 0.521 m ２ / g.

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