RU2746733C2 - Carbonized biomass cooling equipment - Google Patents

Abstract

FIELD: biomass.SUBSTANCE: invention relates to a device for composite sheet production. Carbonized biomass cooling equipment contains a carbonation furnace designed to produce carbonized biomass as a result of carbonation of molded biomass, a device for sorting by size, located downstream from the carbonation furnace and designed for sorting carbonized biomass by size, and a cooling device located downstream from the device for sorting by size and intended for cooling the sorted by size carbonized biomass, in which the molded biomass is obtained by molding the powdered biomass from the feedstock without a binder, and the cooling device provides cooling of the carbonized biomass as a result of spraying water on it.EFFECT: invention provides for efficient production of a composite sheet, which includes fused parts having through holes, with the low maintenance device.6 cl, 28 dwg, 10 tbl, 11 ex

Description

The technical field to which the invention relates

The invention relates to an apparatus for cooling carbonated biomass.

State of the art

Typically, as disclosed in JP No. 4088933, a biocoke excellent in strength is obtained by pressure-molding pulverized biomass while heating it to effect semi-carbonization.

Disclosure of invention

Technical problem

However, in JP No. 4088933, there is a problem that the cooling efficiency is low due to the cooling of the product after molding in the pressurized state and the natural cooling in air. Even in the case of attempting to use water cooling to improve the cooling efficiency, water cooling under pressure will be difficult, and the water cooling will cause a part of the biocoke, which is a molded product of pulverized biomass, to break down, making the product difficult to handle. In particular, in the non-stationary state, in which no heating is carried out, there is a risk of possible decomposition of the molded biocoke, which leads to clogging in the production plant. Alternatively, if, for simplicity, cooling is carried out by placing the biocoke in a bath of water and the like after carbonization (heating), the collection process will become complicated due to the flotation of the solid biomass fuel due to its low relative density.

The present invention has been made to solve the above problems, and one object of the present invention is to improve the cooling efficiency of the semi-carbonated molded biomass while reducing plugging in the production plant.

Solution of a problem

The present invention includes a carbonization furnace for producing carbonated biomass by carbonizing molded biomass; a sizing device downstream of the carbonization furnace for sizing carbonated biomass; and a cooling device downstream of the screener for cooling the sized carbonated biomass; where the molded biomass is obtained by molding the pulverized biomass of the feedstock, and the cooling device provides cooling of the carbonated biomass by spraying water thereon.

The beneficial effect of the invention

In accordance with the present invention, it is proposed to improve the cooling efficiency of the semi-carbonated molded biomass while reducing clogging in the production plant.

Brief Description of Drawings

FIG. 1 is a graph showing COD and pH values versus solid temperature of biomass solid fuels.

FIG. 2 is a graph showing the correlation between the temperature of the solid during the heating step and the grindability index and pulverization rate for the obtained solid biomass fuels.

FIG. 3 is a graph showing particle size distribution for solid biomass fuels subjected to degradation testing.

FIG. 4 is a graph showing the results of a water immersion test (solid moisture content) for solid biomass fuels.

FIG. 5 is a graph showing solid strength (rotational strength) before and after a water immersion test.

FIG. 6 is a graph showing solid strength (mechanical resistance) before and after a water immersion test.

FIG. 7 is a graph showing the BET specific surface area of solid fuels.

FIG. 8 is a graph showing the average pore diameter for the surface of solid fuels.

FIG. 9 is a graph showing the cumulative pore volume for the surface of solid fuels.

FIG. 10 is a graph showing the yield of biomass solid fuels.

FIG. 11 is a graph showing the spontaneous combustion index (SPI) of biomass solid fuels.

FIG. 12 is a cross-sectional photograph before immersion in water in Example A-2.

FIG. 13 is a cross-sectional photograph after immersion in water (2 seconds) in Example A-2.

FIG. 14 is a cross-sectional photograph after immersion in water (20 seconds) in Example A-2.

FIG. 15 is a cross-sectional photograph before immersion in water of Comparative Example A.

FIG. 16 is a cross-sectional photograph after immersion in water (2 seconds) in Comparative Example A.

FIG. 17 is a cross-sectional photograph after immersion in water (20 seconds) in Comparative Example A.

FIG. 18 is a diagram showing the (estimated) mechanism for the development of solid state crosslinking in a gas turbine material.

FIG. 19 is an illustration showing the analysis results using the IR-PF method for the outer surface of pellets of solid biomass fuels.

FIG. 20 is an illustration showing the analysis results using the IR-PF method for the cross-section of the center of pellets of solid biomass fuels.

FIG. 21 is an illustration showing the analysis results using the IR-PF method for an acetone extract solution of solid fuels based on biomass.

FIG. 22 is an illustration showing the analysis results using the IR-PF method for solid biomass solid fuels after an acetone extract was prepared.

FIG. 23 is an illustration showing GC-MS analysis results for an acetone extract of biomass solid fuels.

FIG. 24 is a photograph showing the shape of the bead after immersion in physiological saline solution in Example B.

FIG. 25 is a graph showing the distribution of sodium before and after immersion in physiological saline solution in Example B.

FIG. 26A is a schematic diagram showing a production plant for cooling carbonated biomass.

FIG. 26B is a schematic diagram showing another example of a production plant for cooling carbonated biomass.

FIG. 27 is a diagram showing the process flow of the present invention.

FIG. 28 is a diagram showing a control flow.

Implementation of the invention

FIG. 26A is a schematic diagram of the present invention, and FIG. 27 is a flowchart of manufacturing operations. The solid biomass fuel obtained from the fuel fabrication step 100 in FIG. 27 becomes a product using a 200 screening step and a 300 cooling step.

In the fuel manufacturing step, biomass-based solid fuel is produced using a known method. The feedstock biomass is molded in a molding step 120 after a crushing-pulverizing step 110, then the molded biomass is heated using the kiln 1 in FIG. 26A in the heating step 130. In the shaping step 120, no binder such as a binder is added and the powdered biomass particles are simply squeezed or compressed to be molded.

The unheated molded biomass right after the molding step 120 (white granules: hereinafter referred to as BG) has low strength due to it being obtained by simply pressing and shaping the pulverized biomass, so it tends to degrade easily during handling. In addition, it expands and disintegrates as a result of the absorption of water.

In the fuel manufacturing step 100 of the present invention, by heating the molded biomass in the range of 150 to 400 ° C (low temperature carbonization) in the heating step 130 (calcining furnace 1), a solid biomass fuel is produced (pelletizing before torrefaction: hereinafter referred to as HDT), characterized by high strength and water resistance, while maintaining its shape in the form of a molded product. Details for the fuel fabrication step 100 will be described below.

The screening step 200 and the cooling step 300 are carried out using the vibrating conveyor 2 shown in FIG. 26A. The vibrating conveyor 2 is divided into two sections using a dividing plate 24, where one of the sections is the screening section 21 and the other is the cooling section 22. The material of the gas turbine engine discharged from the kiln 1 is transported as a result of the vibration of the flat plate 22b and as a result of being pushed out by the material of the gas turbine which is continuously supplied from the kiln 1. The material of the gas turbine is discharged as a product using the screening section 21 and the cooling section 22. Despite the inclination of the vibratory conveyor 2 in FIG. 26A, a horizontal device that is not inclined may be used.

Sizing of the HDM material and fine powder (screening step 200) is carried out by vibrating the HDM material on the screen 21a in the screening section 21. The hole size of the screen 21a can be changed according to the desired value. The gas turbine material that has disintegrated during manufacture, or the gas turbine material smaller than the predetermined size, falls out of the sieve 21a and is processed in a different technological process. The material of the gas turbine engine remaining on the sieve is transported to the cooling section 22.

Cooling section 22 includes a spray section 22a and a vibrating flat plate 22b, where the spray section 22a is configured to spray water onto the flat plate 22b. The gas turbine material on the flat plate 22b is cooled by spraying water (cooling step 300) and then discharged as a product. As it should be noted, the cooling can be carried out only by spraying water or using air cooling in conjunction with the provision of an air nozzle and the like in addition to the spray section 22a. In addition, a two-way spray nozzle for air and water can be used.

The flat plate 22b is a smooth plate that has no holes and no concavity-convexity, and a metal plate or a resin plate is used for this. The smooth plate embodiment allows the gas turbine engine material to slide easily in the cooling section 22, resulting in smooth transport in the cooling section 22.

Due to the separation of the screening section 21 and the cooling section 22, when using the separation plate 24, it is possible to prevent the sprayed water in the cooling section 22 from entering the screening section 21. Accordingly, the absorption of water by the fine powder which has been sorted into the sizing section 21, and thus clogging in the sizing section 21 can be reduced.

A thermometer 11 is disposed at the outlet 1 of the kiln 1, and the control section 30 is configured to spray water and stop the water spray based on temperature measurements. As it should be noted, the thermometer 11 can be located in a different position as long as it is located in such a position that allows the thermometer to measure the temperature of the kiln 1.

In the present invention, despite the possibility of obtaining a HDT material characterized by high strength and water resistance, as a result of heating the BG material in the kiln 1, if the temperature of the kiln 1 corresponds to a predetermined value or less, unheated BG material or molded biomass will be discharged from the kiln 1, which is not characterized by sufficient strength and water resistance. If they are fed to the vibrating conveyor 2, due to their unsatisfactory water resistance, they will swell and disintegrate after absorbing water in the spray section 22 and cause clogging in the production plant.

Accordingly, if the temperature measured using the thermometer 11 is lower than the predetermined value, it will be considered a low temperature insufficient to manufacture the material of the gas turbine engine, and the control section 30 will stop spraying water using the spray section 22a. As a result of doing this, even if the BG material or the insufficiently heated material of the gas turbine engine is discharged from the kiln at a low kiln temperature, decomposition in the spray section 22 will be suppressed, and clogging in the production plant can be avoided.

FIG. 28 is a flow chart of continuing and stopping water spraying based on temperature using the control section 30. In step S1, the temperature at the outlet from the kiln 1 is measured using a thermometer 11. In step S2, it is judged whether the measured temperature T to a predetermined (α) value or less; if the answer is "YES", water spraying will be stopped at step S3, while if the answer is "NO", water spraying will be carried out at step S4.

Especially in the start-up phase or in the non-stationary state of the kiln 1 or in the low-temperature state, unheated BG material or insufficiently heated molded biomass is discharged from the kiln 1, therefore stopping the operation of the water spray prevents decay and clogging in the production plant.

If the transportation of the BG material in the kiln 1 stops when the kiln 1 is stopped and the temperature reaches a predetermined or lower value, the BG material will remain inside the kiln 1. In this case, a large amount of thermal decomposition gas is generated due to the carbonization of the BG material even at a low temperature. which makes one more complicated technological process necessary for gas processing. In addition, excessively carbonated BG material is unfavorable for the fuel, since the amount of the remaining volatile component in the BG material decreases, and requires additional processing, which leads to an increase in the number of additional stages. Accordingly, stopping the conveying in the kiln 1 is not preferable.

On the other hand, in the case of stopping the supply of the BG material at a low temperature, but continuing the transportation in the kiln 1, non-carbonated BG material or insufficiently heated molded biomass will be produced. Therefore, even at a low temperature, the conveying is not stopped, so that the generation of a large amount of thermal decomposition gas and excessive carbonization is prevented, and the spraying of water on the discharged BH material is stopped, so that clogging is suppressed.

As it should be noted, the thermometer 11 directly measures not the temperature of the atmosphere at the outlet of the kiln 1, but the temperature of the gas turbine material at the outlet of the kiln 1. Although the present invention provides a gas turbine (solid fuel) material characterized by water resistance and high strength , as a result of carbonization of the BG material at a predetermined or higher temperature, an excessive increase in temperature accelerates carbonation more than necessary and decreases thermal yield, which leads to insufficient fuel properties. To maintain maximum thermal yield and obtain water resistance and strength, precise temperature control is required: and therefore the temperature of the HDT material is measured directly to effect high-precision carbonation. Thermometer 11 can be of any type as long as it can directly measure the temperature of the gas turbine material at the outlet of the kiln 1, and a contact type thermometer or a non-contact type thermometer can be used, such as for use infrared radiation.

<Effect>

(1) The apparatus includes a kiln 1 (carbonization kiln), designed to produce carbonized biomass (GDT) as a result of carbonization of molded biomass, a sizing section 21 (device for sorting by size), located downstream of the kiln 1 and designed for sizing carbonated biomass (HDB), and a cooling section 22 (cooling device) located downstream of the screening section 21 and designed to cool the sorted carbonated biomass (HDB), where molded biomass is obtained by shaping the pulverized biomass feedstock, and wherein the cooling section 22 cools the carbonated biomass (CBC) by spraying water.

In the case of cooling of the carbonated biomass as a result of its immersion in water, it will be difficult to handle it due to the floatation of the carbonated biomass on the water and its distribution on the surface of the water. On the other hand, even in the case of cooling by spraying water, the molded biomass will tend to decompose back to particles due to the molding of the pulverized biomass. Therefore, there is a risk of possible clogging in the production plant due to the absorption of the pulverized biomass water in the event of water spraying while not taking proper measures. However, plugging can be avoided by carrying out water spraying after the carbonated biomass is sorted. In addition to water spraying, a combination of air cooling and water spraying can be used, or a two-way air and water nozzle can be used.

(2) Cooling section 22 includes a vibrating flat plate 22b (flat plate) and a spraying section 22a for spraying water on the flat plate 22b, where the flat plate 22b is a metal plate or a resin plate, and the carbonated biomass (CDT) is transported to vibration.

Due to the disintegration of a part of the carbonated biomass (CDT) during transportation, even after sorting by size, a certain amount remains carbonated biomass, characterized by a small diameter. The smaller the diameter, the greater the tendency for the particles to adhere to each other as a result of the spraying of water, making handling of the material difficult during transport. In this case, when the carbonated biomass is cooled on the grid, taking into account the decantation of water, the carbonated biomass subjected to water spray may accumulate due to the resistance of the concavity-convexity of the grid, and the conveying efficiency may decrease, resulting in clogging in the production unit. However, efficient conveying can be carried out using a metal plate or a resin plate with low slip resistance relative to carbonated biomass in order to reduce drag during conveying.

(3) The control section 30 (control device) is provided for stopping water spraying when using the spraying section 22a when the temperature at the outlet from the kiln 1 corresponds to a predetermined value or less. In an unsteady state, such as a start-up phase or a shutdown phase, due to the equality of the temperature of the kiln 1 to a predetermined value or less (low temperature, insufficient for the production of the gas turbine material), uncarbonated molded biomass or insufficiently carbonized molded biomass are produced, characterized by low strength or low water resistance. They can swell and disintegrate, leading to blockages in the production plant. However, blockage can be avoided by stopping the spraying of water.

(4) The thermometer 11 can directly measure the temperature of the carbonated biomass (HDT). Despite the possibility of obtaining a water-resistant and high-strength material GDT (solid fuel) as a result of carbonization of the BG material at a predetermined or higher temperature, excessive carbonization worsens the thermal yield. Therefore, by directly measuring the temperature of the HDT material, carbonization can be carried out with high precision, which makes it possible to produce a product characterized by water resistance and high strength, while ensuring a thermal yield.

(5) A separating section 24 is provided for separating the screening section 21 and the cooling section 22. By separating these sections, it is possible to prevent sprayed water from entering the screening section 22, and thus product build-up and blockage are suppressed. sorting time by size.

Instead of the vibrating conveyor 2 in the above embodiment, the sizing step and the cooling step can be carried out using the system as shown in FIG. 26B. System 402 includes apparatus with vibrating sieve 403A and cooling vibrating conveyor 403B. The shaker apparatus 403A and the cooling vibratory conveyor 403B are configured to provide separate structures. The apparatus with a vibrating sieve 403A is positioned in the direction of conveying the material of the gas turbine engine along the process flow upstream, and the cooling vibrating conveyor 403B is located downstream of the process flow. Description of the functions of structures common to the configuration in FIG. 26A will be omitted to avoid redundancy in the description.

The shaker apparatus 403A includes a screening section 421 equipped with a screen 421a. As with the configuration in FIG. 26A, the gas turbine material is fed from a rotary kiln (not shown in FIG. 26B) onto a screen 421a. The material of the gas turbine engine is transported with simultaneous vibration on the 421a sieve, as a result of which the screening is carried out by size (the stage of sorting by size) of the material of the gas turbine engine and fine powder. Despite the inclination of the apparatus with the shaker 403A, a horizontal device that is not inclined can be used.

As for the opening size of the screen 421a, as mentioned in the above embodiment, it can be changed appropriately according to the desired value. Materials that have disintegrated during manufacture, or fines from gas turbine engines that do not reach a predetermined size, fall under the 421a sieve and are processed separately. The gas turbine material retained on the screen 421a is discharged from the outlet 421b from the vibrating screen apparatus 403A.

The cooling vibrating conveyor 403B includes a cooling section 422 provided with a water spray section 422a and a vibrating flat plate 422b and the like, and the material of the turbine engine from the vibrating sieve apparatus 403A is supplied to the flat plate 422b. Although not shown, the cooling vibratory conveyor 403B is also provided with a control section for controlling the operation of the water spray section 422a and the like, as in the configuration in FIG. 26A. In one example, the flat plate 422b is a smooth plate with no holes and no concavity-convexity, and a metal plate or a resin plate is used. An embodiment of a smooth plate allows easy sliding of the material of the gas turbine engine, which allows for smooth conveying. Despite the inclination of the vibration cooling apparatus 403B, a horizontal device that is not inclined can be used.

Also in this example, the cooling can be carried out only by spraying water, or it can be carried out using air cooling in combination with spraying water. The spray nozzle can be a two-stream nozzle for air and water. Further, similar to the aforementioned embodiment, in one embodiment, it is preferable to be able to control the water spray when using the water spray section 422a to stop spraying water at a temperature lower than a predetermined value as measured using the thermometer 11 of the kiln 1 (see FIG. . 26A). As should be noted, the technical issues disclosed in FIG. 26B may be combined with or substituted by the corresponding questions disclosed in other embodiments without departing from the scope of the present invention.

A method for manufacturing a solid biomass fuel (BDT) produced in the above-described fuel manufacturing step 100 will be described in detail as follows.

[Manufacturing of solid biomass fuels (GDT) at the fuel manufacturing stage]

Solid biomass fuel is a molded solid product obtained by using steps including a molding step of squeezing and shaping biomass that has been crushed and pulverized to a debris or powder state to obtain biomass blocks, and a heating step, which consists in heating blocks of biomass. The shaped and heated solid product is used as fuel (corresponding to the HDT material mentioned below). Since solid biomass fuels do not require a steam treatment step and use of a binder, cost increases are suppressed. In the present description of the invention, blocks of biomass obtained using the molding process and prior to the heating step are also referred to as "blocks of unheated biomass". The blocks of unheated biomass correspond to the BG material mentioned above.

The biomass as a raw material can be any wood-based material and herbaceous material, and no particular limitation is imposed on tree species and parts thereof, and the like, but examples include false vine, Canadian spruce, cedar, cypress, European red pine, almond old growth tree, almond shell, xylem part of acacia, acacia bark, walnut shell, sago palm, PFG material (empty fruit bunch, which is a residue from palm oil processing), dipterocarp, rubber tree and the like. They can be used individually or in a mixture of two or more.

In the molding process, biomass blocks are produced using known molding techniques. The biomass blocks are preferably in the form of pellets or briquettes, and their size is arbitrary. In the heating step, the molded biomass blocks are heated.

In the biomass solid fuel obtained after the heating step, the COD (Chemical Oxygen Demand) value of the immersion water used for immersion in water is preferably 3000 ppm. and less. In addition, the ratio of COD values expressed as (COD of biomass solid fuel after heating step / unheated biomass solid fuel COD) for biomass solid fuel is preferably 0.98 or less. In this case, the COD (Chemical Oxygen Demand) value for immersion water used to immerse biomass solid fuels (which can simply be referred to as "COD") denotes the COD value estimated according to JIS K0102 (2010) -17 for an immersion water sample when determining the COD value obtained in accordance with Japan Environment Agency Announcement No. 13 "(A) a method for detecting a metal or the like contained in an industrial waste", 1973.

The solid biomass fuel obtained after the heating step has a Hardgrove Grind Index (RI) according to JIS M 8801, preferably in the range of 15 or more to 60 or less, and more preferably 20 or more to 60, and less. In addition, the specific surface area determined using the BET method is in the range from 0.15 to 0.8 m ² / g, and more preferably from 0.15 to 0.7 m ² / g. It is preferable when the equilibrium level of moisture content after immersion in water is in the range from 15 to 65% (wt.), And more preferably from 15 to 60% (wt.).

The biomass solid fuel of the present invention is characterized by a ratio of fuel components (bound carbon / volatile matter) in the range from 0.2 to 0.8, gross calorific value per dry weight of fuel in the range from 4800 to 7000 (kcal / kg), molar ratio between oxygen O and carbon C (O / C) in the range from 0.1 to 0.7; and the molar ratio between hydrogen H and carbon C (H / C) in the range from 0.8 to 1.3. When the biomass solid fuel exhibits physical properties in the aforementioned ranges, the COD value of the discharged water during storage can be reduced, degradation can be reduced, and the handling convenience during storage can be improved. The solid biomass fuel of the present invention can be obtained by adjusting, for example, the biomass tree species used as the raw material, their parts and the heating temperature in the heating step, and the like. The value of the result of the approximate analysis (technical analysis), the value of the result of the final analysis (elemental analysis) and the gross calorific value in the present specification are based on JIS M 8812, 8813 and 8814.

The method of making a solid biomass fuel of the present invention includes a molding step of shaping the pulverized biomass for biomass that has been crushed and pulverized to obtain blocks of unheated biomass, and a heating step of heating the blocks of unheated biomass, into whereby a heated solid product is obtained, where the heating temperature in the heating step is preferably in the range of 150 ° C to 400 ° C. When the temperature of the heating step falls within the above range, a solid biomass fuel having the above properties can be obtained. The heating temperature is appropriately determined depending on the biomass feedstock materials and the shape and size of the biomass blocks, but is preferably in the range of 150 to 400 ° C, more preferably 200 to 350 ° C. Moreover, it is preferably in the range of 230 to 300 ° C. However, in addition, it is preferably in the range from 250 to 290 ° C. The heating time in the heating step is not particularly limited, but is preferably in the range of 0.2 to 3 hours. The particle size of the pulverized biomass is not particularly limited, but the average size ranges from about 100 to 3000 µm, and preferably from 400 to 1000 µm. As a method for measuring the particle size of the pulverized biomass, known measurement methods can be used. Due to the retention of mutual bonding or adhesion in the pulverized biomass as a result of solid state crosslinking in the solid biomass fuel (DFT) of the present invention in accordance with the disclosure below, the particle size of the pulverized biomass is not specifically limited until as long as it is within the molding range. In addition, since grinding into fine powder causes an increase in costs, the particle size can be in a known range as long as both cost and formability can be consistent with each other.

In the case of designation of the symbol A for the bulk density of unheated biomass blocks before the heating stage and designation of the symbol B for the bulk density of the heated solid product after the heating stage, it will be preferable when B / A = from 0.7 to 1. No specific restrictions are imposed on the value of the bulk density A as long as it is in such a known range that blocks of unheated biomass can be obtained by molding pulverized biomass. The bulk density varies depending on the type of biomass feedstock materials, and thus can be set to an appropriate value. In addition, in the case of designating the IRC value (Hardgrove Grindability Index of JIS M8801) for blocks of unheated biomass with the H1 symbol and designating the IRC value for heated solids with the H2 symbol, it will be preferable when the H2 / H1 ratio = from 1, 1 to 2.5. By conducting the heating in such a way that one or both of the B / A and H2 / H1 values are within these ranges, it is possible to obtain a solid biomass fuel characterized by improved ease of handling during storage by reducing decay while reducing COD values for discharged water during storage.

As used herein, the characteristics of solid biomass fuels can be defined in a preferred range depending on the biomass tree species used as feedstock material. Below in this document will be described one example, but the present invention is not limited to these types of trees and their combinations. Below in this document will be described, respectively, the preferred ranges with respect to the types of raw materials for biomass used in the present invention, and the properties of the resulting solid fuels (corresponding to the material of the gas turbine, as mentioned below) and the method of their manufacture.

[Types of biomass feedstock material and solid fuel properties]

(Fake beetle, canadian spruce, cedar, cypress: solid fuel A)

Within the framework of one aspect of the present invention, when the feedstock material contains at least one species selected from fake thistle, Canadian spruce, cedar and cypress, the properties of a solid biomass fuel (which hereinafter may be referred to as "solid fuel A ") are as follows.

Its COD value is preferably 1000 ppm. and less, more preferably 900 ppm. and less, furthermore more preferably 800 ppm. or less, and its COD value ratio is preferably 0.80 or less, more preferably 0.70 or less, and furthermore more preferably 0.68 or less.

The equilibrium moisture content after immersion in water (as described below) is preferably in the range of 15 wt% to 45 wt%, more preferably 18 wt% to 35 wt%, and in addition, more preferably from 18% (wt.) to 32% (wt.).

The specific surface area determined using the BET method is preferably in the range from 0.25 m ² / g to 0.8 m ² / g, more preferably from 0.28 m ² / g to 0.6 m ² / g, and furthermore more preferably 0.32 m ² / g to 0.5 m ² / g.

Its IRC value is preferably in the range from 20 to 60, more preferably from 20 to 55, and furthermore more preferably from 22 to 55. Since the IRC value for coal (bituminous coal) suitable for use as a boiler fuel in the production of electrical energy is about 50, an IRC value closer to about 50 is preferred in view of the fact that mixing and grinding is carried out together with the coal. The ratio of the IRC values (as described below) is preferably in the range of 1.0 to 2.5.

Its fuel ratio is preferably in the range from 0.2 to 0.8, more preferably from 0.2 to 0.7, and furthermore more preferably from 0.2 to 0.65.

Its gross calorific value on a dry weight basis of fuel is preferably in the range from 4800 to 7000 kcal / kg, more preferably from 4900 to 7000 kcal / kg, and further more preferably from 4950 to 7000 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.1 to 0.62, more preferably from 0.1 to 0.61, and furthermore more preferably from 0.1 to 0.60.

Its molar ratio between hydrogen H and carbon C (H / C) is preferably in the range from 0.8 to 1.3, more preferably from 0.85 to 1.3, and furthermore more preferably from 0.9 to 1.3.

The foregoing description represents a preferred range of properties for solid fuel A.

In addition, in the case of manufacturing solid fuel A, the heating temperature in the heating step will preferably be in the range of 200 to 350 ° C, more preferably 210 to 330 ° C, and further more preferably 220 to 300 ° C. ...

(European red pine: solid fuel B)

Within one aspect of the present invention, when the European red pine feedstock material is available, the properties of a solid biomass fuel (which may be referred to herein as “solid fuel B” hereinafter) are as follows.

Its COD value is preferably 900 ppm. and less, more preferably 800 ppm. and less, furthermore more preferably 700 ppm. or less, and its COD value ratio is preferably 0.75 or less, more preferably 0.68 or less, and furthermore more preferably 0.64 or less.

The equilibrium level of moisture content after immersion in water is preferably in the range from 15% (w / w) to 45% (w / w), more preferably from 18% (w / w) to 40% (w / w), and furthermore preferably from 18% (wt.) to 31% (wt.).

The specific surface area determined using the BET method is preferably in the range from 0.30 m ² / g to 0.7 m ² / g, more preferably from 0.30 m ² / g to 0.6 m ² / g, and furthermore, more preferably 0.30 m ² / g to 0.5 m ² / g.

Its MRI value is preferably in the range from 25 to 60, more preferably from 30 to 55, and furthermore more preferably from 35 to 55. The ratio of the MRI values (as described below) is preferably in the range from 1.0 to 2, five.

Its fuel ratio is preferably in the range from 0.2 to 0.8, more preferably from 0.2 to 0.7, and furthermore more preferably from 0.2 to 0.65.

Its gross calorific value on dry weight of fuel is preferably in the range from 4950 to 7000 kcal / kg, more preferably from 5000 to 7000 kcal / kg, and further more preferably from 5100 to 7000 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.1 to 0.60, more preferably from 0.2 to 0.60, and further more preferably from 0.3 to 0.60.

Its molar ratio between hydrogen H and carbon C (H / C) is preferably in the range from 0.8 to 1.3, more preferably from 0.85 to 1.3, and furthermore more preferably from 0.9 to 1.3.

The foregoing description represents a preferred range of properties for solid fuel B.

In addition, in the case of manufacturing the solid fuel B, the heating temperature in the heating step will preferably be in the range of 200 to 350 ° C, more preferably 220 to 300 ° C, and further more preferably 240 to 290 ° C. ...

(Old growth almond tree: solid fuel C)

Within one aspect of the present invention, when the almond tree feedstock material is present, the properties of biomass solid fuels (which may be referred to herein as “solid C” hereinafter) are as follows.

Its COD value is preferably 2100 ppm. and less, more preferably 2000 ppm. and less, moreover, more preferably 1500 ppm. or less, and its COD value ratio is preferably 0.80 or less, more preferably 0.75 or less, and furthermore more preferably 0.55 or less.

The equilibrium level of moisture content after immersion in water is preferably in the range from 25% (w / w) to 60% (w / w), more preferably from 30% (w / w) to 50% (w / w), and furthermore preferably from 30% (wt.) to 45% (wt.).

The specific surface area determined using the BET method is preferably in the range from 0.20 m ² / g to 0.70 m ² / g, more preferably from 0.22 m ² / g to 0.65 m ² / g, and furthermore, more preferably 0.25 m ² / g to 0.60 m ² / g.

Its IRI value is preferably in the range from 15 to 60, more preferably from 18 to 55, and furthermore more preferably from 20 to 55. The ratio of the IRI values (as described below) is preferably in the range from 1.0 to 2, 0.

Its fuel ratio is preferably in the range from 0.2 to 0.8, more preferably from 0.25 to 0.7, and furthermore more preferably from 0.3 to 0.65.

Its gross calorific value on dry weight of fuel is preferably in the range from 4800 to 7000 kcal / kg, more preferably from 4800 to 6500 kcal / kg, and furthermore more preferably from 4900 to 6500 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.10 to 0.70, more preferably from 0.20 to 0.60, and furthermore more preferably from 0.30 to 0.60.

Its molar ratio between hydrogen H and carbon C (H / C) is preferably in the range from 0.8 to 1.3, more preferably from 0.85 to 1.3, and furthermore more preferably from 0.9 to 1.20.

The foregoing description represents a preferred range of properties for solid fuel C.

In addition, in the case of manufacturing the solid fuel C, the heating temperature in the heating step will preferably be in the range of 200 to 350 ° C, more preferably 220 to 300 ° C, and further more preferably 240 to 290 ° C. ...

(Mixture of almond shell and almond old growth tree: solid fuel D)

Within one aspect of the present invention, when the raw material is a mixture of almond shell and almond old growth, the properties of solid biomass fuels (which may be referred to herein as “solid fuel D” hereinafter) are as follows.

Its COD value is preferably 2500 ppm. and less, more preferably 2000 ppm. and less, moreover, more preferably 1500 ppm. or less, and its COD value ratio is preferably 0.75 or less, more preferably 0.68 or less, and furthermore more preferably 0.50 or less.

The equilibrium level of moisture content after immersion in water is preferably in the range from 15% (w / w) to 50% (w / w), more preferably from 20% (w / w) to 40% (w / w), and furthermore preferably from 20% (wt.) to 35% (wt.).

The specific surface area determined using the BET method is preferably in the range from 0.20 m ² / g to 0.70 m ² / g, more preferably from 0.27 m ² / g to 0.70 m ² / g, and furthermore, more preferably 0.30 m ² / g to 0.60 m ² / g.

Its MRI value is preferably in the range from 20 to 60, more preferably from 20 to 55, and furthermore more preferably from 23 to 55. The ratio of the MRI values (as described below) is preferably in the range from 1.0 to 2, 0.

Its fuel ratio is preferably in the range from 0.2 to 0.8, more preferably from 0.30 to 0.7, and furthermore more preferably from 0.35 to 0.65.

Its gross calorific value on a dry weight basis of fuel is preferably in the range from 4800 to 7000 kcal / kg, more preferably from 4800 to 6500 kcal / kg, and furthermore more preferably from 4900 to 6300 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.10 to 0.70, more preferably from 0.20 to 0.60, and furthermore more preferably from 0.30 to 0.55.

Its molar ratio between hydrogen H and carbon C (H / C) is preferably 0.8 to 1.3, more preferably 0.8 to 1.25, and furthermore more preferably 0.85 to 1.20.

The foregoing description represents a preferred range of solid fuel D properties.

In addition, in the case of manufacturing the solid fuel D, the heating temperature in the heating step will preferably be in the range from 200 to 350 ° C, more preferably from 220 to 300 ° C, and furthermore more preferably from 240 to 290 ° C. ...

(Xylem part of acacia: solid fuel E)

Within one aspect of the present invention, when the xylem acacia feedstock material is available, the properties of biomass solid fuels (hereinafter referred to as “solid fuel E”) are as follows.

Its COD value is preferably 950 ppm. and less, more preferably 850 ppm. and less, furthermore more preferably 800 ppm. or less, and its COD value ratio is preferably 0.95 or less, more preferably 0.85 or less, and furthermore more preferably 0.80 or less.

The equilibrium moisture content after immersion in water is preferably in the range from 20% (w / w) to 60% (w / w), more preferably from 20% (w / w) to 55% (w / w), and furthermore preferably from 23% (wt.) to 53% (wt.).

The specific surface area determined using the BET method is preferably in the range from 0.40 m ² / g to 0.70 m ² / g, more preferably from 0.50 m ² / g to 0.70 m ² / g, and furthermore, more preferably 0.55 m ² / g to 0.70 m ² / g.

Its fuel ratio is preferably in the range from 0.2 to 0.6, more preferably from 0.2 to 0.5, and furthermore more preferably from 0.2 to 0.4.

Its gross calorific value on dry weight of fuel is preferably in the range from 4800 to 7000 kcal / kg, more preferably from 4800 to 6000 kcal / kg, and furthermore more preferably from 4800 to 5500 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.40 to 0.70, more preferably from 0.45 to 0.70, and furthermore more preferably from 0.48 to 0.65.

Its molar ratio between hydrogen H and carbon C (H / C) is preferably in the range from 0.8 to 1.3, more preferably from 1.0 to 1.3, and furthermore more preferably from 1.1 to 1.3.

The foregoing description represents a preferred range of properties for solid fuel E.

In addition, in the case of manufacturing the solid fuel E, the heating temperature in the heating step will preferably be in the range of 200 to 350 ° C, more preferably 220 to 300 ° C, and further more preferably 240 to 290 ° C. ...

(Acacia bark: solid fuel F)

Within one aspect of the present invention, when the raw material is acacia bark, the properties of a solid biomass fuel (which may be referred to herein as “solid fuel F” hereinafter) are as follows.

Its COD value is preferably 2500 ppm. and less, more preferably 2000 ppm. and less, moreover, more preferably 1200 ppm. or less, and its COD value ratio is preferably 0.30 or less, more preferably 0.20 or less, and furthermore more preferably 0.15 or less.

The equilibrium level of moisture content after immersion in water is preferably in the range from 15% (w / w) to 50% (w / w), more preferably from 20% (w / w) to 45% (w / w), and furthermore preferably from 25% (wt.) to 40% (wt.).

The specific surface area determined using the BET method is preferably in the range from 0.35 m ² / g to 0.55 m ² / g, more preferably from 0.40 m ² / g to 0.55 m ² / g, and furthermore, more preferably 0.40 m ² / g to 0.50 m ² / g.

Its fuel ratio is preferably in the range from 0.4 to 0.8, more preferably from 0.42 to 0.75, and furthermore more preferably from 0.45 to 0.75.

Its gross calorific value on a dry weight basis of fuel is preferably in the range from 4800 to 7000 kcal / kg, more preferably from 5000 to 7000 kcal / kg, and furthermore more preferably from 5200 to 6500 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.25 to 0.60, more preferably from 0.30 to 0.60, and furthermore more preferably from 0.30 to 0.55.

Its molar ratio between hydrogen H and carbon C (H / C) is preferably 0.8 to 1.3, more preferably 0.8 to 1.2, and furthermore more preferably 0.9 to 1.2.

The foregoing description represents a preferred range of properties for solid fuel F.

In addition, in the case of manufacturing the solid fuel F, the heating temperature in the heating step will preferably be in the range of 200 to 350 ° C, more preferably 220 to 300 ° C, and further more preferably 240 to 290 ° C. ...

(Mixture of almond shells and walnut shells: solid fuel G)

Within one aspect of the present invention, when the raw material is a mixture of almond shell and walnut shell, the properties of a solid biomass fuel (which may be referred to herein as “solid fuel G” hereinafter) are as follows.

Its COD value is preferably 2500 ppm. and less, more preferably 2100 ppm. and less, moreover, more preferably 1500 ppm. or less, and its COD value ratio is preferably 0.65 or less, more preferably 0.55 or less, and furthermore more preferably 0.45 or less.

The equilibrium moisture content after immersion in water is preferably in the range from 20% (w / w) to 45% (w / w), more preferably from 20% (w / w) to 40% (w / w), and furthermore preferably from 25% (wt.) to 35% (wt.).

The specific surface area determined using the BET method is preferably in the range from 0.15 m ² / g to 0.35 m ² / g, more preferably from 0.19 m ² / g to 0.33 m ² / g, and furthermore, more preferably 0.20 m ² / g to 0.30 m ² / g.

Its RPI value is preferably in the range from 18 to 60, and more preferably from 20 to 55, and more preferably from 20 to 60. The ratio of the RPI values (as described below) is preferably 1.0 or more.

Its fuel ratio is preferably in the range from 0.2 to 0.7, more preferably from 0.25 to 0.65, and furthermore more preferably from 0.28 to 0.60.

Its gross calorific value on dry weight of fuel is preferably in the range from 4800 to 7000 kcal / kg, more preferably from 4800 to 6000 kcal / kg, and furthermore more preferably from 5000 to 6000 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.30 to 0.65, more preferably from 0.40 to 0.70, and furthermore more preferably from 0.40 to 0.60.

Its molar ratio between hydrogen H and carbon C (H / C) is preferably in the range from 0.8 to 1.3, more preferably from 0.9 to 1.25, and furthermore more preferably from 0.9 to 1.2.

The foregoing description represents a preferred range of properties for solid fuel G.

In addition, in the case of manufacturing the solid fuel G, the heating temperature in the heating step will preferably be in the range of 200 to 350 ° C, more preferably 220 to 300 ° C, and further more preferably 240 to 290 ° C. ...

(Sago: solid fuel H)

Within one aspect of the present invention, when the sago feedstock material is available, the properties of a solid biomass fuel (which may be referred to herein as “solid fuel H” hereinafter) are as follows.

Its COD value is preferably 2000 ppm. and less, more preferably 1600 ppm. and less, furthermore more preferably 800 ppm. or less, and its COD value ratio is preferably 0.85 or less, more preferably 0.60 or less, and furthermore more preferably 0.4 or less.

The equilibrium level of moisture content after immersion in water is preferably in the range from 20% (w / w) to 35% (w / w), more preferably from 20% (w / w) to 33% (w / w), and furthermore preferably from 22% (wt.) to 30% (wt.).

The specific surface area determined using the BET method is preferably in the range from 0.15 m ² / g to 0.35 m ² / g, more preferably from 0.18 m ² / g to 0.33 m ² / g, and furthermore, more preferably 0.18 m ² / g to 0.30 m ² / g.

Its RPI value is preferably in the range from 20 to 60, more preferably from 25 to 55, and furthermore more preferably from 30 to 55. The ratio of the RPI values (as described below) is preferably in the range from 1.0 to 2, 5, more preferably 1.3 to 2.3, and furthermore more preferably 1.5 to 2.2.

Its fuel ratio is preferably in the range from 0.2 to 0.8, more preferably from 0.25 to 0.8, and furthermore more preferably from 0.5 to 0.8.

Its gross calorific value on dry weight of fuel is preferably in the range from 4800 to 7000 kcal / kg, more preferably from 4900 to 6500 kcal / kg, and further more preferably from 5000 to 6000 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.20 to 0.65, more preferably from 0.20 to 0.60, and furthermore more preferably from 0.2 to 0.55.

Its molar ratio between hydrogen H and carbon C (H / C) is preferably in the range from 0.8 to 1.3, more preferably from 0.85 to 1.3, and furthermore more preferably from 0.85 to 1.2.

The foregoing description represents a preferred range of properties for H.

In addition, in the case of manufacturing the solid fuel H, the heating temperature in the heating step will preferably be in the range of 200 to 350 ° C, more preferably 220 to 300 ° C, and further more preferably 240 to 290 ° C. ...

(PFG: solid fuel I)

In one aspect of the present invention, when the feedstock material is PFG (an empty fruit cluster that is the residue from palm oil processing), the properties of solid biomass fuels (which may be referred to herein as "solid fuel I" ) are as follows.

Its COD value is preferably 2350 ppm. and less, more preferably 2300 ppm. and less, furthermore more preferably 2000 ppm. or less, and its COD value ratio is preferably 0.98 or less, more preferably 0.96 or less, and furthermore more preferably 0.85 or less.

The equilibrium level of moisture content after immersion in water is preferably in the range from 23% (w / w) to 45% (w / w), more preferably from 20% (w / w) to 40% (w / w), and furthermore preferably from 20% (wt.) to 35% (wt.).

The specific surface area determined using the BET method is preferably in the range from 0.25 m ² / g to 0.65 m ² / g, more preferably from 0.30 m ² / g to 0.60 m ² / g, and furthermore, more preferably 0.35 m ² / g to 0.55 m ² / g.

Its fuel ratio is preferably in the range from 0.25 to 0.8, more preferably from 0.30 to 0.8, and furthermore more preferably from 0.36 to 0.8.

Its gross calorific value on dry weight of fuel is preferably in the range from 4800 to 7000 kcal / kg, more preferably from 4900 to 7000 kcal / kg, and further more preferably from 5000 to 7000 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.15 to 0.65, more preferably from 0.15 to 0.60, and furthermore more preferably from 0.15 to 0.55.

Its molar ratio between hydrogen H and carbon C (H / C) is preferably in the range from 0.5 to 1.3, more preferably from 0.55 to 1.3, and furthermore more preferably from 0.6 to 1.2.

The foregoing description represents a preferred range of properties for solid fuel I.

In addition, in the case of producing solid fuel I, the heating temperature in the heating step will preferably be in the range of 200 to 350 ° C, more preferably 220 to 300 ° C, and furthermore more preferably 240 to 260 ° C. ...

(Dipterocarp: solid fuel J)

Within one aspect of the present invention, when the feedstock material is dipterocarp, the properties of a solid biomass fuel (which may be referred to herein as “solid fuel J” hereinafter) are as follows.

Its COD value is preferably 330 ppm. and less, more preferably 320 ppm. and less, moreover, more preferably 300 ppm. or less, and its ratio of COD values is preferably 0.98 or less, more preferably 0.95 or less, and furthermore more preferably 0.90 or less.

The equilibrium level of moisture content after immersion in water is preferably in the range from 15% (w / w) to 30% (w / w), more preferably from 15% (w / w) to 27% (w / w), and furthermore preferably from 18% (wt.) to 25% (wt.).

Its fuel ratio is preferably in the range from 0.2 to 0.6, more preferably from 0.2 to 0.5, and furthermore more preferably from 0.2 to 0.45.

Its gross calorific value on dry weight of fuel is preferably in the range from 4800 to 7000 kcal / kg, more preferably from 4800 to 6500 kcal / kg, and furthermore more preferably from 4800 to 6000 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.3 to 0.60, more preferably from 0.35 to 0.60, and furthermore more preferably from 0.40 to 0.60.

Its molar ratio between hydrogen H and carbon C (H / C) is preferably in the range from 0.9 to 1.2, more preferably from 0.95 to 1.2, and furthermore more preferably from 1.0 to 1.2.

The foregoing description represents a preferred range of solid fuel properties J.

In addition, in the case of manufacturing the solid fuel J, the heating temperature in the heating step will preferably be in the range of 200 to 350 ° C, more preferably 220 to 300 ° C, and further more preferably 230 to 290 ° C. ...

(Rubber wood: solid fuel K)

Within one aspect of the present invention, when a rubber wood feedstock material is available, the properties of a biomass solid fuel (which may be referred to herein as “K solid fuel” hereinafter) are as follows.

Its fuel ratio is preferably in the range from 0.2 to 0.8, and more preferably from 0.2 to 0.7. Its gross calorific value on a dry weight basis of fuel is preferably in the range from 4800 to 7000 kcal / kg.

Its molar ratio between oxygen O and carbon C (O / C) is preferably in the range from 0.1 to 0.70. Its molar ratio between hydrogen H and carbon C (H / C) is preferably 0.8 to 1.3.

The foregoing description represents a preferred range of properties for solid fuel K.

In addition, in the case of manufacturing the solid fuel J, the heating temperature in the heating step will preferably be in the range of 200 to 350 ° C, more preferably 220 to 300 ° C, and further more preferably 230 to 290 ° C. ...

As the inventors of the present invention contemplate, in the method for producing solid biomass fuel, due to the demonstration by the method of such an order of steps, when the heating step of heating the unheated biomass blocks is carried out after the shaping step, the pulverized biomass maintains mutual bonding or adhesion when used. components originating from the biomass of the feedstock material, without the use of a binder, which makes it possible to produce biomass-based solid fuels with high water resistance that do not degrade when immersed in water. In accordance with the analysis of the inventors of the present invention, the following discoveries are made with regard to the mechanism by which solid biomass fuels become water-resistant.

The inventors of the present invention performed IR-PF analysis, GC-MS analysis and SEM observations on three types of biomass solid fuels made using different production methods, specifically, unheated solid fuel produced as a result of molding pulverized biomass (white granules: which hereinafter may be referred to as BG) and solid fuel obtained by heating after molding the pulverized biomass (granulation before torrefaction: which below can be denoted as BHT), and analyzed the mechanism of water resistance of solid fuels based on biomass. No binders were used in the BG material or in the BDT material in this document.

First, using the IR-PF method, acetone extracts of the corresponding solid fuels were analyzed. In the BDT material obtained after the heating step, the content of the hydrophilic COOH groups is small, but the C = C bond content is large compared to that of the unheated BG material. This involves a change in the chemical structure of the components that make up the biomass, and the acquisition of hydrophobicity by it as a result of heating.

In addition, the components of the acetone extract for the respective solid fuels were analyzed as part of the analysis using the GC-MS method. As it is assumed, as a result of heating, terpenes such as abietic acid and its derivatives (which hereinafter may be referred to as “abietic acid and the like”) thermally decomposed, and this fact relates to the water resistance of solid fuels based on biomass. Abietic acid and the like are the main components of rosin contained in pine and the like.

FIG. 18 is a diagram illustrating the (evaluative) mechanism for the development of solid state crosslinking in a HDT material. In the case of the HDT material, in the heating step after the shaping step, the molten liquid of abietic acid will elute in the gap between the biomass elements (the gap between adjacent particles of pulverized biomass that have been compacted by shaping after pulverization: herein, biomass may be referred to as “Pulverized biomass”) with increasing temperature, and evaporation and thermal decomposition of abietic acid occurs to form hydrophobic materials that are fixed in the gap between the particles of pulverized biomass, which leads to the development of crosslinking (crosslinking in solid state). Thus, without the addition of a binder, when using abietic acid and the like, produced from the biomass feedstock material, inter-bonding or adhesion is maintained in the pulverized biomass. Thus, according to theoretical assumptions, the pulverized biomass particles are combined or bound to each other, which prevents water penetration, and the water resistance is improved.

On the other hand, in the case of the BG material which is unheated and obtained only by molding the pulverized biomass, unlike the aforementioned HDT material, in the pulverized biomass there is no solid crosslinking between the powder particles. Due to the presence of a large amount of the hydrophilic group COOH and the like on the surface of the pulverized biomass of the feedstock constituting the BG material, an easy flow of water is noted. The infiltrated water expands the gap between the particles of the pulverized biomass even further, and thus molded granules and the like are easily degraded.

In addition, in the case of solid fuels formed after heating the pulverized biomass (granulation after torrefaction; hereinafter referred to as HPT), the individual particles of the pulverized biomass themselves become hydrophobic at the surface due to the elution of abietic acid and the like. ... However, due to the pulverization and molding after they become hydrophobic by heating, crosslinking between the pulverized biomass particles is not expected unlike the aforementioned HDT material. Therefore, in the case of the HPT material, for which heating is carried out before molding, water easily penetrates into the gap between the compacted particles of the pulverized biomass, and thus, it has an unsatisfactory water resistance as compared to the HPT material.

The melting point of abietic acid or its derivatives is in the range of about 139 to 142 ° C, and the boiling point is about 250 ° C. Thus, abietic acid and the like are melted by heating at a temperature close to the melting point to undergo crosslinking in a liquid state, and abietic acid and the like undergo thermal decomposition at a temperature close to the boiling point to develop crosslinking in a solid state. condition.

As noted, terpenes, including abietic acid, are generally found in biomass (see Hokkaido Forest Products Research Institute monthly report 171, April 1966, Public Interest Incorporated Association Japan Wood Protection Association, "Wood Preservation" Vol. 34- 2 (2008), etc.). Although there are slight differences in the level of content depending on the type of biomass (see the publication "use of essential oil", Ohira Tatsuro, Japan Wood Society the 6th Research Subcommittee Report p72, Table 1, Japan Wood Society 1999, etc.) all examples <Example A> to <Example I> described below demonstrated the formation of water resistance as a result of heating to 230 ° C or more (decomposition does not occur even after immersion in water, see table 6), and therefore, it is considered that heating biomass generally at a temperature in the range from at least 230 ° and more to 250 ° C or more provides water resistance.

FIG. 19-22 are illustrations showing analysis results using the IR-PF method for biomass solid fuels of the present invention. The feedstock material is European pine from Example B below, and the analysis was performed on a heated solid fuel (HDT) obtained by pulverizing and shaping the feedstock material to obtain a pellet shape and heating at 250 ° C. In addition, data is also shown for unheated solid fuel (BH) obtained by pulverizing and molding the same raw material but without heating. Both on the outer surface of the granule (Fig. 19) and in the cross section of the center (Fig. 20), the number of COOH groups corresponds to the ratio BG> HDT, and the number of C = C bonds corresponds to the ratio HDT> BG. In addition, the amount of the COOH group eluted into the acetone extract (Fig. 21) corresponds to the ratio BG> HDT, which indicates that the HDT material contains fewer hydrophilic COOH groups. In addition, in solids after extraction with acetone (FIG. 22), the HDT material contains more C = C bonds than the BG material. Thus, as it must be understood, the HDT material is characterized by excellent water resistance.

FIG. 23 is an illustration showing GC-MS analysis results for an acetone extract solution. The feedstock materials are European pine from example B, the same as for the aforementioned FIGS. 19-22, and the analysis was carried out for heated solid fuel (HDT) obtained by pulverizing and shaping the feedstock material to obtain a pellet shape and heating at 250 ° C, and unheated solid fuel (BG). As shown in FIG. 23, the eluted amount of abietic acid and the like, which is one type of terpenes, in acetone is less in the case of the HDT material than in the case of the BG material. Thus, it is believed that the results show melting by heating to undergo liquid crosslinking and evaporation of abietic acid and the like to solid state crosslinking.

In addition, in the case of the HDT material, the solid fuel strength is improved due to the development of crosslinking in the solid state, and therefore, as expected, without the addition of a binder by heating in the range of at least 230 ° C or more to 250 ° With or more, which is similar to that for water resistance, good grindability (IRC index described below, pulverization rate) and good handling (disintegration test described below) are obtained. As mentioned above, when using the HDT material, the COD value decreases. It is believed that this is due to the evaporation of the tar component of the biomass feedstock material upon heating, and at the same time, the solidified abietic acid and the like coat the surface of the solid fuel based on the BDT material, which further increases the hydrophobicity of the solid fuel surface, preventing the elution of the tar component. remaining in the biomass feedstock material.

Example

<Example A>

(Examples A-1 to A-6)

Solid biomass fuel A (HDF) was obtained using a molding step of pulverizing the biomass after crushing and shaping the pulverized biomass, followed by a heating step. No binder is used at any stage. The raw material used for the biomass is a mixture of 40% (w / w) thissolite false sugars, 58% (w / w) Canadian spruce, 1% (w / w) cedar and 1% (w / w) cypress. In the molding process of each example, the feedstock material was molded into pellets with a diameter of 8 mm. In the heating step of each example, 4 kg of raw material was loaded into an electric batch furnace having a diameter of 600 mm and heated to target temperatures (heating temperatures in Table 1) in the respective examples at a heating rate of 2 ° C / min. Below in this document, the terms "target temperature" and "heating temperature" refer to the same value. In examples A-1 to A-6, the temperature was not kept at the target temperature (heating temperature) (this also applies to the following examples B to K). Table 1 shows the heating temperature in the heating step of Examples A-1 to A-6 and the properties of the resulting solid biomass fuel A obtained after the heating step.

(Comparative example A)

Comparative Example A is an unheated solid biomass fuel (BH) that is obtained only by molding after crushing and pulverizing, but not using a heating step. In comparative example A, a binder was also not used. The biomass of the feedstock is the same as in example A-1. Table 1 also shows the properties of the resulting solid fuel from Comparative Example A.

In Table 1, the RPI value is based on JIS M 8801 in accordance with the description of the invention, and a higher value indicates better grindability. Table 1 shows the gross calorific value (dry mass of fuel), the ratio of the fuel components calculated based on the values of the results of the approximate analysis (calculated on the basis of air-dry matter), and the values of the results of the final analysis (in the air-dry state) and molar ratios for oxygen O, carbon C and hydrogen H obtained from the final analysis.

For the solid biomass fuels obtained in the above examples and comparative examples, additional analyzes were performed in accordance with the description of the invention below.

[COD]

FIG. 1 shows the correlations between the heating temperature during the heating step and the COD (Chemical Oxygen Demand) and pH (pH value described below) values for immersion water when the resulting solid biomass fuels are immersed in water. An immersion water sample for COD determination was obtained in accordance with Japan Environment Agency Announcement No. 13 "(A) a method for detecting a metal or the like contained in an industrial waste", 1973 and the COD value was analyzed in accordance with JIS K0102 (2010) -17.

Based on the results in FIG. 1, the COD value of Comparative Example A (BG: biomass solid fuel obtained by spinning alone without a heating step) is high, that is, about 1200 ppm. In contrast, the COD values for biomass solid fuels that were heated at 230 ° C or more are less than 800 ppm, indicating low elution of the tar component. Accordingly, as demonstrated, the solid biomass fuels of Examples A-1 to A-6 are fuels exhibiting excellent handling characteristics due to low elution of the tar component even during outdoor storage. COD values for solid biomass fuels from examples A-1 to A-6 heated at 230 ° C or more decrease as the heating temperature increases. This assumes that the COD value decreases as a result of evaporation of tar and the like due to heating. Therefore, even in the case of a heating temperature less than 230 ° C, namely, a heating temperature in the range of 150 ° C or more to less than 230 ° C, lower COD values would be expected as compared to the values in Comparative Example A.

[pH]

The solid fuels of Examples A-1 to A-6 and Comparative Example A were immersed in water at a solid to liquid ratio of 1: 3, and the pH values were measured. As shown in FIG. 1, despite the observation of slightly low values for Example A-2 and Example A-3, the pH values are approximately 6 in all Examples A-1 to A-6, indicating no specific change from the unheated Comparative Example A. Therefore, as demonstrated, no particular problem arises with respect to the pH values for the drained water when the examples A-1 to A-6 are stored outdoors.

[Grindability]

FIG. 2 shows the relationship between the heating temperature in the heating step and the Hardgrove Grind Index (HRI) and the pulverization rate (as described below) of the resulting biomass solid fuel A for the biomass solid fuels of Comparative Example A and Examples A- 1 to A-6.

As can be clearly seen from the results in Table 1 and FIG. 2, the properties were changed by heating in Examples A-1 to A-6, and the IRC values (based on JIS M 8801) were larger than the corresponding values from Comparative Example A (BG: unheated biomass solid fuel after molding ). The typical RPI for coal (bituminous coal) is about 50, and the pulverizing characteristics of Examples A-1 to A-6 are close to those of coal and are better than Comparative Example A.

The pulverization rate in FIG. 2 is the mass of the milled material per unit of time (g / min) as determined by measuring the mass of the milled sample, which is the fraction passing through the 150 µm sieve after pulverizing the 700 cc sample. cm when using a ball mill. In this document, the measurement was carried out using a ball mill in accordance with JIS M4002, where in a cylindrical container having an inner diameter of 305 mm × an axis length of 305 mm, balls from conventional ball bearings were loaded in accordance with the definition in JIS B1501 (F 36 , 5 mm × 43 balls, Ф 30.2 mm × 67 balls, Ф 24.4 mm × 10 balls, Ф 19.1 mm × 71 balls and Ф 15.9 mm × 94 balls) and the container was rotated at a speed of 70 rpm ./min. Heating improves the pulverization rate, in particular, heating at 230 ° C or more significantly increases the pulverization rate. As it can be considered, the elution and solidification associated with heating organic ingredients such as tar will increase the hardness of the biomass solid fuel and improve the pulverization efficiency. Therefore, even in the case of a heating temperature in the range of 150 ° C or more to less than 230 ° C, an IRC value and a pulverizing speed that are improved in comparison with the values for unheated Comparative Example A would be expected.

[Decay test]

Table 2 shows the cumulative sieve percentage of Biomass A solid fuel after the decay test, and FIG. 3 is a particle size distribution diagram. In order to evaluate the handling characteristics of the granules, a disintegration test was performed. A 1 kg sample was packed in a plastic bag and dropped 20 times from a height of 8.6 m and subjected to a rotational strength test based on JIS Z 8841 to measure particle size distribution. The resulting particle size distribution is shown in FIG. 3. In this document, as a sample having a convenient storage particle size and the like, a sample having a particle size distribution is defined in which the amount of particles passing through a 2 mm sieve is 30 wt%, and less, and the amount of particles passing through a sieve of 0.5 mm is 15 wt% or less. As shown by the results in Table 2 and FIG. 3, although the particle size of the specimen after the rotational strength test becomes finer as the heating temperature increases, all specimens meet the evaluation criteria described above and are therefore easy to handle without any problem.

table 2

Sieve opening Comparative example A Example A-1 A-2 A-3 A-4 A-5 A-6 (mm) (% (mass.)) (% (mass.)) (% (mass.)) (% (mass.)) (% (mass.)) (% (mass.)) (% (mass.)) sixteen 100.0 100.0 100.0 100.0 100.0 100.0 100.0 9.5 90.5 100.0 100.0 100.0 100.0 100.0 100.0 4.75 12.9 14.4 19.5 20.9 32.3 19.1 18.4 3.35 10.2 10.1 14.9 16.9 26.2 15.8 16.8 2 8.0 7.4 11.2 12.7 20.0 13.4 14.5 one 6.3 5.8 9.0 10.4 16.1 11.6 12.3 0.5 5.1 4.7 7.2 8.6 13.2 10.0 10.3 0.212 3.0 2.8 4.0 4.9 8.6 6.8 6.3 0.1 1,2 1.0 1,2 1.7 3.5 2.7 2.4 0.075 0.7 0.6 0.6 0.8 1.7 1.5 1,3

[Immersion in water]

Table 3 and FIG. 4 shows the results of a water immersion test for solid fuels based on biomass A. The solid fuels of the respective examples and the comparative example were immersed in water and removed after a predetermined period of time shown in Table 3 and FIG. 4. After wiping off the water, the moisture content of the solid was measured. The solid fuel of Comparative Example A (BG) was subject to degradation due to immersion in water, and it was not possible to measure the moisture content of the solid. In contrast, in the solid fuel of Example A-1, the moisture level reached equilibrium within about 10 hours after immersion, and the equilibrium moisture level was about 27 wt%. In the solid fuel of Example A-2, the moisture level reached equilibrium after about 100 hours, and the equilibrium moisture level was about 25 wt%. Also in the solid fuels of Examples A-3 to A-5, the moisture level reached equilibrium at about 23 wt% after about 100 hours. Also in the solid fuel of Example A-6, the moisture content reached approximately equilibrium after approximately 100 hours, and the equilibrium moisture content was approximately 28 wt% (while the dispersion was greater than in Examples A-3 to A-5, as it seems, this is due to the scatter of characteristics for the raw materials). These results are believed to be obtained because the elution and solidification of organic ingredients, such as tar, associated with heating rendered the surface of the solid biomass fuel hydrophobic, indicating that Examples A-1 to A-6 (HDT ) beneficial properties as a solid fuel, which is often stored outdoors.

Table 3

Dive time (hour) 0 6 24 48 72 96 144 168 192 240 Moisture level after immersion (% (mass)) Etc. A-1 2.83 27.34 28.76 28.81 27.35 27.79 27.97 Etc. A-2 2.37 21.91 23.74 25.02 24.59 24.71 23,80 Etc. A-3 1.71 14.39 19.66 20.30 22.09 22.85 23.00 Etc. A-4 1.13 12.00 16.78 18.43 20.31 23.83 22.58 22.41 Etc. A-5 1.31 11.10 14.87 17.16 18.67 23.93 22.09 23.04 Etc. A-6 2.48 9.99 14.94 17.05 18.73 25.02 27.21 28.13 26.97

Etc. = Example.

[Solid strength before and after immersion in water]

(Rolling strength)

FIG. 5 shows the results of the solid strength measured before and after immersion in water (based on the rotational strength test method from JIS Z-8841) for Examples A-1 to A-6 and Comparative Example A. As mentioned above, the solid fuel of Comparative Example A (BG) was subject to degradation by immersion in water, and measurement of rotational strength after immersion was not possible. For Examples A-1 to A-6 (HDT), the samples used were corresponding samples dried for 22 hours at 35 ° C. in a thermostatic oven after wiping off water on the surface of solid fuels that had reached an equilibrium moisture level. In Examples A-1 to A-6 (HDT), which were subjected to the heating step, the strength did not decrease significantly, and pulverization hardly proceeded even in comparison with Comparative Example A before immersion in water (BG), and thus thus, as can be said, the ease of handling is maintained.

(Mechanical resistance)

FIG. 6 is a diagram showing the result measured for mechanical resistance before and after immersion in water. For the solid fuels of Examples A-1 to A-6 and Comparative Example A, the mechanical resistance MC was determined based on the following equation in accordance with the United States agriculture industry's standard ASAE S 269.4 and German Industrial Standard DIN EN 15210-1. In the equation, m0 is the mass of the sample before rotational processing, m1 is the remaining sieve weight of the sample after rotational processing, where the sieve used was a plate sieve having circular holes with a diameter of 3.15 mm.

MS = (m1 / m0) × 100

With regard to the mechanical resistance similar to the rotational strength, in Examples A-1 to A-6 (HDT) which were subjected to the heating step, the strength did not decrease significantly, and the pulverization hardly proceeded even in comparison with Comparative Example A. before immersion in water (HD), and thus, as indicated, the ease of handling was maintained.

[Spontaneous combustion characteristics]

Spontaneous combustion performance was evaluated based on the "Spontaneous combustion test" from The Manual of Tests and Criteria, the United Nations: Regulations for the Carriage and Storage of Dangerous Goods by Ship, 16th revised edition. 1 to 2 cm ^{3 of the} solid biomass fuel of Example A-2 (heating temperature: 250 ° C) was dropped onto the inorganic insulation board from a height of 1 m, and it was determined whether ignition occurred during the fall or within five minutes after the fall. The test was carried out six times. Since no ignition occurred for 6 samples, Example A-2 (DGT) was identified as not falling into package category I from the aforementioned UN manual of tests and criteria.

[Self-heating characteristics]

Self-heating performance was evaluated based on the "Spontaneous Combustion Test" from Regulations for the Carriage and Storage of Dangerous Goods by Ship, 16th revised edition. A sample container (stainless steel mesh cube with a side length of 10 cm) was charged with solid biomass fuel from Example A-2 (heating temperature 250 ° C), which was suspended inside a thermostatic oven at a temperature of 140 ° C, and the temperature of the material was continuously measured over 24 hours. A material that is found to have ignited or a temperature rise of more than 200 degrees is defined as a self-heating material and is additionally subjected to the same test using a 2.5 cm sample container and either ignition or a temperature rise of more than than 60 degrees. As determined from the test results, Example A-2 (HDT) does not belong to the category of self-heating material.

[Pore size distribution]

(Specific surface area determined using the BET method)

FIG. 7 is a graph showing the BET specific surface area measurement for solid fuel A. The BET specific surface area was determined using an automatic specific surface area / pore size distribution apparatus (Nippon Bell Co., Ltd. BELSORP-min II) for the solid fuel samples from Examples A-1 to A-6 and Comparative Example A, which were cut to a size in the range of 2 to 6 mm, the container was filled and degassed under vacuum for 2 hours at 100 ° C as part of the pre-treatment. Nitrogen gas was used as the adsorption gas. Based on the results in FIG. 7, the specific surface area determined using the BET method increases with increasing heating temperature, which demonstrates the development of pore formation during heating (pyrolysis).

(Average pore diameter, cumulative pore volume)

FIG. 8 is a graph showing the average pore diameter on the surface of the solid fuel A, and FIG. 9 is a graph showing cumulative pore volume. The average pore diameter and total pore volume were measured using the same equipment used for the BET specific surface area. The term "pore" as used herein means a cavity having a diameter in the range of 2 nm to 100 nm. The average pore diameter becomes smaller with increasing heating temperature, as in example A-2 and subsequent examples, indicating the formation of a large number of small pores. This appears to be due to the degradation of cellulose.

[Output]

FIG. 10 is a graph showing the yield of biomass solid fuel A after the heating step (solid yield and thermal yield). The solids yield is the weight ratio before and after heating, and the thermal yield is the ratio of the gross heats of combustion before and after heating. As mentioned above, the temperature was not kept at the target temperature (heating temperature) in each example (this also applies to the following examples from B to K).

As demonstrated by the results of examples A-1 to A-6, in accordance with the present invention at a low cost, a solid fuel based on biomass A (HDF) can be obtained, for which a decrease in the COD value, an improvement in grindability, a decrease in adsorption water, improving the strength of the solid and improving the yield.

[Spontaneous combustion characteristics]

The spontaneous combustion performance of the solid fuel of Example A-2 was measured according to the following method. 1 kg of samples was loaded into a container and placed in a thermostatic oven at 80 ° C. Air was passed through the sample and the concentrations of O2, CO and CO2 in the resulting gas were measured. Based on the concentration before and after heating, based on the following equation (1), the degree of adsorption of O2, the degree of CO formation, and the degree of CO2 formation as a result of heating the samples were calculated to calculate the self-heating index (SPI).

Spontaneous combustion index (SPI) = {degree of adsorption of О2 × heat of adsorption of О2 × (1/100)} + {degree of formation of СО × (heat of formation of СО + (1/2) × heat of formation of Н2О × Н / С) × (1 / 100)} + {degree of formation of СО2 × (heat of formation of СО2 + (1/2) × heat of formation of Н2О × Н / С) × (1/100)} ... formula (1)

The adsorption rate, formation rate and H / C value for the solid fuel of Example A-2 are as follows.

O2 adsorption degree 0.42 [ml / kg⋅min]

CO formation degree 0.03 [ml / kg⋅min]

CO2 formation rate 0.02 [ml / kg⋅min]

H / C (molar ratio between hydrogen and carbon in solid fuel from example A-2) 1.28 [mol / mol] (see table 1)

In addition, the heat of adsorption and the corresponding heat of formation used in equation (1) are as follows.

Heat of adsorption of O2 253 [kJ / mol] (the same value as the heat of adsorption of O2 on coal)

Heat of formation of CO 110.5 [kJ / mol]

Heat of formation of Н2О 285.83 [kJ / mol]

Heat of formation of СО2 393.5 [kJ / mol]

The WIS index for solid fuel from Example A-2 was calculated based on the above, and the WIS was found to be 1.3. In this document, due to the similarity of the properties of the solid fuel based on biomass A to those of coal, the heat of adsorption of O2 was used the same as the heat of adsorption on coal.

Using the same method as that used to calculate the WIS index from Example A-2, the WIS index from Examples A-1 to A-3, A-6 and the WIS index from Example A-2 were calculated after the decay test ( see table 2, fig. 3). The calculation results are shown in FIG. 11. For comparison, FIG. 11 also shows the WIS index for bituminous coal from Table 4. The horizontal axis in FIG. 11 is the moisture content based on moisture input and the WIS value for bituminous coal in FIG. 11 is calculated for four samples that are obtained by adding water to the bituminous coal shown in Table 4 to produce four samples with different moisture levels.

A lower value of the WIS index indicates lower characteristics of spontaneous combustion, as demonstrated in formula (1). Therefore, when comparing examples from A-1 to A-3, A-6, example A-2 after the decomposition test (see table 2 and Fig. 3) and bituminous coal in the case of a comparable level of moisture content, solid biomass fuels (GDT ) of the present invention will have a lower WIS (Spontaneous Combustion Index) than bituminous coal and thus have the same WIS (Self-Combustion Index) levels as bituminous coal having a high moisture content. Accordingly, biomass solid fuel A (BST) can be said to be a good fuel exhibiting a reduced risk of ignition during handling.

Table 4

Bituminous coal Approximate Analysis Moisture level % (wt.) (based on air-dry matter) 3.3 Ash residue 12.3 Volatile matter 30.5 Bonded carbon 53.9 Higher calorific value kcal / kg (based on dry weight of fuel) 7135 Final analysis Ash residue wt% (% (mass) (based on air-dry matter) 12.8 Carbon 73.6 Hydrogen 4.5 Oxygen 6.9 Nitrogen 1.7 Combustible sulfur 0.46

[Surface Photo]

FIG. 12-14 are cross-sectional photographs taken using the SEM method for the solid fuels of Example A-2 (GDT) before and after immersion in water. FIG. 12 is a pre-dive photograph. FIG. 13 is a photograph 2 seconds after the dive, and FIG. 14 is a photograph 20 seconds after the dive. Similarly, FIG. 15-17 are cross-sectional photographs taken using the SEM method for the solid fuels of Comparative Example A (BG) before and after immersion in water. FIG. 15 is a pre-dive photograph. FIG. 16 is a photograph 2 seconds after the dive, and FIG. 17 is a photograph 20 seconds after the dive. In Example A-2 and Comparative Example A, the term "cross section after immersion" means a cross section obtained by cutting a solid fuel after 2 seconds or 20 seconds after immersion. In addition to this, magnification and scale in each case are shown at the bottom of the photographs.

Based on the comparison of photographs before and after immersion in water, the pores enlarged after immersion in water in Comparative Example A (Figs. 15-17). As suggested, since Comparative Example A (BG) is a molded product from milled biomass, the biomass absorbed water when immersed, resulting in enlarged pores (gaps between particles of pulverized biomass). Thus, it is believed that water additionally enters the enlarged pores, separating the elements of the milled biomass from each other, which causes the disintegration of the hardest fuel (see Fig. 4).

In contrast, on the surface of the solid fuel of Example A-2 (FIGS. 12-14), the pores did not expand as much even after immersion in water, and the change due to immersion was small. As suggested, in Example A-2, solid state crosslinking developed between the particulate biomass as a result of heating, and water absorption was made difficult due to improved hydrophobicity, causing little change due to immersion. Therefore, due to the retention of bonding or adhesion between the elements of the biomass that has been crushed as a result of crosslinking in the solid state, even after immersion, disintegration as in comparative example A is less likely to occur. Therefore, for the heated solid fuels of Examples A-1 to A-6 (GDT), as shown in FIG. 4, biomass-based solid fuels were obtained in which degradation was reduced by exposure to rainwater and the like, and handling characteristics during outdoor storage were ensured.

<Example B>

In Examples B-1 to B-4 (HDT), except for the use of European red pine biomass feedstock, the biomass feedstock material was heated to target temperatures (heating temperatures described in Table 5) in the same manner as and in Example A. Table 5 and Table 6 show the properties of the resulting solid biomass fuel B (Examples B-1 to B-4) obtained after the heating step. Similarly, the properties of Comparative Example C (BG) were also demonstrated. As in Example A, in Examples B-1 to B-4 and Comparative Example B, no binder was used. Since the moisture levels after immersion in water represent the corresponding characteristics after immersion for more than 100 hours (168 hours in example B), the moisture level in solid fuel B is considered to have reached equilibrium. Methods for measuring the properties of solid biomass fuels are the same as the corresponding methods described in the above example A. The grindability in a ball mill described in table 6 was measured as follows.

[Grinding capacity in ball mill]

The pulverization time for each biomass solid fuel B was 20 minutes, and the mass fraction passed through the 150 µm sieve after 20 minutes was determined as the pulverizing point. In this document, the measurement was carried out using a ball mill in accordance with JIS M4002, where in a cylindrical container having an inner diameter of 305 mm × an axis length of 305 mm, balls from conventional ball bearings were loaded in accordance with the definition in JIS B1501 (F 36 , 5 mm × 43 balls, Ф 30.2 mm × 67 balls, Ф 24.4 mm × 10 balls, Ф 19.1 mm × 71 balls and Ф 15.9 mm × 94 balls) and the container was rotated at a speed of 70 rpm ./min. A higher value indicates an improvement in grindability. It was confirmed that as the heating temperature was increased, the pulverization point increased.

Comparative example B decomposed immediately after immersion in water. In contrast, in examples B-1, B-3 and B-4, the binding or adhesion between the pulverized biomass particles is maintained even after immersion in water (168 hours), and they are not degraded. Thus, due to the retention of solid forms even after immersion, it was possible to measure the moisture content level, and thus the formation of water resistance was confirmed. In addition, in comparison with Comparative Example B, grindability is improved and the COD value is also decreased. In terms of water resistance (moisture content after immersion), the solid biomass fuels of Example B-3 are especially excellent, and in terms of yield, the solid biomass fuels of Examples B-2 and B-3 have shown particularly excellent physical properties. ...

In addition, Example B-2 is believed to have excellent water resistance and grindability based on the development of solid state crosslinking and is a fuel having a reduced COD value.

<Example C>

Except for using almond old growth tree biomass feedstock, the biomass feedstock material was heated to target temperatures (heating temperatures described in Table 5) in the same manner as in Example A (Examples C-1 to C -4: GTD). The grindability in the ball mill was measured in the same manner as in the above example B. Table 5 and Table 6 show the properties of the resulting solid biomass fuel C obtained after the heating step. Similar to Example B, since the moisture levels after immersion in water represent the corresponding characteristics after immersion for more than 100 hours (168 hours in example C), the moisture level is considered to have reached equilibrium. Likewise, the properties of Comparative Example C (BG) were also demonstrated. In Examples C-1 to C-4 and Comparative Example C, no binder was used.

Comparative example C underwent degradation immediately after immersion in water. In contrast, in Examples C-1 to C-4, the bonding or adhesion between the pulverized biomass particles was maintained even after immersion in water and did not degrade, indicating improved water resistance. In addition to this, an improvement in grindability and a decrease in the COD value are indicated. In terms of COD value and water resistance (moisture content after immersion), examples C-2, C-3 and C-4 are excellent, and examples C-1, C-2 and C-3 are excellent in terms of thermal yield. As used herein, while the RPI of Example C-1 is lower than Comparative Example C, this appears to be due to variances in feedstock material characteristics and measurement uncertainties, and therefore, as expected, Example C-1 characterized by an IRC equal to or greater than at least that of Comparative Example C.

<Example D>

With the exception of the use of a mixture in the form of (30 wt% almond shell + 70 wt% almond old growth tree) as a biomass feedstock material, the biomass feedstock material was heated to target temperatures (heating temperatures described in Table 5 ) in the same way as in example A (examples D-1 to D-4: GTD). The grindability in a ball mill was measured in the same manner as in the above example B. Table 5 and Table 6 show the properties of the resulting solid biomass fuel D obtained after the heating step. Since moisture levels after immersion in water represent the corresponding characteristics after immersion for more than 100 hours (168 hours in example D), the moisture level is considered to have reached equilibrium. Likewise, the properties of Comparative Example D (BG) were also demonstrated. In Examples D-1 to D-4 and Comparative Example D, no binder was used.

Comparative Example D decomposed immediately after immersion in water. In contrast, in Examples D-1 to D-4, the bonding or adhesion between the pulverized biomass particles was maintained even after immersion in water and did not degrade, indicating improved water resistance. In addition to this, an improvement in grindability and a decrease in the COD value are indicated. From the point of view of the COD value, examples D-2, D-3 and D-4 are excellent, and from the point of view of thermal yield, examples D-2, D-3 and D-4 are excellent. Examples D-1, D-2 and D-3 showed particularly excellent physical properties.

<Example E>

With the exception of using the xylem part of acacia as a raw material for biomass and molding it into a tablet form and except for using a tube furnace characterized by a value of ϕ70 mm, as a heating apparatus, the raw material for biomass was heated to target temperatures (heating temperatures described in table 5) in the same way as in example A, (examples E-1 to E-3: HDT). Table 5 and Table 6 show the properties of the resulting biomass solid fuel E obtained after the heating step. Since the moisture levels after immersion in water represent the corresponding characteristics after immersion for more than 100 hours (168 hours in example E), the moisture level is considered to have reached equilibrium. Likewise, the properties of Comparative Example E (BG) were also demonstrated. In Examples E-1 to E-3 and Comparative Example E, no binder was used. In example E, the pH value was measured by immersing solid fuels at a ratio between the amounts of solids and liquids of 1: 13. In this document, the immersion time from Comparative Example E in Table 6 is the time when the pH value was measured, that is, it means that that the pH was measured 96 hours after immersion of the solid fuel of Comparative Example E.

Comparative Example E decomposed immediately after immersion in water. However, in Examples E-1 to E-3, the bonding or adhesion between the pulverized biomass particles is maintained and not degraded, demonstrating water resistance. From the point of view of water resistance (moisture content after immersion), examples E-2 and E-3 are excellent, and from the point of view of thermal yield, examples E-1 and E-2 are excellent. In Example E, the above-described solid-state crosslinking also proceeds in the HDT material heated in the range of 240 to 270 ° C according to the evaluation, and therefore the water resistance, COD value and grindability and the like are considered excellent. While the thermal yield from Example E-1 is greater than 100%, this was due to variances in characteristics for raw materials and measurement errors.

<Example F>

Except for using acacia bark biomass feedstock material, the biomass feedstock material was heated to target temperatures (heating temperatures described in Table 5) in the same manner as in Example E (Examples F-1 to F- 4: GTD). Table 5 and Table 6 show the properties of the resulting solid biomass fuel F obtained after the heating step. Since the moisture levels after immersion in water represent the corresponding characteristics after immersion for more than 100 hours (168 hours in example F), the moisture level is considered to have reached equilibrium. Likewise, the properties of Comparative Example F (BG) were also demonstrated. In Examples F-1 to F-4 and Comparative Example F, no binder was used. In example F, the pH value was measured by immersion of solid fuels at a ratio between the amounts of solids and liquids of 1: 13. In this document, the immersion time of Comparative Example F in Table 6 is the time when the pH value was measured, that is, it means that that the pH was measured after 96 hours after immersion of the solid fuel of Comparative Example F.

Comparative example F underwent decomposition after one hour after immersion in water. However, in Examples F-1 to F-4, the bonding or adhesion between the pulverized biomass particles is maintained and not degraded, demonstrating water resistance. In terms of COD value and water resistance (moisture content after immersion), examples F-2, F-3, and F-4 are excellent, and examples F-1, F-2 and F-3 are excellent in terms of thermal yield.

<Example G>

Except for the use of a mixture in the form of (70 wt% almond shell + 30 wt% walnut shell) as a raw material for biomass and except for the use of a tube furnace characterized by a value of ϕ70 mm as a heating apparatus the biomass feedstock material was heated to target temperatures (heating temperatures described in Table 5) in the same manner as in Example A (Examples G-1 to G-4: HDT). Table 5 and Table 6 show the properties of the resulting biomass solid fuel G obtained after the heating step. Since the moisture levels after immersion in water represent the corresponding characteristics after immersion for more than 100 hours (144 hours in example G), the moisture level is considered to have reached equilibrium. Likewise, the properties of Comparative Example F (BG) were also demonstrated. In Examples G-1 to G-4 and Comparative Example G, no binder was used.

Comparative example G degraded immediately after immersion in water. However, in Examples G-1 to G-4, the bonding or adhesion between the pulverized biomass particles is maintained and not degraded, demonstrating water resistance. In terms of COD value and water resistance (moisture content after immersion), examples G-2, G-3, and G-4 are excellent, and examples G-1, G-2 and G-3 are excellent in terms of thermal yield. While the thermal yield of Example G-2 is greater than 100%, this was due to variation in characteristics for raw materials and measurement errors.

<Example H>

Except for being used as a sago palm biomass feedstock material, the biomass feedstock material was heated to target temperatures (heating temperatures described in Table 5) in the same manner as in Example A (Examples H-1 to H- 4: GTD). The grindability in a ball mill was measured in the same manner as in the above example B. Table 5 and Table 6 show the properties of the resulting solid biomass fuel H obtained after the heating step. Since the moisture levels after immersion in water represent the corresponding characteristics after immersion for more than 100 hours (168 hours in example H), the moisture level is considered to have reached equilibrium. Likewise, the properties of Comparative Example H (BG) were also demonstrated. In Examples H-1 to H-4 and Comparative Example H, no binder was used. In the example In this document, the immersion time of Comparative Example H in Table 6 is the time when the pH value was measured, that is, it means that the pH value was measured 24 hours after the solid fuel of Comparative Example H was immersed.

Comparative example H underwent degradation after three hours after immersion in water. However, in Examples H-1 to H-4, the bonding or adhesion between the pulverized biomass particles is maintained and not degraded, demonstrating water resistance. In terms of COD, pH (somewhat low) and water resistance (moisture content after immersion), examples H-2, H-3 and H-4 are excellent, and examples H-1, H- are excellent in terms of thermal yield. 2 and H-3.

<Example I>

Except for using the PFG material (empty fruit cluster, which is the residue from the processing of palm oil) as the biomass feedstock material, the biomass feedstock material was heated to target temperatures (heating temperatures described in Table 5) in the same manner as and in example A, (examples I-1 to I-4: HDT). Table 5 and Table 6 show the properties of the resulting solid biomass fuel I obtained after the heating step. Since the moisture levels after immersion in water represent the corresponding characteristics after immersion for more than 100 hours (168 hours in example I), the moisture level is considered to have reached equilibrium. Likewise, the properties of Comparative Example I (BG) were also demonstrated. In Examples I-1 to I-4 and Comparative Example I, no binder was used.

The mechanical resistance before and after immersion in water for Example I-3, which was heated at 270 ° C, and Example I-4, which was heated at 300 ° C, was measured using the following method. Polypropylene container for 1000 cubic meters cm was filled using 50 g of sample and rotated at 60 rpm for 30 minutes (1800 rotations in total) using a Mazemazeman (trade mark) SKH-15DT device manufactured by MISUGI LTD. The sample after rotational processing was sieved using a sieve having circular holes with a diameter of 3.15 mm, and the mechanical resistance (MS) was calculated using the following equation:

MS = (m1 / m0) × 100

In the equation, m0 is the mass of the sample before rotational processing, m1 is the remaining mass of the sample on the sieve after rotational processing.

Comparative example I decomposed immediately after immersion in water. However, in Examples I-1 to I-4, the bonding or adhesion between the pulverized biomass particles is maintained and not degraded, demonstrating water resistance. In terms of COD value and water resistance (moisture content after immersion), Examples I-2, I-3, and I-4 are excellent, and Examples I-1, I-2, and I-3 are excellent in terms of thermal yield.

<Example J>

Except for using dipterocarp as biomass feedstock material, the biomass feedstock material was heated to target temperatures (heating temperatures described in Table 5) in the same manner as in Example A (Examples J-1 and J-2: GT). Table 5 and Table 6 show the properties of the resulting biomass solid fuel J obtained after the heating step. Since moisture levels after immersion in water represent the corresponding characteristics after immersion for more than 100 hours (168 hours in example J), the moisture level is considered to have reached equilibrium. Likewise, the properties of Comparative Example J (BG) were also demonstrated. In Examples J-1 and J-2 and Comparative Example J, no binder was used.

Comparative Example J decomposed immediately after immersion in water. However, in Examples J-1 and J-2, the bonding or adhesion between the pulverized biomass particles is maintained and not degraded, demonstrating water resistance. Excellent results were also obtained for the COD value.

<Example K>

Except for using a rubber wood biomass feedstock and excluding using a tube furnace having a ϕ70 mm value as a heating apparatus, the biomass feedstock material was heated to target temperatures (heating temperatures described in Table 5) by the same way, as in example A, (example K-1). Table 5 and Table 6 show the properties of the resulting biomass solid fuel K obtained after the heating step. Likewise, the properties of Comparative Example K (BG) were also demonstrated. In the Examples and Comparative Example, no binder was used.

Comparative example K is believed to undergo degradation by immersion in water, like the other comparative examples. On the other hand, presumably, Example K-1 is not subject to degradation even by immersion in water due to the aforementioned solid crosslinking, and an improvement in grindability, a decrease in COD value, and the like will be obtained. While Example K-1 was heated at 270 ° C, the same effect is expected for a heating temperature in the range of 230 to 270 ° C in the same manner as described above.

<Water absorption distribution>

In order to compare the water resistance of HPT and HDT materials, the distribution of sodium in solid fuels based on biomass after water absorption using a physiological saline solution was considered. As a sample of the HPT material, a solid fuel obtained by heating the European red pine feedstock material at 250 ° C. and molding into pellets having a diameter of 6 mm was used. Solid fuel (solid fuel B) obtained by molding the European red pine feedstock material into pellets having a diameter of 6 mm and heating them at 250 ° C was used as a sample of the gas turbine engine material. The HDT and HPT materials were immersed in physiological saline solution at 0.9% (w / w) for 5 days. As a result, as the appearance of the granules in FIG. 24, the HDT material retained its granular shape (FIG. 24, left), while the HPT material underwent significant degradation (FIG. 24, right). In addition, for each material selected from HPT and HDT materials, samples before and after immersion in physiological saline solution at 0.9% (w / w) for 5 days were analyzed in their cross-section as part of the analysis using the EPMA method (Electron Probe MicroAnalyser) to compare the Na distribution. In the HDT material, the Na distribution remains on the surface of the granules and does not penetrate into their inner space, while in the HPT material, Na is widely distributed in the inner space of the granules (see Fig. 25). This means less penetration of physiological saline into the HDT material as compared to the HPT material. As it is assumed on the basis of this result, in the HDT material, the products of thermal decomposition of the extracted components produce crosslinking in the solid state in the gap between the adjacent particles of pulverized biomass and become hydrophobic, which prevents the penetration of water, while in the HPT material, due to the presence of water the possibility of penetration into the gap between the particles of the powdered biomass, water penetrates into the inner space of the granules and expands the gaps between the particles of the powdered biomass, which leads to decomposition.

[Degree of expansion before and after immersion in water]

The pellet lengths of solid fuels from examples A-1 and A-3 were measured before and after immersion in water. For pellet length, ten pellets were selected before immersion and their length was measured using an electronic gauge (manufactured by Mitutoyo: CD-15CX, reproducible accuracy is 0.01 mm and the second decimal place was rounded off) and again the length of the same pellets was measured using electronic gauge after 72 hours of immersion in water. In the case of a diagonal for the end of the granule, before and / or after immersion, the length was measured up to the outermost portion of the end. Table 7 shows the measurement results. As shown in Table 7, the pellet length in example A-1 increased by 4.6% on average, while in example A-3 it increased by 0.2% on average.

Table 7

L1 (mm) before immersion L2 (mm) 72 hours after dive (Medium) length expansion ratio Example A-1 Example A-3 Example A-1 Example A-3 Example A-1 Example A-3 17.4 18.9 20.1 15.9 {(L2 - L1) / L1} × 100% 17.9 18.7 17.1 18.1 19.8 17.9 20.8 13.5 16.5 17.5 18.0 17.5 19.7 15.0 19.5 17.7 18.0 13.8 18.6 14.7 18.1 16.2 19.6 18.9 20.2 17.8 19.7 17.6 17.5 17.4 18.2 19.0 18.2 14.9 20.1 15.6 average 18.33 on average 16.81 average 19.17 on average 16.85 4.6 0.2

Note: In Table 7, the values in the same row do not correspond to the same pattern.

In addition, using the same electronic gauge and the same measurement method as in Table 7, the pellet diameters for solid fuels of Examples A-1 to A-6 were measured before and after immersion in water. Table 8 shows the measurement results. The measured value for the diameter of the pellet is the average of ten samples, randomly selected, respectively, from examples A-1 to A-6.

Table 8

Before immersion in water After immersion in water Expansion ratio of diameter {(φ2 - φ1) / φ1} × 100% Initial diameter φ1 (mm) Time (h) Φ2 size (mm) Comparative example A Φ 8.0 24 - - Example A-1 Φ 7.8 168 Φ 8.4 7,7 Example A-2 Φ 7.7 168 Φ 8.1 5.2 Example A-3 Φ 7.5 168 Φ 7.8 4.0 Example A-4 Φ 7.5 168 Φ 7.7 2.7 Example A-5 Φ 7.3 168 Φ 7.5 2.7 Example A-6 Φ 7.2 144 Φ 7.3 1.4

As indicated in Table 7 and Table 8, a higher temperature in the heating step results in a lower expansion ratio. Expansion appears to be inhibited by passing solid state crosslinking due to heating. While the diameter expansion ratio from Table 8 is greater than the length expansion ratio from Table 7, this appears to be due to the longer immersion times in Table 7, and also due to the pellet shape in Example A, which was mainly compacted. in the radial direction, and therefore the expansion in the radial direction becomes large. As it should be noted, in Table 8, the diameter expansion ratio remains at 10% or less even in Example A-1, which is characterized by the largest expansion ratio. In example A, the expansion ratios of diameter and length are preferably 10% or less, and more preferably 7% or less. The volume expansion ratio is preferably 133% or less, and more preferably 123% or less.

While Table 7 and Table 8 show the expansion ratios from Example A, the expansion ratios from Examples B to J will be calculated based on the results from Table 6. The expansion ratio was calculated using the following equation (2) which was used for the example BUT.

Expansion ratio = {(value after dive - value before dive) / value before dive} × 100 ... (2)

Example B is in the form of granules, and thus the degree of expansion of the diameter was calculated based on equation (2) using the granule diameter before immersion (original dimensions from Table 6) and the diameter of the granules after immersion (size after immersion from Table 6), and the result is 15% or less (note that equation (2) is used to calculate the expansion ratios of the diameter of Example B below in this document). Since the ratio of the length expansion ratio <the diameter expansion ratio can be estimated for the pellet shape as in Example A, the length expansion ratio of Example B can be up to 15% or less. Thereafter, the volume expansion ratio is calculated to be 152% or less (volume after immersion in relation to the volume of 100% before immersion; and the same applies to the following examples C and below in this document). In example B, the expansion ratio of the diameter is preferably 20% or less, and more preferably 10% or less. The volume expansion ratio is preferably 173% or less, and more preferably 133% or less.

Example C is also in the form of granules, the expansion ratio of the diameter before and after immersion is 7.2% or less, and the expansion ratio of the length is 7.2% at the most; and thus, the volume expansion ratio is 123% or less (the volume expansion ratio for granules in the following examples will be calculated in the same way). In Example C, the diameter expansion ratio is preferably 13% or less, and more preferably 7% or less. The volume expansion ratio is preferably 144% or less, and more preferably 123% or less.

In Example D (in the form of pellets), the diameter expansion ratio before and after immersion is 8.8%, and the volume expansion ratio based on it is 129% or less. In Example D, the diameter expansion ratio is preferably 10% or less, and more preferably 8% or less. The volume expansion ratio is preferably 133% or less, and more preferably 126% or less.

Example E is in the form of tablets, the diameter expansion ratio (ϕ) is 2.5% or less, the height expansion ratio (H) is 40% or less, and the volume expansion ratio is 147% or less. The expansion ratio of the diameter is preferably 5% or less, and more preferably 2.3% or less. The height expansion ratio is preferably 50% or less, more preferably 20% or less. The volume expansion ratio is preferably 165% or less, and more preferably 126% or less.

In Example F (in the form of tablets), the diameter expansion ratio is 4.0% or less, the height expansion ratio is 15% or less, and the volume expansion ratio is 124% or less. In this document, the post-dive altitude of Example F-3 appears to be the result of measurement uncertainty or variation due to individual differences. The expansion ratio of the diameter is preferably 5% or less, more preferably 3% or less. The height expansion ratio is preferably 40% or less, and more preferably 10% or less. The volume expansion ratio is preferably 154% or less, and more preferably 117% or less.

In Example G (in the form of pellets), the diameter expansion ratio before and after immersion is 8.8% or less, and the volume expansion ratio based on it is 129% or less. The expansion ratio of the diameter is preferably 10% or less, and more preferably 8% or less. The volume expansion ratio is preferably 133% or less, and more preferably 126% or less.

In Example H (in the form of pellets), the diameter expansion ratio before and after immersion is 6.9% or less, and the volume expansion ratio based on it is 122% or less. The expansion ratio of the diameter is preferably 10% or less, and more preferably 7% or less. The volume expansion ratio is preferably 133% or less, and more preferably 123% or less.

In Example I (in the form of pellets), the diameter expansion ratio before and after immersion is 4.1% or less, and the volume expansion ratio based on it is 113% or less. The expansion ratio of the diameter is preferably 10% or less, and more preferably 5% or less. The volume expansion ratio is preferably 133% or less, and more preferably 116% or less.

In Example J (in the form of pellets), the diameter expansion ratio before and after immersion is 5.4% or less, and the volume expansion ratio based on it is 117% or less. The expansion ratio of the diameter is preferably 20% or less, and more preferably 10% or less. The volume expansion ratio is preferably 173% or less, and more preferably 133% or less.

In accordance with the above description of the invention, for solid fuels (HDF) of the present invention using biomass as a feedstock material, the ratio of length expansion (including diameter and height) before and after immersion is preferably 40% or less in each case, and the volume expansion ratio is preferably about 275% or less. In addition, it is more preferable when the expansion ratios of the diameter and length are 30% or less, and the volume expansion ratio is about 220% or less. However, in addition, it is more preferable when the expansion ratio of the diameter and length is 20% or less, and the expansion ratio of the volume is about 173% or less. However, in addition, it is more preferable when the expansion ratios of the diameter and length are 10% or less, and the volume expansion ratio is about 133% or less. If the expansion ratio after immersion in water is within a certain range corresponding to the above, the solid biomass fuel (BST) will not decompose even by immersion, which demonstrates its water resistance.

For each raw material based on rubber wood, acacia, and dipterocarp, a HDT material was separately prepared and tested. The test results are shown in Tables 9 and 10 below. In the test results from Tables 9 and 10, the rubber tree is described as example a, acacia as example b, and dipterocarp as example c.

NUMERIC DESIGNATIONS OF REFERENCE POSITIONS

1 CARBONIZATION OVEN

2 VIBRATION CONVEYOR

11 THERMOMETER

21 COARSE SORTING SECTION (COARSE SORTING DEVICE)

22 COOLING SECTION (COOLING DEVICE)

22a SPRAY SECTION (WATER SPRAYER)

22b FLAT PLATE

24 SECTION SECTION

30 CONTROL SECTION (CONTROL UNIT)

100 STAGE OF FUEL PRODUCTION

110 STAGE OF GRINDING INTO POWDER

120 STAGE OF FORMATION

130 HEATING STAGE

200 STAGE SORT BY LARGEST

300 COOLING STAGE

402 SYSTEM

403A APPARATUS WITH VIBRATING Sieve

403V COOLING VIBRATION CONVEYOR

421 LARGE SORTING SECTION

421a SITO

421b OUTLET

422 COOLING SECTION

422a WATER SPRAY SECTION

422b FLAT PLATE

Claims (15)

1. Apparatus for cooling carbonized biomass, containing: a carbonization furnace for producing carbonated biomass by carbonizing molded biomass, a sizing device downstream of the carbonation furnace for sizing carbonated biomass, and a cooling device located downstream of the sizing device for cooling the sorted carbonated biomass, in which the molded biomass is obtained by molding the pulverized biomass feedstock without a binder, and The cooling device cools the carbonated biomass by spraying water on it. 2. Equipment according to claim 1, in which the cooling device comprises a vibrating flat plate and a spray section for spraying water onto the flat plate, wherein the flat plate is a metal plate or a resin plate, and the carbonated biomass is conveyed by vibration. 3. Apparatus according to claim 1 or 2, additionally containing a thermometer designed to measure the temperature at the outlet of the carbonation oven, and a control device for stopping the spraying device when the temperature measured by the thermometer matches a predetermined value or less. 4. Apparatus according to claim 3, wherein the thermometer is configured to directly measure the temperature of the carbonated biomass. 5. Apparatus according to claim 1, further comprising a separation section for separating the sizing apparatus and the cooling apparatus. 6. Apparatus according to claim 1, wherein the carbonization furnace is configured to carbonize the molded biomass at a temperature of 150 to 400 ° C.

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