KR20180133445A - Cooling system of biomass carbide - Google Patents

Abstract

A carbonization furnace for carbonizing the biomass formed body to obtain biomass carbide; a classification unit installed on the downstream side of the carbonization furnace to classify the biomass carbonized material; And a cooling means for cooling the mass carbide. The biomass formed body is a compact obtained by pulverizing raw material biomass and molding the same, and the cooling means cools the biomass carbide by spraying.

Description

Cooling system of biomass carbide

The present invention relates to a cooling apparatus for biomass carbide.

Conventionally, in Patent Document 1, the pulverized biomass is semi-carbonized by heating while heating to obtain a biocoke having high strength.

Japanese Patent No. 4088933

However, in the above-described Patent Document 1, there is a problem that the cooling efficiency is low because it is cooled in a pressurized state after molding and natural cooling by the atmosphere. Even if cooling is carried out by water cooling to improve the cooling efficiency, water cooling in a pressurized state is difficult, and since the biocosm is a biomass formed after the pulverization, part of the biomac is differentiated and becomes difficult to handle. Particularly, in the case of an abnormal state in which heating is not performed, there is a fear that the formed bio-coke collapses and the equipment is clogged. Or for simplification, it is cooled by putting it in a water tank after it is carbonized (heated), the biomass solid fuel becomes suspended because it has a light specific gravity and becomes cumbersome.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to reduce facility clogging while efficiently cooling the semi-carbonized biomass molding.

The present invention provides a method for producing biomass, comprising the steps of: a carbonization furnace for carbonizing a biomass formed body to obtain biomass carbide; a classification unit disposed downstream of the carbonization furnace for classifying the biomass carbonized material; And a cooling means for cooling the classified biomass carbide, wherein the biomass formed body is a formed body obtained by pulverizing raw material biomass and molding the cooled biomass, and the cooling means cooling the biomass carbide by spraying .

According to the present invention, the cooling of the semi-carbonized biomass formed body is efficiently performed while reducing facility clogging.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing the solid-temperature-COD, pH of a biomass solid fuel.
2 is a graph showing the correlation between the solid temperature in the heating process and the grindability and grinding speed of the obtained biomass solid fuel.
3 is a graph showing the particle size distribution of the biomass solid fuel subjected to the differentiation test.
FIG. 4 is a diagram showing the result of immersion test (solid water content) of the biomass solid fuel. FIG.
5 is a graph showing solid strength (rotational strength) before and after immersion in water.
6 is a graph showing the solid strength (mechanical durability) before and after immersion in water.
7 is a diagram showing the BET specific surface area of the solid fuel.
8 is a view showing the average pore diameter of the solid fuel surface.
9 is a view showing the total pore volume of the solid fuel surface.
10 is a diagram showing the yield of the biomass solid fuel.
11 is a diagram showing the natural exothermicity index (SCI) of the biomass solid fuel.
Fig. 12 is a cross-sectional photograph before immersion in water in Example A-2. Fig.
13 is a cross-sectional photograph of Example A-2 after immersion in water (2 seconds).
14 is a cross-sectional photograph of Example A-2 after immersion in water (20 seconds).
15 is a cross-sectional photograph of Comparative Example A before immersion in water.
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 mechanism (estimation) of the high (solid) crosslinking development in PBT.
19 is a view showing FT-IR analysis results of the outer surface of the pellet of the biomass solid fuel.
20 is a view showing FT-IR analysis results of the cross-sectional center of the pellet of the biomass solid fuel.
21 is a view showing FT-IR analysis results of acetone extract of biomass solid fuel.
22 is a graph showing FT-IR analysis results of a solid after extracting acetone from a biomass solid fuel.
23 is a graph showing the GC-MS analysis result of the acetone extract of the biomass solid fuel.
24 is a diagram showing a pellet shape after immersion in physiological saline in Example B. Fig.
25 is a view showing the distribution of sodium before and after immersion in physiological saline in Example B. Fig.
26A is a schematic view showing a cooling facility of biomass carbide.
26B is a schematic view showing another example of a cooling facility for biomass carbide
27 is a diagram showing the process flow of the present invention.
28 is a diagram showing a control flow.

[Embodiment Mode]

26A is a schematic view of the present invention, and FIG. 27 is a process flow. The biomass solid fuel obtained by the fuel producing process 100 of FIG. 27 becomes a product through the classification step 200 and the cooling step 300.

In the fuel manufacturing process 100, a biomass solid fuel is produced using known methods. The raw material biomass is subjected to crushing and crushing process 110 and then formed in a forming process 120 and then heated in the heating process 130 using the kiln 1 shown in Fig. 26A. In the molding step 120, a binder such as a binder is not added, and the biomass powder is simply formed by compressing and pressing the biomass powder.

The unvulcanized white pellets (hereinafter referred to as WPs) immediately after the molding step 120 are low in strength because they are simply subjected to pressure molding of the biomass component, and are easily differentiated during handling. It also expands due to absorption and collapses.

In the fuel producing process 100 of the present invention, the biomass molded body is heated (low-temperature carbonized) in the heating step 130 (kiln (1)) at 150 to 400 ° C to maintain the strength and water resistance (Hereinafter referred to as " Pelletizing Before Torrefaction ") is produced. Further details of the fuel manufacturing process 100 will be described later.

The classification step 200 and the cooling step 300 are performed using the vibration conveyor 2 of Fig. 26A. The vibratory conveyor 2 is divided into two compartments by a partition plate 24 and serves as a classifier 21 and a cooling unit 22 respectively. The PBT discharged from the kiln 1 is conveyed by being pushed out by the vibration of the flat plate 22b and the PBT supplied sequentially from the kiln 1 and discharged as a product through the classifying portion 21 and the cooling portion 22 . Further, although the vibration conveyor 2 shown in Fig. 26A is inclined, it may be a horizontal non-inclined conveyor.

In the distributor 21, the PBT is oscillated on the sieve 21a to classify the PBT and the derivative (classification step 200). The eye size of the sieve 21a may be appropriately changed according to a desired value. A small PBT that has collapsed during manufacture or does not reach a predetermined size falls down under the body 21a and is processed separately. The PBT remaining on the body 21a moves to the cooling section 22. [

The cooling section 22 has a water spraying section 22a and a vibrating flat plate 22b and water spraying section 22a sprinkles water on the flat plate 22b. (Cooling process 300) is performed by spraying the PBT on the flat plate 22b, and the product is discharged as a product. Further, cooling may be performed only, or an air nozzle or the like may be provided in addition to the water spraying portion 22a, and cooling by air may be used in combination. Also, the water spray nozzle may be a two-fluid nozzle of air + water.

The flat plate 22b is a flat plate without holes or unevenness, and a metal plate or a resin plate is used. By making the plate smooth, the PBT in the cooling portion 22 is easily slipped, and the movement in the cooling portion 22 is smooth.

In addition, since the partition plate 24 is spaced between the classifying portion 21 and the cooling portion 22, the water sprinkled in the cooling portion 22 is prevented from entering the partition portion 21. As a result, absorption of the fine particles classified in the classifying portion 21 is suppressed, and clogging in the classifying portion 21 can be reduced.

A thermometer 11 is installed at the exit of the kiln 1, and the control unit 30 executes or stops spraying based on the measured temperature. Further, the thermometer 11 may be located at another position as long as the temperature of the kiln 1 can be measured.

In the present invention, PB is obtained by heating the WP in the kiln (1) for the first time. However, when the temperature of the kiln (1) is lower than the predetermined value, WP, The biomass formed body with insufficient water resistance is discharged from the kiln 1. When they are supplied to the vibration conveyor 2, the water spraying portion 22 expands or collapses due to absorption due to the lack of water resistance, which causes the equipment clogging.

Therefore, when the temperature measured by the thermometer 11 is lower than the predetermined value, it is determined that the temperature is insufficient for manufacturing the PBT, and the controller 30 stops spraying the sprayer 22a. As a result, even when the WP or the PBT having insufficient heating is discharged when the temperature of the kiln 1 is low, the collapse of the water spraying portion 22 can be suppressed and the facility clogging can be reduced.

Fig. 28 is a flowchart of spraying on / off based on temperature, which is executed by the control unit 30. Fig. In step S1, the thermometer 11 measures the exit temperature T of the kiln (1). In step S2, whether or not the measured temperature T is equal to or smaller than the predetermined value? Is determined. If YES, watering is stopped in step S3, and if NO, watering is executed in step S4.

Particularly, when the temperature of the kiln 1 is low or the temperature is low, for example, when the kiln 1 is in an unsteady state, WP or unheated biomass compact is discharged from the kiln 1, thereby suppressing collapse and facility clogging Lt; / RTI >

When the kiln 1 is stopped and the temperature becomes lower than a predetermined value, the WP is stopped in the kiln 1 when the conveyance of the WP in the kiln 1 is stopped. In this case, even if the temperature is lowered, the carbonization of the WP proceeds and a large amount of pyrolysis gas is generated, and gas treatment is required, which is troublesome. Further, the excessively carbonized WP is disadvantageous as a fuel because the amount of residual volatile matter is small, and the number of steps is further increased because it is necessary to separately treat the WP. Therefore, stopping the conveyance in the kiln 1 is not preferable.

On the other hand, even when the supply of WP is cut off at low temperature, if the conveyance in the kiln 1 is continued, the WP or the biomass formed body with insufficient heating is discharged. Therefore, even if the temperature is low, the transportation is not stopped, thereby avoiding the generation of a large amount of pyrolysis gas and excessive carbonization, and stopping spraying of the discharged WP to inhibit clogging.

The thermometer 11 directly measures the temperature of the PBT at the exit of the kiln (1), not the ambient temperature at the exit of the kiln (1). In the present invention, PB is solidified and carbonized at a predetermined temperature or higher to obtain a PBT (solid fuel) having water resistance and strength. However, excessively increased temperature leads to deterioration of the yield of heat by advancing carbonization more than necessary. High-temperature carbonization is performed by directly measuring the temperature of the PBT, since strict temperature control is required in order to exhibit water resistance and strength while ensuring maximum heat yield. The thermometer 11 may be a contact type thermometer or a noncontact type thermometer such as an infrared ray as long as the temperature of the PBT at the exit of the kiln 1 can be directly measured.

[effect]

(1) a kiln (1) (carbonization furnace) for obtaining a biomass carbide (PBT) by carbonizing a biomass formed body, and a distributor (2) disposed on the downstream side of the kiln (1) for classifying biomass carbide And a cooling section 22 (cooling means) provided on the downstream side of the classifying section 21 for cooling the classified biomass carbide (PBT) 21,

The biomass molded body is a molded body obtained by crushing the raw material biomass and molding it, and the cooling portion 22 cools the biomass carbide (PBT) by water spraying.

When the biomass carbide is cooled by immersion in water, handling is difficult because the biomass carbide floats on the water and diffuses to the water surface. On the other hand, even when cooled by water spraying, the biomass formed body is likely to be differentiated again because the pulverized material is molded. If the biomass is cooled, the biomass powder may be absorbed and the equipment may be clogged. Therefore, clogging can be avoided by spraying after classification. In addition to water spraying, air cooling and water spraying may be used in combination, or a two-fluid nozzle of air + water may be used.

(2) The cooling section 22 has a vibrating flat plate 22b (flat plate) and a water spraying section 22a sprinkled on the flat plate 22b. The flat plate 22b is a metal plate or a resin plate, To transport the biomass carbide (PBT).

Since the biomass carbide (PBT) partially collapses during transportation, the biomass carbide of a small diameter remains to a certain degree even after classification. Small diameters are liable to adhere to each other due to water spraying, which makes handling during transportation difficult. When the biomass carbide is cooled on the mesh in consideration of the drainage, the biomass carbide sprinkled by the irregularity resistance of the mesh is deposited, and the conveyance becomes inefficient and there is a fear of clogging. Therefore, by using a metal plate or a resin plate with low sliding resistance against biomass carbide, it is possible to reduce the resistance at the time of transportation and carry out efficient transportation.

(3) When the outlet temperature of the kiln 1 is equal to or lower than a predetermined value, a control unit 30 (control means) for stopping spraying water spraying unit 22a is provided. Since the kiln 1 is at a low temperature below a predetermined value (low temperature insufficient for producing PBT) in an abnormal state such as at the time of starting and stopping, the unburnt biomass formed body WP or the carbonization is insufficient, The biomass molded bodies are discharged, but they swell and collapse due to water spray, which may cause clogging of the facility. Therefore, spraying can be stopped to prevent clogging.

(4) The thermometer 11 made it possible to directly measure the temperature of the biomass carbide (PBT). Carbonization of WP at a predetermined temperature or higher results in PBT (solid fuel) having water resistance and strength, while excessive carbonization deteriorates the yield of heat. Therefore, by directly measuring the temperature of the PBT, high-precision carbonization can be carried out, and water resistance and strength can be obtained while ensuring the heat yield.

(5) A spacing part (24) for separating the classifying part (22) and the cooling part (23) is provided. By separating them, infiltration of water spray into the partition portion 22 can be reduced, and deposition and closure during classification can be suppressed.

The classification process and the cooling process may be performed using a system as shown in Fig. 26B instead of the vibration conveyor 2 in the above-described mode. The system 402 includes a vibrating body device 403A and a cooling vibration conveyor 403B. The vibrating body device 403A and the cooling vibrating conveyor 403B are formed separately and the vibrating body device 403A is disposed on the upstream side of the PBT conveying direction and the cooling vibration conveyor 403B is disposed on the downstream side. Further, in order to avoid redundant description of the functions and structures common to the configuration of Fig. 26A, description thereof will be omitted.

The vibrating body device 403A has a classifying portion 421 provided with a body 421a. On the body 421a, PBT is supplied from a rotary kiln (not shown in Fig. 26B) similarly to the construction of Fig. 26A. The PBT is conveyed while oscillating on the body 421a, so that classification (classifying step) of the PBT and the differential is performed. Further, although the oscillator device 403A in the drawing is inclined, it may be a horizontal one that is not inclined.

It is the same as the above-described embodiment that the eye size of the body 421a can be appropriately changed in accordance with a desired value. A small PBT that has collapsed during manufacture or does not reach a predetermined size falls down under the body 421a and is separately processed. The PBT remaining on the body 421a is discharged from the discharge portion 421b of the vibrating body device 403A.

The cooling vibration conveyor 403B has a cooling section 422 provided with a water spraying section 422a and a vibrating flat plate 422b and the like and PBT from the vibrating body apparatus 403A is supplied onto the flat plate 422b . Although not shown, the cooling oscillation conveyor 403B is also provided with a control section for controlling the operation of the water spraying section 422a and the like as in the configuration of Fig. 26A. The flat plate 422b is, for example, a flat plate without holes or irregularities, and a metal plate or a resin plate is used. By making the plate smooth, the PBT is easy to slide, and the movement is smooth. Although the cooling vibration conveyor 403B in the drawing is inclined, it may be a horizontal non-inclined conveyor.

Also in this example, cooling may be carried out only, or air cooling may be used in combination. The water spray nozzle may be a two-fluid nozzle of air + water. In the same manner as in the above-described embodiment, when the temperature measured by the thermometer 11 (see Fig. 26A) of the kiln 1 is lower than the predetermined value, the water spraying by the water spraying portion 422a is controlled to be stopped It is preferable in one form. It is to be noted that the technical matters disclosed as Fig. 26B can be combined with, or substitute with, the contents disclosed as other forms, so long as they do not depart from the spirit of the present invention.

The production method of the biomass solid fuel (PBT) produced in the above-described fuel production process 100 will be described in detail as follows.

[Production of biomass solid fuel (PBT) in a fuel production process]

The biomass solid fuel is produced by crushing the biomass after crushing the biomass, compressing and molding the biomass which is in the form of crumb or powder to form a mass, a heating step of heating the mass after the molding process, It is fueled by water (equivalent to the PBT described below). This biomass solid fuel does not require a process of steam explosion and a binder, so that an increase in cost can be suppressed. In the present specification, the mass obtained by the molding process and before the heating process is also referred to as " unheated mass product ". This unheated mass corresponds to the above-mentioned WP.

The biomass to be used as the raw material may be of woody or supersaturated type, and species and parts thereof are not particularly limited. Examples of the biomass include, but are not limited to, bean sprout, hempseed, cedar, cypress, European sprouts, almonds, almond bark, , An acacia bark, a walnut shell, an accident palm, an EFB (empty fruit bun), a melancholic tree, and a rubber tree, and one of these may be a mixture of two or more species .

 In the forming process, it is made into a bulk material using known molding techniques. The mass water is preferably pellets or briquets, and the size is arbitrary. In the heating step, the molded mass is heated.

 It is preferable that the biomass solid fuel obtained after the heating step has a chemical oxygen demand (COD) of 3000 ppm or less in the immersion index when immersed in water. Further, it is preferable that the biomass solid fuel has a COD ratio of 0.98 or less, which is expressed as COD of biomass solid fuel after heat treatment or COD of biomass solid fuel of unheated heat. Here, the COD (chemical oxygen demand) (also simply referred to as "COD") of the saliva index when the biomass solid fuel was immersed in water was used to prepare a sample of the saliva index for COD measurement in 1973, (A) COD value measured in accordance with JIS K 0102 (2010) -17, which is carried out according to the method of assaying metals contained in industrial wastes.

The biomass solid fuel obtained after the heating step has a grindability index (HGI) of 15 or more and 60 or less, more preferably 20 or more and 60 or less, based on JIS M 8801. Further, the BET specific surface area is preferably 0.15 to 0.8 m ² / g, more preferably 0.15 to 0.7 m ² / g. The equilibrium water content after immersion in water is preferably 15 to 65 wt%, more preferably 15 to 60 wt%.

The biomass solid fuel has a fuel ratio (fixed carbon / volatile matter) of 0.2 to 0.8, a drying reference upper heating value of 4800 to 7000 (kcal / kg), a molar ratio O / C of 0.1 to 0.7 of oxygen O and carbon C, The molar ratio H / C of carbon C is 0.8 to 1.3. When the physical property value of the biomass solid fuel is within the above range, the COD in the waste water at the time of storage can be reduced while the differentiation can be reduced, and the handling property at the time of storage can be improved. The biomass solid fuel can be obtained, for example, by adjusting the species of the biomass used as the raw material, the site, and the heating temperature in the heating process. Industrial analysis values, elemental analysis values, and high calorific values in this specification are based on JIS M 8812, 8813, and 8814.

A method of producing a biomass solid fuel includes a forming step of obtaining a unheated mass by molding a biomass powder of crushed and pulverized biomass and a heating step of heating the unheated mass to obtain a heated solid, The heating temperature in the heating step is preferably 150 ° C to 400 ° C. By setting the temperature of the heating process within this range, a biomass solid fuel having the above characteristics can be obtained. The heating temperature is appropriately determined depending on the shape and size of the biomass and the mass of the raw material, but is preferably 150 to 400 占 폚, more preferably 200 to 350 占 폚. More preferably 230 to 300 占 폚. More preferably 250 to 290 ° C. The heating time in the heating step is not particularly limited, but is preferably 0.2 to 3 hours. The particle size of the biomass powder is not particularly limited, but an average thereof is about 100 to 3000 占 퐉, preferably 400 to 1000 占 퐉 on average. In addition, a known measuring method may be used for measuring the particle size of the biomass powder. As described later, in the case of the biomass solid fuel (PBT), the connection or adhesion between the biomass powders is maintained by high-bridging, so that the particle size of the biomass powders is not particularly limited as long as it is within the moldability range. In addition, since fine pulverization is a factor of raising the cost, it may be in a known range if the particle size is within a range in which cost and formability are both compatible.

When the bulk density of the unheated mass before the heating process is A and the bulk density of the heated solid after the heating process is B, B / A is preferably 0.7 to 1. The value of the bulk density A is not particularly limited as far as it is a known range in which a unheated mass can be obtained by molding the biomass powder. In addition, the bulk density may vary depending on the kind of the raw material biomass, so that it may be appropriately set. When HGI (hard graph crushability index of JIS M 8801) of the unheated mass is H1 and HGI of the heated solid is H2, it is preferable that H2 / H1 = 1.1 to 2.5. Heating is performed so that the value of one or both of B / A and H2 / H1 is within this range to reduce the COD in the wastewater at the time of storage and to improve the handling property at the time of storage to obtain a biomass solid fuel .

The characteristics of the biomass solid fuel may be determined in accordance with the species of the biomass used as the raw material. Hereinafter, an example thereof will be described, but the present invention is not limited to these species and combinations thereof. Hereinafter, the preferred ranges for the kinds of the biomass raw materials used in the present invention, the properties of the obtained solid fuel (corresponding to PBT described later), and the production method thereof are respectively shown.

[Types of raw biomass and properties of solid fuel]

(Dong, Hemp, cedar and cypress: solid fuel A)

As an aspect of the present invention, the characteristics of the biomass solid fuel (hereinafter, sometimes referred to as solid fuel A) in the case where the raw material contains at least one species selected from the group consisting of untransformed, Hemisphere, cedar, same.

The content of COD is preferably 1000 ppm or less, more preferably 900 ppm or less, and even more preferably 800 ppm or less. The COD ratio is preferably 0.80 or less, more preferably 0.70 or less, and even more preferably 0.68 or less.

But it is preferably 15 wt% to 45 wt%, more preferably 18 wt% to 35 wt%, and even more preferably 18 wt% to 32 wt% with respect to the equilibrium water content (described later) after immersion in water.

That the BET specific surface area of 0.25m ² / g to 0.8m ² / g is desirable and, 0.28m ² / g to 0.6m ² / g is preferable, and more than 0.32m ² / g to 0.5m ² / g More preferable.

The HGI is preferably 20 to 60, more preferably 20 to 55, and even more preferably 22 to 55. Considering that HGI of coal (bituminous coal) suitable for power generation boiler fuel is about 50 and mixed and pulverized with coal, the closer to 50, the better. The HGI ratio (to be described later) is preferably 1.0 to 2.5.

The fuel ratio is preferably 0.2 to 0.8, more preferably 0.2 to 0.7, still more preferably 0.2 to 0.65.

The higher calorific value on the drying basis is preferably 4800 to 7000 kcal / kg, more preferably 4900 to 7000 kcal / kg, and even more preferably 4950 to 7000 kcal / kg.

The molar ratio O / C of oxygen O to carbon C is preferably from 0.1 to 0.62, more preferably from 0.1 to 0.61, still more preferably from 0.1 to 0.60.

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

The preferred ranges of properties of the solid fuel A are described above.

Further, when producing the solid fuel A, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 210 to 330 占 폚, and still more preferably 220 to 300 占 폚.

(European shipment: solid fuel B)

As one form of the present invention, the characteristics of the biomass solid fuel (hereinafter sometimes referred to as solid fuel B) when the raw material is the European feed is as follows.

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

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

That the BET specific surface area of 0.30m ² / g to 0.7m ² / g is desirable and, 0.30m ² / g to 0.6m ² / g is preferable, and more than 0.30m ² / g to 0.5m ² / g More preferable.

The HGI is preferably 25 to 60, more preferably 30 to 55, still more preferably 35 to 55. The HGI ratio (to be described later) is preferably 1.0 to 2.5.

The fuel ratio is preferably 0.2 to 0.8, more preferably 0.2 to 0.7, still more preferably 0.2 to 0.65.

The higher calorific value of the drying standard is preferably 4950 to 7000 kcal / kg, more preferably 5000 to 7000 kcal / kg, and still more preferably 5100 to 7000 kcal / kg.

The molar ratio O / C of oxygen O to carbon C is preferably from 0.1 to 0.60, more preferably from 0.2 to 0.60, still more preferably from 0.3 to 0.60.

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

The preferred ranges of properties of the solid fuel B are described above.

Further, when producing the solid fuel B, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 220 to 300 占 폚, and still more preferably 240 to 290 占 폚.

(Almond tree: solid fuel C)

As one form of the present invention, the characteristics of the biomass solid fuel (hereinafter sometimes referred to as solid fuel C) when the raw material is an almond old tree are as follows.

The COD ratio is preferably 2100 ppm or less, more preferably 2000 ppm or less, more preferably 1500 ppm or less, and the COD ratio is preferably 0.80 or less, more preferably 0.75 or less, and still more preferably 0.55 or less.

The equilibrium water content after immersion in water is preferably 25 wt% to 60 wt%, more preferably 30 wt% to 50 wt%, and still more preferably 30 wt% to 45 wt%.

That the BET specific surface area of 0.20m ² / g to 0.70m ² / g is desirable and, 0.22m ² / g to 0.65m ² / g is desirable and, 0.25m ² / g to 0.60m ² / g than More preferable.

It is preferably 15 to 60, more preferably 18 to 55, and even more preferably 20 to 55 for HGI. The HGI ratio (to be described later) is preferably 1.0 to 2.0.

The fuel ratio is preferably 0.2 to 0.8, more preferably 0.25 to 0.7, still more preferably 0.30 to 0.65.

The higher calorific value on the drying basis is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6500 kcal / kg, and still more preferably 4900 to 6500 kcal / kg.

The molar ratio O / C of oxygen O and carbon C is preferably from 0.10 to 0.70, more preferably from 0.20 to 0.60, still more preferably from 0.30 to 0.60.

The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, still more preferably 0.9 to 1.20.

The preferred ranges of properties of the solid fuel C are described above.

Further, when producing the solid fuel C, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 220 to 300 占 폚, and further preferably 240 to 290 占 폚.

(Mixture of almond husk and almond husk: solid fuel D)

As an embodiment of the present invention, the characteristics of the biomass solid fuel (hereinafter sometimes referred to as solid fuel D) when the raw material is a mixture of almond husks and almond seeds are as follows.

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

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

The BET specific surface area is preferably 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 from 0.30 m ² / g to 0.60 m ² / g More preferable.

The HGI is preferably 20 to 60, more preferably 20 to 55, and still more preferably 23 to 55. The HGI ratio (to be described later) is preferably 1.0 to 2.0.

The fuel ratio is preferably 0.2 to 0.8, more preferably 0.30 to 0.7, still more preferably 0.35 to 0.65.

The higher calorific value of the drying standard is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6500 kcal / kg, and still more preferably 4900 to 6300 kcal / kg.

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

The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.8 to 1.25, still more preferably 0.85 to 1.20.

Hereinabove, preferred ranges of properties of the solid fuel D are described.

Further, when producing the solid fuel D, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 220 to 300 占 폚, and further preferably 240 to 290 占 폚.

(Acacia woody part: solid fuel E)

As one form of the present invention, the characteristics of the biomass solid fuel (hereinafter sometimes referred to as solid fuel E) when the raw material is an acacia wood part are as follows.

The content of COD is preferably 950 ppm or less, more preferably 850 ppm or less, further preferably 800 ppm or less, and the COD ratio is preferably 0.95 or less, more preferably 0.85 or less, and even more preferably 0.80 or less.

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

That the BET specific surface area of 0.40m ² / g to 0.70m ² / g is desirable and, 0.50m ² / g to 0.70m ² / g is desirable and, 0.55m ² / g to 0.70m ² / g than More preferable.

The fuel ratio is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, still more preferably 0.2 to 0.4.

The higher calorific value of the drying standard is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6000 kcal / kg, and even more preferably 4800 to 5500 kcal / kg.

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

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

The preferred ranges of properties of the solid fuel E are described above.

Further, when producing the solid fuel E, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 220 to 300 占 폚, and further preferably 240 to 290 占 폚.

(Acacia bark: solid fuel F)

As one form of the present invention, the properties of a biomass solid fuel (hereinafter, sometimes referred to as a solid fuel F) in the case where the raw material is an acacia bark are as follows.

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

The equilibrium water content after immersion in water is preferably 15 wt% to 50 wt%, more preferably 20 wt% to 45 wt%, and still more preferably 25 wt% to 40 wt%.

That the BET specific surface area of 0.35m ² / g to 0.55m ² / g is desirable and, 0.40m ² / g to 0.55m ² / g is desirable and, 0.40m ² / g to 0.50m ² / g than More preferable.

The fuel ratio is preferably 0.4 to 0.8, more preferably 0.42 to 0.75, and still more preferably 0.45 to 0.75.

The higher calorific value of the drying standard is preferably 4800 to 7000 kcal / kg, more preferably 5000 to 7000 kcal / kg, and still more preferably 5200 to 6500 kcal / kg.

The molar ratio O / C of oxygen O to carbon C is preferably 0.25 to 0.60, more preferably 0.30 to 0.60, and still more preferably 0.30 to 0.55.

The molar ratio H / C of the hydrogen H and the carbon C is preferably 0.8 to 1.3, more preferably 0.8 to 1.2, still more preferably 0.9 to 1.2.

The preferred ranges of properties of the solid fuel F are described above.

Further, when producing the solid fuel F, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 220 to 300 占 폚, and further preferably 240 to 290 占 폚.

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

As one form of the present invention, the characteristics of the biomass solid fuel (hereinafter sometimes referred to as solid fuel G) when the raw material is a mixture of an almond shell and a walnut shell are as follows.

The COD ratio is preferably 2500 ppm or less, more preferably 2100 ppm or less, more preferably 1500 ppm or less, and the COD ratio is preferably 0.65 or less, more preferably 0.55 or less, still more preferably 0.45 or less.

The equilibrium water content after immersion in water is preferably 20 wt% to 45 wt%, more preferably 20 wt% to 40 wt%, and still more preferably 25 wt% to 35 wt%.

That the BET specific surface area of 0.15m ² / g to 0.35m ² / g is desirable and, 0.19m ² / g to 0.33m ² / g is preferable, and more than 0.20m ² / g to 0.30m ² / g More preferable.

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

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

The higher calorific value on the drying basis is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6000 kcal / kg, and still more preferably 5000 to 6000 kcal / kg.

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

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

The preferred ranges of properties of the solid fuel G are described above.

Further, when producing the solid fuel G, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 220 to 300 占 폚, and further preferably 240 to 290 占 폚.

(Accidental coconut: solid fuel H)

As one form of the present invention, the characteristics of the biomass solid fuel (hereinafter, sometimes referred to as solid fuel H) when the raw material is an accidental cow are as follows.

The content of COD is preferably not more than 2000 ppm, more preferably not more than 1600 ppm, further preferably not more than 800 ppm, and the COD ratio is preferably not more than 0.85, more preferably not more than 0.60,

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

That the BET specific surface area of 0.15m ² / g to 0.35m ² / g is desirable and, 0.18m ² / g to 0.33m ² / g is desirable and, 0.18m ² / g to 0.30m ² / g than More preferable.

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

The fuel ratio is preferably 0.2 to 0.8, more preferably 0.25 to 0.8, still more preferably 0.5 to 0.8.

The higher calorific value of the drying standard is preferably 4800 to 7000 kcal / kg, more preferably 4900 to 6500 kcal / kg, and still more preferably 5000 to 6000 kcal / kg.

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

The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, still more preferably 0.85 to 1.2.

The preferred ranges of properties of the solid fuel H are described above.

Further, when producing the solid fuel H, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 220 to 300 占 폚, and even more preferably 240 to 290 占 폚.

(EFB: solid fuel I)

As an embodiment of the present invention, the characteristics of the biomass solid fuel (hereinafter sometimes referred to as solid fuel I) when the raw material is EFB (compartment of palm oil processed residues) are as follows.

The content of COD is preferably 2350 ppm or less, more preferably 2300 ppm or less, still more preferably 2000 ppm or less, and the COD ratio is preferably 0.98 or less, more preferably 0.96 or less, and even more preferably 0.85 or less.

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

That the BET specific surface area of 0.25m ² / g to 0.65m ² / g is desirable and, 0.30m ² / g to 0.60m ² / g is desirable and, 0.35m ² / g to 0.55m ² / g than More preferable.

The fuel ratio is preferably 0.25 to 0.8, more preferably 0.30 to 0.8, still more preferably 0.36 to 0.8.

The higher calorific value of the drying standard is preferably 4800 to 7000 kcal / kg, more preferably 4900 to 7000 kcal / kg, and still more preferably 5000 to 7000 kcal / kg.

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

The molar ratio H / C of hydrogen H to carbon C is preferably 0.5 to 1.3, more preferably 0.55 to 1.3, still more preferably 0.6 to 1.2.

The preferred ranges of properties of the solid fuel I are described above.

Further, when producing the solid fuel I, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 220 to 300 占 폚, and further preferably 240 to 260 占 폚.

(Meranti: solid fuel J)

As one form of the present invention, the properties of the biomass solid fuel (hereinafter sometimes referred to as solid fuel J) when the raw material is methanol are as follows.

The content of COD is preferably 330 ppm or less, more preferably 320 ppm or less, further preferably 300 ppm or less, and the COD ratio is preferably 0.98 or less, more preferably 0.95 or less, and even more preferably 0.90 or less.

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

The fuel ratio is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, still more preferably 0.2 to 0.45.

The higher calorific value of the drying standard is preferably 4800 to 7000 kcal / kg, more preferably 4800 to 6500 kcal / kg, and even more preferably 4800 to 6000 kcal / kg.

The molar ratio O / C of oxygen O to carbon C is preferably from 0.3 to 0.60, more preferably from 0.35 to 0.60, still more preferably from 0.40 to 0.60.

The molar ratio H / C of hydrogen H to carbon C is preferably 0.9 to 1.2, more preferably 0.95 to 1.2, further preferably 1.0 to 1.2.

The preferred ranges of properties of the solid fuel J are described above.

Further, when producing the solid fuel J, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 220 to 300 占 폚, and further preferably 230 to 290 占 폚.

(Rubber tree: solid fuel K)

As one form of the present invention, the characteristics of the biomass solid fuel (hereinafter sometimes referred to as solid fuel K) when the raw material is a rubber tree are as follows.

The fuel ratio is preferably 0.2 to 0.8, more preferably 0.2 to 0.7. The higher calorific value of the drying standard is preferably 4800 to 7000 kcal / kg.

The molar ratio O / C of oxygen O to carbon C is preferably 0.1 to 0.7. The molar ratio H / C of hydrogen H to carbon C is preferably 0.8 to 1.3.

The preferred ranges of properties of the solid fuel K are described above.

Further, when producing the solid fuel J, the heating temperature in the heating step is preferably 200 to 350 占 폚, more preferably 220 to 300 占 폚, and further preferably 230 to 290 占 폚.

The inventors of the present invention have found that, in a method for producing a biomass solid fuel, by using a sequence of a step of performing a heating step of heating a unheated mass after a forming process, a component derived from a raw material biomass is used It is presumed that the biomass solid fuel can be produced that has high water resistance and is not collapsed even by immersion in water. The inventors' understanding has led to the following knowledge on the mechanism by which the biomass solid fuel acquires water resistance.

The inventors of the present invention have found that when three types of biomass solid fuels having different production methods are used, specifically, unfired solid fuel (White Pellet) (hereinafter sometimes referred to as WP) in which pulverized biomass is formed and pulverized biomass FT-IR analysis, GC-MS analysis, observation by SEM and the like are performed on the solid fuel (Pelletizing Before Torrefaction (hereinafter sometimes referred to as PBT) obtained by heating after molding and heating, and the water resistance of the biomass solid fuel The mechanism was analyzed. In addition, neither binder nor PBT is used.

First, the acetone extract of each solid fuel was analyzed by FT-IR. As a result, the PBT obtained through the heating process had a lower content of hydrophilic COOH group than that of unswounded WP, but the content of C═C bond was large , It has been suggested that the chemical structure of the components constituting the biomass changes by heating to become hydrophobic.

GC-MS analysis of the acetone extract components of the solid fuels showed that terpenes such as abietic acid and its derivatives (hereinafter also referred to as " abietic acid ") were pyrolyzed by heating, It is suggested that it is concerned with the water resistance of solid fuel. Abiotic acid and the like are the main components of rosin contained in pine trees and the like.

18 is a diagram showing a mechanism (estimation) of high crosslinking development in PBT. In the case of PBT, in the heating step after the molding step, the liquid resulting from the melting of abietic acid due to the rise in temperature is separated from the gap between the pulverized biomass (hereinafter sometimes referred to as biomass powder) (The gap of the adjacent biomass powder), and the evaporation of the abiotic acid and the thermal decomposition occur, and the hydrophobic water is fixed to the gap between the biomass powders, so that the crosslinking (high crosslinking) develops. Thus, the connection or adhesion of the biomass powder is maintained by abietic acid or the like originating from the raw material biomass without adding a binder. Therefore, it is considered that the biomass powder is connected or adhered to each other to inhibit water ingress, thereby improving water resistance.

On the other hand, in the case of WP, since only the biomass powder is molded, and heating is not performed, there is no hyperbranched bridge between the biomass powders like the PBT. As described above, since there are many hydrophilic COOH groups on the surface of the biomass powder constituting the WP, water penetration is easy and the penetrated water greatly expands the gap between the biomass powders, and the molded pellets collapse It becomes easy to become.

Further, in the case of a solid fuel formed after heating the biomass powder (sometimes referred to as PAT), the individual biomass powder itself is heated by heating to dissolve the surface of the biomass powder However, since hydrophobicity is obtained by heating and pulverization is carried out, it is considered that crosslinking of the biomass powder is not formed like PBT. Therefore, in the PAT which is heated before molding, it is estimated that the water penetrates easily into the gap between the compacted biomass powders and is poor in water resistance as compared with PBT.

The abietic acid or its derivative has a melting point of about 139 to 142 캜 and a boiling point of about 250 캜. Therefore, it is presumed that, upon heating, abietic acid or the like is melted near the melting point to cause liquid cross-linking, and abietic acid or the like is thermally decomposed in the vicinity of the boiling point to develop high cross-linking.

In addition, terpenes including abietic acid are included in the general biomass (Hokkaido National Livestock Research Institute monthly report 171, April 1966, Japan Wood Preservation Association "Wood Preservation" Vol.34-2 (2008), etc.) . Although there is a slight difference in the content depending on the type of biomass (see Utilization of Essential Oils, Ohiradatsuo, Report of the 6th Study Session of the Japanese Society of Wood Science, p72, Table 1, Japanese Wood Society 1999, etc.) In Example I, since water resistance (not collapsed even after immersion in water) is manifested by heating at 230 DEG C or more, water resistance is imparted to the biomass in general by heating at least 230 DEG C to 250 DEG C or more .

19 to 22 are graphs showing FT-IR analysis results of the biomass solid fuel. The raw material is the European stock feed of Example B, and the solid fuel (PBT) heated at 250 占 폚 after being pulverized and molded into pellets is analyzed. In addition, the same raw material is pulverized, and uncoloured (WP) is shown together. The amount of COOH group is WP > PBT and the amount of C = C bond is PBT > WP in both the outer surface of the pellet (Fig. 19) and the center of the cross section (Fig. In addition, the COOH group elution amount with respect to the acetone extract (Fig. 21) was WP > PBT, and the PBT showed a small hydrophilic COOH group. Further, in the solid after extraction with acetone (Fig. 22), PBT has more C = C bond than WP. Thus, it can be seen that PBT is superior in water resistance.

23 is a graph showing the GC-MS analysis results of the acetone extract. 19 to 22, the solid fuel (PBT) heated at 250 占 폚 and the unpolished WP (WP) were used as the raw material, which was molded into pellets after crushing. As shown in Fig. 23, in PBT, elution amount of acetyl such as abietic acid, which is one kind of terpenes, is less than WP, and abietic acid is melted by heating to form a liquid cross-link, It is considered that high-crosslinking is formed.

In PBT, the strength of the solid fuel is improved by the development of high-crosslinking, and it is possible to improve the grindability (HGI, grinding speed to be described later) without adding a binder by heating at least 230 deg. It is presumed that good handling property (differentiation test described later) is obtained. In PBT, the COD is reduced as described above. This is because the tar of the biomass raw material is volatilized by heating, and the solid fuel surface of the PBT is covered with the solidified abietic acid or the like, and the solid fuel surface is hydrophobic So that elution of the tar component remaining in the biomass raw material is suppressed.

Example

<Example A>

(Examples A-1 to A-6)

The biomass solid fuel A (PBT) was obtained by crushing the biomass, crushing the crushed biomass, molding the crushed biomass, and heating process thereafter. No binder was used in any process. As the raw material biomass, a mixture of 40% by weight of dough, 58% by weight of Hempen, 1% by weight of cedar, and 1% by weight of cypress was used. In each example molding step, it was molded into a pellet shape having a diameter of 8 mm. In the heating step of each example, 4 kg of each raw material was charged into a 600 mm electric furnace, and the temperature was raised to a target temperature (heating temperature in Table 1) in each example at a heating rate of 2 캜 / min And heated. Hereinafter, the target temperature and the heating temperature are the same. In each of Examples A-1 to A-6, the holding at the target temperature (heating temperature) was not performed (the following Examples B to K are also the same). Table 1 shows the heating temperatures in the heating processes of Examples A-1 to A-6 and the properties of the biomass solid fuel A obtained after the heating process.

(Comparative Example A)

Comparative Example A is an unheated biomass solid fuel (WP) which is molded only after crushing and grinding, and which is not subjected to a heating step. No binder was used for Comparative Example A. The raw material biomass is the same as Example A-1. The properties of the solid fuel of Comparative Example A are also shown in Table 1.

In Table 1, as described above, HGI is based on JIS M 8801, and the higher the value, the better the crushability. Table 1 also shows the results of the elemental analysis values (basis norms) and the results of oxygen O, carbon C (dry basis) obtained based on the high calorific value (dry standard), the industrial analysis value , And hydrogen (H), respectively.

For each of the biomass solid fuels obtained in the above Examples and Comparative Examples, the following analysis was further conducted.

[COD]

Fig. 1 shows the correlation between the heating temperature in the heating step and the COD (chemical oxygen demand) and pH of the saliva index obtained when the obtained biomass solid fuel was immersed in water (pH will be described later). The production of the needle index samples for the COD measurement was analyzed according to JIS K 0102 (2010) -17 according to the method of assaying the metals contained in the industrial wastes in Annex 13 (1973) of the Environment Agency of Japan, 1973.

From Fig. 1, the COD of Comparative Example A (WP: biomass solid fuel not subjected to heating and heating only) was as high as about 1200 ppm. On the other hand, the biomass solid fuel heated at 230 ° C or higher showed a COD of 800 ppm or less, indicating that the elution of tar was low. Therefore, the biomass solid fuels of Examples A-1 to A-6 were found to be excellent in handling properties because of less elution of tar in the case of outdoor storage. The COD of the biomass solid fuels of Examples A-1 to A-6 heated at 230 DEG C or more is decreased as the heating temperature is increased. This is because the COD value due to the volatilization of tar or the like due to heating It is estimated that the COD value is lower than that of Comparative Example A even if the heating temperature is lower than 230 占 폚, that is, the heating temperature is lower than 150 占 폚 and lower than 230 占 폚.

[pH]

The solid fuels of Examples A-1 to A-6 and Comparative Example A were immersed in a solid ratio (solid ratio) of 1: 3 and the pH was measured. From Fig. 1, although the value is slightly lower for Examples A-2 and A-3, the pH is substantially around 6 in all Examples A-1 to A-6 and is not particularly changed as compared with Comparative Example A before heating Respectively. Therefore, there is no particular problem with respect to the pH of the wastewater discharged when the samples A-1 to A-6 are stored outdoors.

[Crushability]

2 shows the correlation between the heating temperature in the heating process and the grinding performance (HGI) and the grinding speed (described later) of the obtained biomass solid fuel A in the same manner as in Comparative Example A and Examples A- Solid fuel &lt; / RTI &gt;

As apparent from Table 1 and Fig. 2, the properties of Examples A-1 to A-6 were changed by heating, and HGI (according to JIS M 8801) was higher than Comparative Example A (WP: unfired heated biomass solid fuel) The value of the base) increased. It can be said that the HGI of general coal (bituminous coal) is around 50, and the crushing properties of Examples A-1 to A-6 are better than those of Comparative Example A in proximity to coal.

The grinding speed in Fig. 2 is a measurement of the weight (g / min) of pulverization per unit time by measuring the weight of a 700 cc sample as a sample after grinding with a ball mill and passing through a 150 mu m sieve. In addition, a ball mill was used in accordance with JIS M4002, and a cylindrical container having an inner diameter of 305 mm and an axial length of 305 mm was loaded with the supplied ball bearings (Φ36.5 mm × 43, Φ30.2 mm × 67, Φ24. 4 mm x 10,? 19.1 mm x 71,? 15.9 mm x 94) were placed and rotated at a speed of 70 rpm. The grinding speed was improved by heating, and the grinding speed was rapidly increased by heating at 230 DEG C or more. It can be said that the grinding performance of the biomass solid fuel A is increased by elution and solidification of organic components such as tar upon heating, and the grinding speed is improved. Therefore, even if the heating temperature in the heating step is not less than 150 ° C and not more than 230 ° C, it is estimated that the HGI and the grinding speed are improved as compared with the unheated comparative example A.

[Differentiation test]

Table 2 shows the ratio of the sub-sieve accumulation of the biomass solid fuel A subjected to the differentiation test, and Fig. 3 shows the particle size distribution thereof. In order to evaluate the handling characteristics of the pellets, a differentiation test was carried out. 1 kg of a sample was dropped into a resin bag at a height of 8.6 m and dropped 20 times, and then subjected to a rotational strength test based on JIS Z 8841, and the particle size distribution was measured. The obtained particle size distribution is shown in Fig. The sample is considered to be a particle capable of handling in transportation, storage and the like when the 2 mm sieve product in the sample particle size distribution is 30 wt% or less and the 0.5 mm product is 15 wt% or less. It can be seen from Table 2 and FIG. 3 that although the sample particle size after the rotational strength test became finer as the solid temperature increased, it was found that any sample passed through the evaluation criteria described above and could be handled without problems.

[Underwater immersion]

Table 3 and Fig. 4 show the results of the immersion test of the biomass solid fuel A in water. The solid fuel of each of the examples and the comparative examples was immersed in water and taken out after a predetermined time shown in Table 3 and Fig. 4 to wipe the water and measure the solid water content. The solid fuel of Comparative Example A (WP) was collapsed by immersion in water, and measurement of solid water was impossible. On the other hand, in the solid fuel of Example A-1, the water content reached equilibrium at about 10 hours after immersion, and the equilibrium water content was about 27 wt%. Further, in the solid fuel of Example A-2, the water content reached equilibrium after about 100 hours elapsed, and the equilibrium water content was about 25 wt%. For Examples A-3 to A-5, equilibrium was also obtained at a moisture content of about 23 wt% after about 100 hours. Example A-6 also reached almost equilibrium after about 100 hours, and the equilibrium water content was about 28 wt% (which is larger than that of Examples A-3 to A-5, but is thought to be due to changes in raw materials). These results suggest that the surface of the biomass solid fuel is changed to be hydrophobic due to elution and solidification of organic components such as tar upon heating. Examples A-1 to A-6 (PBT) Which is advantageous as a solid fuel.

[Solid strength before and after immersion in water]

(Rotational strength)

Fig. 5 shows the results of measurement of solid strength (based on JIS Z 8841 rotational strength test method) before and after immersion in water for Examples A-1 to A-6 and Comparative Example A. Fig. As described above, in Comparative Example A (WP), the rotation strength after immersion was impossible because it was collapsed after immersion in water. For Examples A-1 to A-6 (PBT), the surface moisture of the solid fuel having reached equilibrium moisture content was wiped off and dried in a constant temperature drier at 35 DEG C for 22 hours. The strength of Examples A-1 to A-6 (PBT) subjected to the heating process was not substantially lowered, and it was difficult to cause differentiation even in comparison with Comparative Example A (WP) before immersion in water, so that handling was maintained.

(Mechanical durability)

6 is a graph showing the results of measurement of mechanical durability before and after immersion in water. For the solid fuels of Examples A-1 to A-6, Comparative Example A, the mechanical durability DU was measured on the basis of the following formula according to American Agricultural Industry Standard ASAE S 269.4 and German Industrial Standard DIN EN 15210-1 . In the formula, m0 denotes the weight of the sample before the rotation treatment, m1 denotes the weight of the body sample after the rotation treatment, and a sieve having a round hole diameter of 3.15 mm was used as the sieve.

DU = (m1 / m0) x100

Similarly to the rotational strength, the strength of Examples A-1 to A-6 (PBT) subjected to the heating process was hardly lowered in terms of mechanical durability, and it was difficult to cause differentiation compared with Comparative Example A (WP) And the handling was maintained.

[Spontaneous flammability]

Evaluation was made based on the "Flammability Test" of "UN Test and Assessment Manual: Manual of Dangerous Goods Vessels Transportation and Storage Regulation, 16th Edition". 1 to 2 cm ³ of the biomass solid fuel of Example A-2 (heating temperature 250 ° C) was dropped onto the inorganic insulating plate at a height of 1 m, and measurement was made six times during the drop or during ignition within 5 minutes after the drop. All six tests were ignited, and Example A-2 (PBT) was determined not to correspond to Container Class I of the UN Test and Assessment Manual above.

[Self-heating property]

Similar to spontaneous ignitability, evaluation was carried out based on the "Self-ignition test" of the "16th Revised Edition of Dangerous Goods Vessels Transportation and Storage Regulations". The biomass solid fuel (heating temperature: 250 ° C) of Example A-2 was charged to a sample vessel (a stainless-steel cube mesh having a side length of 10 cm), suspended in a thermostat, and the temperature of the material was measured continuously at a temperature of 140 ° C for 24 hours Respectively. A substance showing ignition or a temperature rise exceeding 200 ° C is regarded as a self-extinguishing substance, and the same test is carried out using a sample container having a side length of 2.5 cm, and whether or not a temperature rise exceeding 60 ° C Respectively. Based on the test results, it was judged that Example A-2 (PBT) does not correspond to a self-extinguishing substance.

[Pore diameter distribution]

(BET specific surface area)

7 is a diagram showing the measurement result of the BET specific surface area of the solid fuel A. FIG. The automatic specific surface area / pore diameter distribution measuring apparatus (BELSORP-min II manufactured by Japan Bell Co., Ltd.) was used for the solid fuels of Examples A-1 to A-6 and Comparative Example A, And filled in a container, followed by vacuum degassing at 100 DEG C for 2 hours to obtain a BET specific surface area. Nitrogen gas was used as the adsorbing gas. 7, it was found that the BET specific surface area increased with the increase of the heating temperature, and the pores developed along with the heating (pyrolysis).

(Average pore diameter, total pore volume)

Fig. 8 shows the average pore diameter of the solid fuel A surface, and Fig. 9 shows the total pore volume. Average pore diameter, and total pore volume were measured using the same apparatus as the BET specific surface area. Here, the term &quot; pore &quot; means a hole having a diameter of 2 nm to 100 nm. The average pore diameter is decreased along with the rise of the heating temperature after Example A-2, and thus a large number of fine pores are generated. This is believed to be due to the decomposition of cellulose.

[yield]

FIG. 10 shows the yield (solid yield and heat yield) of the biomass solid fuel A after the heating process. The solid yield is the weight ratio before and after heating, and the heat yield is the heating value ratio before and after heating. In addition, as described above, the holding at the target temperature (heating temperature) in each of the embodiments is not performed (the following examples B to K are also the same).

 From the results of Examples A-1 to A-6 above, according to the present invention, the biomass solid fuel A (PBT) for reducing the COD, improving the grinding property, reducing the absorption, improving the solid strength and improving the yield can be obtained at low cost Respectively.

[Natural pyrogenicity]

The spontaneous exothermicity of the solid fuel of Example A-2 was measured by the following method. 1 kg of the sample was put into a vessel, the reactor was put into a thermostatic chamber at 80 ° C, and air was supplied to the sample, and the concentration of O 2, CO, and CO 2 in the obtained gas was measured. From the concentrations before and after heating, the O2 adsorption amount, the CO generation amount and the CO2 generation amount based on the heating of the sample are calculated and the natural exothermicity index (SCI) is calculated based on the following formula (1).

Naturally exothermic index (SCI) = {O2 adsorption amount * O2 (1/100)} + {CO2 generation amount * (CO2 generation amount * (1/2) * H2O generation heat * H / C) * Generation heat + (1/2) * H2O generation heat * H / C) * (1/100)} ... Equation (1)

The adsorption amount, the generation amount, and the H / C in the solid fuel of Example A-2 are as follows.

O2 adsorption amount 0.42 [ml / kg · min]

CO generation amount 0.03 [ml / kg · min]

CO2 Emission 0.02 [ml / kg ㆍ min]

H / C (molar ratio of hydrogen to carbon in the solid fuel of Example A-2) 1.28 [mol / mol] (see Table 1)

The heat of adsorption and the heat of generation used in the formula (1) are as follows.

O2 Adsorption heat 253 [kJ / mol] (O2 for coal The same value as the adsorption heat)

CO generation rate 110.5 [kJ / mol]

H2O formation heat 285.83 [kJ / mol]

CO2 Generated heat 393.5 [kJ / mol]

Based on the above, the SCI of the solid fuel relating to Example A-2 was calculated and found to be SCI = 1.3. In addition, since biomass solid fuel A is close to coal, The heat of adsorption was the same as the adsorption heat for coal.

The same method as in the calculation of the SCI in Example A-2 was used to calculate the SCI for Examples A-1 to A-3, A-6 and Example A-2 after the differentiation test (Table 2, Respectively. The calculation results are shown in Fig. For comparison, FIG. 11 also shows the bitumen SCI of Table 4. The horizontal axis in Fig. 11 is the moisture content of the arrival criterion. In the bituminous coal SCI shown in Fig. 11, four kinds of samples having different moisture contents were added to the bituminous coal shown in Table 4, and SCI Respectively.

Examples A-1 to A-3, A-6, and Example A-2 after the differentiation test (Table 2 and Table 4) after the differentiation test show that the lower the SCI value is, the lower the natural exothermicity. 3) and bituminous coal are compared, the biomass solid fuel (PBT) of the present invention has lower SCI (natural pyrogenicity) than that of bituminous coal, and the SCI ). As a result, the biomass solid fuel A (PBT) can be said to be a good fuel in which the possibility of ignition during handling is reduced.

[Surface Photo]

Figs. 12 to 14 are SEM photographs of cross-sections of solid fuel (PBT) before and after immersion in water in Example A-2. Fig. 12 shows the state before immersion, Fig. 13 shows after two seconds of immersion, and Fig. 14 shows after 20 seconds of immersion. 15 to 17 are SEM photographs of cross-sections before and after immersion in water in Comparative Example A (WP). Fig. 15 shows the SEM images before immersion, Fig. 16 shows after 2 seconds of immersion, and Fig. 17 shows after 20 seconds of immersion. In both Example A-2 and Comparative Example A, the cross-section after immersion was a cross-section obtained by cutting the solid fuel after immersing for 2 seconds or 20 seconds. It also shows the scale and scale under each photo.

 Comparing the photographs before and after immersion in water, in Comparative Example A (Figs. 15 to 17), the pores are enlarged after immersion in water. This is presumed to be due to the fact that the biomass is absorbed by immersion, and the pores (the gap between the biomass powders) are enlarged because Comparative Example A (WP) is a compact of biomass pulverized as described above. Therefore, it is considered that the pulverized biomass is separated by the intrusion of water into the enlarged pores, and the solid fuel itself collapses (see Fig. 4).

On the other hand, the solid fuel surface of Example A-2 (Figs. 12 to 14) does not significantly enlarge the pores even after immersing in water, and the change due to immersion is small. In Example A-2, high-crosslinking of the biomass powder was developed by heating, hydrophobicity was improved, absorption became difficult, and it was estimated that the change due to immersion was small. Therefore, even after the immersion, since the connection or adhesion between the pulverized biomass due to the high crosslinking is maintained, it is less likely to collapse as in Comparative Example A. Therefore, as shown in Fig. 4, in the solid fuel of Examples A-1 to A-6 (PBT) subjected to heating, collapse due to rainwater or the like was suppressed and a biomass solid fuel secured in handling properties during outdoor storage was obtained lost.

<Example B>

In Examples B-1 to B-4 (PBT), the temperature was raised to the target temperature (heating temperature described in Table 5) and heated in the same manner as in Example A, except that the European biomass was used as the raw material biomass. Table 5 and Table 6 show the properties of the biomass solid fuel B (Examples B-1 to B-4) obtained after the heating process. The same applies to Comparative Example B (WP). As in Example A, no binder was used in all of Examples B-1 to B-4 and Comparative Example B. Since the water after immersion in water is after immersion for 100 hours or more (Example B: 168 hours), it is considered that water in the solid fuel B substantially reaches equilibrium. The measurement method of each property of the biomass solid fuel is the same as that of the above Example A. The ball millability shown in Table 6 was measured as follows.

[Ball millability]

The pulverization time of each biomass solid fuel B was set at 20 minutes, and the weight ratio of 150 mu m after 20 minutes was regarded as the pulverization point. In addition, a ball mill was used in accordance with JIS M4002, and a cylindrical container having an inner diameter of 305 mm and an axial length of 305 mm was loaded with the supplied ball bearings (Φ36.5 mm × 43, Φ30.2 mm × 67, Φ24. 4 mm x 10,? 19.1 mm x 71,? 15.9 mm x 94) were placed and rotated at a speed of 70 rpm. The higher the value, the better the crushability. It was confirmed that the grinding point rises with an increase in the heating temperature.

 Comparative Example B collapsed immediately after immersion in water. On the other hand, with respect to Examples B-1, B-3 and B-4, the connection or adhesion of the biomass powders was maintained even after immersion in water (168 hours), and no collapse was observed. As a result, the solid shape was maintained even after the immersion, so moisture measurement was possible and the water resistance was able to be confirmed. In comparison with Comparative Example B, the pulverizability was improved and the COD was also reduced. Example B-3 is particularly excellent in view of water resistance (immersion water), and the biomass solid fuel of Examples B-2 and B-3 exhibits particularly excellent physical properties in terms of yield.

It is also presumed that Example B-2 is a fuel having excellent water resistance and crushability based on the development of high-crosslinking, and also having reduced COD.

<Example C>

(Example C-1 to Example C-4: PBT) by heating to the target temperature (heating temperature described in Table 5) in the same manner as in Example A except that almond seeds were used as raw material biomass. The ball mill grindability was measured in the same manner as in Example B above. The properties of the biomass solid fuel C obtained after the heating process are shown in Tables 5 and 6. As in Example B, water after immersion in water is regarded as equilibrium because it is after immersion for 100 hours or more (168 hours in Example C). Comparative Example C (WP) was also shown in the same manner. Further, no binders were used in all of Examples C-1 to C-4 and Comparative Example C.

Comparative Example C collapsed immediately after immersion in water. On the contrary, in Examples C-1 to C-4, the connection or bonding of the biomass powders was maintained even after submerged in water, and there was no collapse, and the water resistance was improved. In addition, improvement in crushability and reduction in COD were observed. Example C-2, Example C-3 and Example C-4 are superior in terms of COD and water resistance (water immersion), and Example C-1, Example C-2 and Example C-3 are superior in terms of heat yield Do. The HGI of Example C-1 is lower than that of Comparative Example C, but this is considered to be due to the fluctuation of the raw materials and the measurement error, and it is estimated that the HGI is at least equal to or higher than that of Comparative Example C.

<Example D>

(Example D-1 to Example D) were heated to the target temperature (heating temperature described in Table 5) in the same manner as in Example A except that the raw material biomass was used (30 wt% of almond husk + 70 wt% -4: PBT). The ball mill grindability was measured in the same manner as in Example B above. The properties of the biomass solid fuel D obtained after the heating process are shown in Tables 5 and 6. &lt; tb &gt; &lt; TABLE &gt; Moisture after immersion in water is considered to be equilibrium after immersion for 100 hours or more (168 hours in Example D). The same was also true for Comparative Example D (WP). Further, no binders were used in all of Examples D-1 to D-4 and Comparative Example D.

 Comparative Example D immediately collapsed after immersion in water. On the other hand, all of the examples D-1 to D-4 did not collapse because the connection or adhesion between the biomass powders was maintained even after soaking in water, and the water resistance was improved. In addition, improvement in crushability and reduction in COD were observed. Example D-2, Example D-3 and Example D-4 were excellent from the viewpoint of COD and Example D-1, Example D-2 and Example D-3 showed particularly excellent properties from the viewpoint of heat yield.

<Example E>

The temperature was raised to the target temperature (the heating temperature described in Table 5) in the same manner as in Example A, except that the acacia wood part was used as raw material biomass, the biomass was molded into a tablet shape, and a tubular furnace with a diameter of 70 mm was used as a heating device (Examples E-1 to E-3: PBT). The properties of the biomass solid fuel E obtained after the heating process are shown in Tables 5 and 6. The water after immersion in water is regarded as equilibrium after immersion for 100 hours or more (168 hours in Example E). The same was also true for Comparative Example E (WP). Further, no binders were used in all of Examples E-1 to E-3 and Comparative Example E. The measurement of the pH in Example E was carried out by immersing the solid fuel at a liquid ratio of 1:13. Herein, the immersion time of Comparative Example E in Table 6 indicates the measurement time of the pH, that is, the pH after immersing the Comparative Example E for 96 hours.

 Comparative Example E immediately collapsed after immersion in water, but Examples E-1 to E-3 showed water resistance without collapsing due to the connection or adhesion between the biomass powders. Example E-2 and Example E-3 are superior from the viewpoint of water resistance (water after immersion in water), and Example E-1 and Example E-2 are superior from the viewpoint of heat yield. In Example E, it is presumed that the above-mentioned high-crosslinking is also formed in PBT heated at 240 to 270 ° C, and it is considered to be excellent in water resistance, COD, grindability and the like. In addition, the heat yield of Example E-1 exceeds 100%, but it is due to variations in raw materials and measurement errors.

<Example F>

(Example F-1 to Example F-4: PBT) were heated to the target temperature (heating temperature described in Table 5) and heated in the same manner as in Example E except that an acacia bark was used as the raw material biomass. The properties of the biomass solid fuel F obtained after the heating process are shown in Tables 5 and 6. The water after immersion in water is regarded as equilibrium after immersion for 100 hours or more (in the case of Example F, 168 hours or more). The same was also true for Comparative Example F (WP). Further, no binders were used in all of Examples F-1 to F-4 and Comparative Example F. The measurement of the pH in Example F was carried out by immersing the solid fuel at a liquid ratio of 1:13. Herein, the immersion time of Comparative Example F in Table 6 indicates the measurement time of the pH, that is, the pH after immersing the Comparative Example F for 96 hours.

 Comparative Example F disintegrated within one hour after immersion in water, but Examples F-1 to F-4 showed water resistance without collapsing due to the connection or adhesion between biomass powders. Example F-2, Example F-3 and Example F-4 were superior in view of COD and water resistance (water immersion after immersion in water), and Example F-1, Example F-2 and Example F- great.

<Example G>

(The heating temperature described in Table 5) was used in the same manner as in Example A, except that a raw material biomass (70 wt% almond shell + 30 wt% walnut shell) was used and a tubular furnace with a diameter of 70 mm was used as a heating apparatus (Examples G-1 to G-4: PBT). The properties of the biomass solid fuel G obtained after the heating process are shown in Tables 5 and 6. Moisture after immersion in water is regarded as equilibrium after immersion for 100 hours or more (144 hours or more in Example G). Comparative Example G (WP) was also shown in the same manner. In addition, no binders were used in all of Examples G-1 to G-4 and Comparative Example G. [

Comparative Example G collapsed immediately after immersion in water, but Examples G-1 to G-4 showed water resistance without collapsing due to the connection or adhesion between the biomass powders. Example G-2, Example G-3 and Example G-4 are superior from the viewpoint of COD and water resistance (water after immersion in water), and Example G-1, Example G- great. In addition, the heat yield of Example G-2 exceeds 100%, but it is due to variation of raw materials and measurement error.

<Example H>

(Example H-1 to Example H-4: PBT) were heated to the target temperature (heating temperature described in Table 5) and heated in the same manner as in Example A except that the accidental coconut was used as the raw material biomass. The ball mill grindability was measured in the same manner as in Example B above. The properties of the biomass solid fuel H obtained after the heating process are shown in Tables 5 and 6. The water content after immersion in water is considered to be equilibrium after immersion for 100 hours or more (168 hours in Example H). Comparative Example H (WP) was also shown in the same manner. Further, all of the binders of Examples H-1 to H-4 and Comparative Example H were not used. The immersion time of Comparative Example H in Table 6 indicates that the pH was measured, that is, the pH after 24 hours after immersion in Comparative Example H was measured.

Comparative Example H collapsed within 3 hours after soaking in water, but Examples H-1 to Example H-4 showed water resistance without collapsing due to the connection or adhesion between the biomass powders. Example H-2, Example H-3 and Example H-4 were excellent in view of COD, pH (slightly low) and water resistance (water after immersion in water) , Example H-3 is excellent.

<Example I>

(Example I-1 to Example I-4) were heated to the target temperature (heating temperature described in Table 5) in the same manner as in Example A except that EFB (chambers of processed palm oil residue) was used as raw material biomass. PBT). The properties of the biomass solid fuel I obtained after the heating process are shown in Tables 5 and 6. The water after immersion in water is regarded as equilibrium after immersion for 100 hours or more (168 hours in Example I). The same was applied to Comparative Example I (WP). In addition, no binders were used in all of Examples I-1 to I-4 and Comparative Example I.

The mechanical durability before and after immersion in water of Example I-3 heated at 270 占 폚 and Example I-4 heated at 300 占 폚 was measured by the following method. 50 g of the sample is charged into a 1,000-cc polypropylene container and rotated at 60 rpm for 30 minutes (total 1,800 revolutions) with MISUGI manufactured by Mazu Mazeman SKH-15DT. The sample after the rotation was sieved into a sieve having a pore size of 3.15 mm,

DU = (m1 / m0) x100

To calculate the mechanical durability (DU). M0 is the weight of the sample before the rotation treatment, and m1 is the weight of the sample after the rotation treatment.

 Comparative Example I immediately disintegrated after immersion in water, but Examples I-1 to I-4 showed water resistance without collapsing due to the connection or adhesion between the biomass powders. Example I-2, Example I-3 and Example I-4 are superior from the viewpoints of COD and water resistance (water after immersion in water), and Examples I-1, I-2 and I- great.

<Example J>

(Example J-1, Example J-2: PBT) was heated to the target temperature (heating temperature described in Table 5) in the same manner as in Example A except that methanol was used as the raw material biomass. Table 5 and Table 6 show the properties of the biomass solid fuel J obtained after the heating process. Moisture after immersion in water is regarded as equilibrium after immersion for 100 hours or more (168 hours in Example J). Comparative Example J (WP) was also shown in the same manner. In addition, no binder was used in all of Examples J-1, J-2, and J.

 Comparative Example J immediately disintegrated after immersion in water, but in Example J-1 and Example J-2, the connection or adhesion between the biomass powders was maintained without collapsing, showing water resistance. Good results were also obtained for COD.

<Example K>

(Example K-1) was heated to the target temperature (heating temperature described in Table 5) in the same manner as in Example A, except that a rubber tree was used as the raw material biomass and a tubular furnace with a diameter of 70 mm was used as the heating apparatus. Table 5 shows properties of the biomass solid fuel K obtained after the heating process. The same applies to the comparative example K (WP). All of the binders were not used.

It is expected that Comparative Example K will also be collapsed by immersion in water in the same manner as the other examples. On the other hand, with respect to Example K-1, improvement in water resistance, grindability and reduction of COD is expected without causing collapse by underwater immersion due to the formation of the high-crosslinking. Example K-1 is heated at 270 DEG C, but the same effect is estimated for the heating temperature of 230 to 270 DEG C as described above.

<Absorption distribution>

In order to compare the water resistance of PAT and PBT, the distribution of sodium after absorption was examined for these biomass solid fuels using saline. As a sample of PAT, a solid fuel made by molding pellets having a diameter of 6 mm after heated at 250 ° C was used as a raw material European shipment. As a sample of the PBT, a solid fuel (solid fuel B) heated at 250 ° C was used after forming the pellet of 6 mm in diameter into the raw material European shipment. PBT and PAT were immersed in 0.9wt% physiological saline solution for 5 days. As a result, as shown in Fig. 24, the pellets maintained the pellet shape (left side in Fig. 24), but the PAT was largely collapsed (right side in Fig. 24). PAT and PBT were compared before and after immersion in physiological saline solution and physiological saline solution of 0.9 wt% for 5 days, respectively, and their cross sections were analyzed by EPMA (Electron Probe MicroAnalyser) analysis. In the Na distribution, PBT remained on the pellet surface and was not penetrated into the inside, whereas PAT was distributed widely to the inside (see FIG. 25). This means that PBT has less invasion of saline than PAT. From these results, it was found that the PBT prevents the intrusion of water because the pyrolysis product of the extracted component bridged the gap between the adjacent biomass powders to become hydrophobic, while the PAT prevents water from entering the gap between the biomass powders It is presumed that the water has penetrated into the pellet, and the gap between the biomass powders has widened, resulting in collapse.

[Expansion rate before and after immersion in water]

For the solid fuel of Examples A-1 and A-3, the pellet length before and after immersion in water was measured. With regard to the pellet length, 10 pellets before immersion were selected and measured by electronic nog- nose (CD-15CX manufactured by Mitutoyo Corporation, repetition accuracy: 0.01 mm, rounded off to the second decimal part) After immersing in water for a while, the length was again measured by electronic nose. When the tip of the pellet was inclined at any time before and after immersion, the length up to the tip of the pellet was measured as the length. The measurement results are shown in Table 7. As shown in Table 7, the pellet length of Example A-1 increased by an average of 4.6% and Example A-3 increased by 0.2% on average.

The pellet diameters of the solid fuel of Examples A-1 to A-6 before and after immersion were measured by the same electronic nose and measuring method as those in Table 7. The measurement results are shown in Table 8. Further, the measured values of the pellet diameters are 10 randomly selected values in each of Examples A-1 to A-6.

From Table 7 and Table 8, it was found that the higher the temperature of the heating process, the lower the expansion rate. It is presumed that the expansion is suppressed by the formation of high crosslinking by heating. The diameter expansion rate in Table 8 was larger than the length expansion rate in Table 7, but this is because the immersion time is longer in Table 7 and the pellet is the case in Example A, so that the expansion is largely increased in the radial direction . In Table 8, even in the case of Example A-1 in which the diameter expansion rate was the maximum, the expansion ratio was 10% or less. In Example A, the diameter and length expansion rate are preferably 10% or less, and more preferably 7% or less. The volume expansion ratio is preferably 133% or less, more preferably 123% or less.

 In Table 7 and Table 8, the expansion ratios of Example A are shown, but the expansion ratios of Examples B to J are calculated based on Table 6. The expansion ratio was calculated using the following formula (2) in the same manner as in Example A.

Expansion ratio = {(value after immersion - value before immersion) / value before immersion} x 100 ... (2)

Example B is pellets and the diameter expansion rate calculated using the pellet diameter before immersion (initial dimension in Table 6) and the pellet diameter after immersion (after immersion in Table 6) based on the formula (2) is 15 % (Hereinafter, the diameter expansion rate is also used in the case of Example B and the following equations (2)). As in Example A, assuming that the length expansion rate in the pellet is assumed to be the < diameter expansion rate, the length expansion rate in Example B is also assumed to be not more than 15% at maximum. When the volume expansion rate is calculated, it is not more than 152% (after immersion for 100% Volume, the same is true for Example C and thereafter). In Example B, the diameter expansion rate is preferably 20% or less, more preferably 10% or less. The volume expansion ratio is preferably 173% or less, more preferably 133% or less.

Example C is also a pellet. The volume expansion rate is 123% or less on the assumption that the diameter expansion rate before and after immersion is 7.2% or less and the length expansion rate is 7.2%. (Hereinafter, the volume expansion rate is also calculated for pellet examples). The diameter expansion rate in Example C is preferably 13% or less, more preferably 7% or less. The volume expansion rate is preferably 144% or less, more preferably 123% or less.

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

Example E is a tablet shape, and has a diameter (?) Expansion rate of 2.5% or less, a height (H) expansion rate of 40% or less, and a volume expansion rate of 147% or less. The diameter expansion ratio is preferably 5% or less, 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.

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

For example G (pellets), the diameter expansion rate before and after immersion is 8.8% or less, and the volume expansion rate based on it is 129% or less. The diameter expansion ratio is preferably 10% or less, more preferably 8% or less. The volume expansion ratio is preferably 133% or less, and more preferably 126% or less.

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

With respect to Example I (pellets), the diameter expansion rate before and after immersion is 4.1% or less, and the volume expansion rate based on this is 113% or less. The diameter expansion ratio is preferably 10% or less, more preferably 5% or less. The volume expansion rate is preferably 133% or less, more preferably 116% or less.

For example J (pellets), the diameter expansion rate before and after immersion is 5.4% or less, and the volume expansion rate based on it is 117% or less. The diameter expansion ratio is preferably 20% or less, more preferably 10% or less. The volume expansion ratio is preferably 173% or less, more preferably 133% or less.

As described above, the solid fuel (PBT) of the present invention using biomass as a raw material preferably has an expansion ratio of 40% or less in all lengths (including diameter and height) before and after immersion, and a volume expansion rate of about 275% Or less. It is more preferable that the expansion ratio of the diameter and the length is 30% or less and the volume expansion rate is about 220% or less. It is more preferable that the expansion ratio of the diameter and the length is 20% or less and the volume expansion rate is about 173% or less. It is more preferable that the expansion ratio of the diameter and the length is 10% or less and the volume expansion rate is about 133% or less. Since the rate of expansion after immersion in water is within a certain range, the biomass solid fuel (PBT) is not collapsed even by immersion and appears to have water resistance.

In addition, PBT was separately prepared for each of the raw materials of rubber wood, acacia, and melanchthy and tested. The test results are shown in Tables 9 and 10 below. In the test results shown in Tables 9 and 10, the rubber tree is denoted by "a", the acacia denoted by "b", and the denominator denoted by "c".

1 carbide
2 Vibratory conveyor
11 Thermometers
21 minute payment (classifying means)
22 Cooling section (cooling means)
22a Sprinkler (sprinkler)
22b Reputation
24 spacing
30 Control unit (control means)
100 fuel manufacturing process
110 Crushing process
120 Molding process
130 Heating process
200 class process
300 cooling process
402 system
403A vibrating body device
403B Cooling vibration conveyor
421 minutes
421a body
421b discharge portion
422 Cooling section
422a sprinkler
422b plate

Claims (5)

A carbonization furnace for carbonizing the biomass formed body to obtain biomass carbide,
Classifying means provided on the downstream side of the carbonization furnace for classifying the biomass carbide,
A cooling means provided downstream of the classifying means for cooling the classified biomass carbide,
And,
The above-mentioned biomass molded article is a molded article obtained by pulverizing and then molding the raw material biomass,
The cooling means comprises cooling the biomass carbide by spraying
And cooling the biomass carbide. The method according to claim 1,
Wherein the cooling means has a vibrating flat plate and a water spraying portion which sprinkles on the flat plate,
The flat plate is a metal plate or a resin plate, and transports the biomass carbide by vibration
And cooling the biomass carbide. 3. The method according to claim 1 or 2,
A thermometer for measuring the temperature of the carbonitrogen outlet is provided,
And a control means for stopping the water spraying means when the temperature measured by the thermometer reaches a predetermined value or less
And cooling the biomass carbide. The method of claim 3,
The thermometer is capable of directly measuring the temperature of the biomass carbide
And cooling the biomass carbide. 5. The method according to any one of claims 1 to 4,
A separating portion for separating the classifying means from the cooling means
And cooling the biomass carbide.

Images