JP2010006911A - Method for producing gasification catalyst-supporting coal utilizing biomass ash - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To establish a method for producing a gasification catalyst-supporting coal which can produce the coal with the gasification catalyst supported thereon at high concentration while reducing cost required for production of the gasification catalyst-supporting coal. <P>SOLUTION: There are prepared an acidic aqueous biomass solution generated upon carbonization treatment of at least one of woody biomass feedstock, herbaceous biomass feedstock, and food residue of vegetable origin, and biomass ash containing a gasification catalyst element of at least one of sodium, potassium and calcium serving as a gasification catalyst of coal. The aqueous biomass solution is brought into contact with the biomass ash to dissolve the gasification catalyst element contained in the biomass ash into the aqueous biomass solution, and then the aqueous biomass solution is brought into contact with coal to produce coal having the gasification catalyst element supported thereon. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing gasification catalyst-supporting coal using biomass ash. More specifically, the present invention relates to a method for producing coal having high catalytic activity suitable for use in biomass gasification using biomass ash.

  Coal gasification combined power generation is expected to be put to practical use as a highly efficient and environmentally friendly power generation system. In recent years, various studies have been conducted for practical application of this coal gasification combined power generation.

  As one of such studies, an attempt has been made to improve the energy conversion efficiency by reducing the gasification temperature by increasing the gasification reactivity of coal by supporting the gasification catalyst on the coal. For example, in Patent Document 1, alkali metal hydroxides, carbonates or chlorides, alkaline earth metal carbonates or chlorides, and transition metal chlorides are used as gasification catalyst materials. It has been proposed that a coal gas is impregnated in a coal solution and dried to allow the catalyst material to be supported on the coal particle to lower the coal gasification temperature.

  Non-Patent Document 1 discloses a technique in which sodium or potassium is supported on coal as a gasification catalyst by impregnating and drying an aqueous solution of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or the like. ing.

Further, Non-Patent Document 1 discloses a technique in which calcium hydroxide is dissolved in water to obtain a calcium hydroxide aqueous solution, and this aqueous solution is impregnated with coal and dried, whereby calcium is supported on the coal as a gasification catalyst. ing.
JP-A-7-207284 Exxon Research and Engineering Company USA, Fuel 1982, 61, 620-626.

  However, when an industrial reagent containing sodium, potassium, or calcium is used as a gasification catalyst, as in the technology disclosed in Patent Document 1 and Non-Patent Document 1, the cost for producing the gasification catalyst-supporting coal is high. As a result, the cost of coal gasification power generation increases.

  In addition, in the method disclosed in Non-Patent Document 1 in which calcium is supported by impregnating and drying a calcium hydroxide aqueous solution, only a very small amount of calcium can be supported on the coal. Is not expected to improve significantly.

  That is, for the spread of coal gasification power generation, establishment of a technique for producing coal having high catalytic activity while reducing the cost of coal gasification power generation is desired.

  Accordingly, an object of the present invention is to provide a method for producing a gasification catalyst-carrying coal that can carry a gasification catalyst on coal at a high concentration while reducing the cost for producing the gasification catalyst-carrying coal. And

  In order to solve such a problem, the inventor of the present application is unable to support calcium in coal at a high concentration by the method of Non-Patent Document 1 using an aqueous calcium hydroxide solution because the solubility of calcium hydroxide in water is 1.6 g / L (20 ° C.) is considered to be very low, and a liquid that dissolves calcium hydroxide at a high concentration was examined. As a result, it has been found that the solubility of calcium hydroxide in an acidic biomass aqueous solution generated when carbonizing bamboo or rice husks, which are herbaceous biomass materials, is very high compared to the solubility in water.

  Next, the inventor of the present application has studied various gasification catalyst extraction sources in place of industrial reagents such as calcium hydroxide. As a result, the biomass ash is brought into contact with the acidic biomass water-soluble liquid to dissolve the components contained in the biomass ash, and then the biomass water-soluble liquid is brought into contact with the pulverized coal to produce the gasification catalyst-supported pulverized coal. As a result of the production, it was found that the gasification reaction rate was improved as compared with raw coal. As a result of further various studies, it was found that the biomass ash used in the experiment contained at least one gasification catalyst element of sodium, potassium and calcium. The present inventors have found that biomass ash containing at least one of them can be used as a gasification catalyst extraction source, leading to the present invention.

  The method for producing a gasification catalyst-supporting coal according to claim 1 based on such knowledge is an acid generated when carbonizing at least one of a woody biomass raw material, a herbaceous biomass raw material, and a plant-derived food residue. A biomass water-soluble liquid and a biomass ash containing a gasification catalyst element of at least one of sodium, potassium and calcium that function as a coal gasification catalyst, and contacting the biomass water-soluble liquid and the biomass ash The gasification catalyst element contained in the biomass ash is dissolved in the biomass water-soluble liquid, and the biomass water-soluble liquid is brought into contact with the coal so that the gasification catalyst element is supported on the coal.

  The acidic biomass aqueous solution generated when carbonizing at least one of the woody biomass raw material, the herbaceous biomass raw material and the plant-derived food residue includes sodium, potassium and calcium contained in the biomass ash. At least one of the gasification catalyst elements is dissolved at a high concentration. Therefore, the biomass water-soluble liquid in which the gasification catalyst is dissolved at a high concentration is brought into contact with the coal to produce coal in which the gasification catalyst is dispersed and supported at a high concentration.

  The gasification catalyst-containing solution according to claim 2 is an acidic biomass water-soluble liquid generated when carbonizing at least one of a woody biomass raw material, a herbaceous biomass raw material, and a plant-derived food residue. In addition, a biomass ash gasification catalyst element containing at least one gasification catalyst element of sodium, potassium, and calcium that functions as a coal gasification catalyst is dissolved. Therefore, according to this gasification catalyst-containing solution, the gasification catalyst element is dissolved in the solution at a high concentration.

  According to the method for producing gasified catalyst-carrying coal according to claim 1, it is possible to produce coal having high catalytic activity in which the gasified catalyst element is dispersed and supported in a high concentration. Moreover, since the gasification catalyst element contained in the waste called biomass ash is used, it is markedly different from the case of producing gasification catalyst-supporting coal using an industrial reagent containing the gasification catalyst element. In addition, the gasification catalyst-supporting coal can be produced at a low cost. In addition, it uses biomass water-soluble liquid obtained from natural raw materials such as woody biomass, herbaceous biomass, and plant-derived food residues as a dissolution medium, so it can be gasified at low cost without causing environmental pollution. Catalyst-supporting coal can be produced.

  According to the gasification catalyst-containing solution according to claim 2, since the gasification catalyst element is dissolved in the solution at a high concentration, the gasification catalyst-containing solution is simply dried after contacting the coal with the coal, It becomes possible to obtain gasification catalyst-supporting coal in which the gasification catalyst element is stably supported at a high concentration.

  The best mode for carrying out the present invention will be described below in detail with reference to the drawings.

  The method for producing a gasification catalyst-supporting coal of the present invention includes an acidic biomass water-soluble liquid generated when carbonizing at least one of a woody biomass raw material, a herbaceous biomass raw material, and a plant-derived food residue; A biomass ash containing a gasification catalyst element of at least one of sodium, potassium, and calcium that functions as a coal gasification catalyst is prepared, and the biomass ash is contained in the biomass ash by contacting the biomass water-soluble liquid with the biomass ash. A gasification catalyst element is dissolved in a biomass water-soluble liquid, and the biomass water-soluble liquid is brought into contact with coal so that the gasification catalyst element is supported on the coal.

  That is, in the method for producing a gasification catalyst-supporting coal of the present invention, an element that functions as a coal gasification catalyst is dissolved in an acidic biomass aqueous solution to prepare a gasification catalyst-containing solution. By contacting with coal, the gasification catalyst element dissolved in the gasification catalyst-containing solution is dispersed and supported on the coal to obtain the gasification catalyst-supporting coal.

  Examples of the woody biomass material used in the present invention include sawdust, bark, and chips. More specifically, cedar chips, cedar bark and the like can be mentioned, but the woody biomass raw material from which an acidic biomass water-soluble liquid can be obtained is not limited thereto.

  Examples of the herbaceous biomass raw material used in the present invention include bamboo, rice husk, sugar cane, rice straw, and rice bowl, but if it is a herbaceous biomass raw material from which an acidic biomass aqueous solution can be obtained, It is not limited.

  Examples of plant-derived food residues used in the present invention include fruit residues such as fruit peels, and residue derived from plant seeds such as roasted coffee coffee, but derived from plants from which an acidic biomass aqueous solution can be obtained. If it is food residue of, it will not be limited to these.

  Moreover, the effect of the present invention can be achieved by using at least one kind of acidic biomass water-soluble liquid obtained by carbonizing any of woody biomass raw material, herbaceous biomass raw material and plant-derived food residue. Of course, two or more types may be used in combination. In addition, when collecting acidic biomass water-soluble liquid, two or more of woody biomass raw material, herbaceous biomass raw material and plant-derived food residue are simultaneously carbonized to collect acidic biomass water-soluble liquid You may make it do. In the following description, the woody biomass material, the herbaceous biomass material and the plant-derived food residue are collectively referred to as “biomass material”.

  An acidic biomass water-soluble liquid is obtained by recovering a gas generated when carbonizing a biomass raw material. However, the components generated when the biomass raw material is carbonized include a water-soluble liquid component and a heavy component (for example, tars) that is insoluble in water and has a high viscosity. Occurs in a gas state. An acidic biomass water-soluble liquid can be obtained by aggregating and capturing the gaseous water-soluble liquid component. Here, if the acidic biomass water-soluble liquid contains heavy components with high viscosity such as tars, when the acidic biomass water-soluble liquid is brought into contact with coal (pulverized coal) and dried, the coal Are likely to agglomerate and form a lump, which may cause inconvenience in the supply of coal into the gasification furnace. Therefore, heavy components with high viscosity need to be separated from the acidic biomass aqueous solution. Hereinafter, a method for recovering an acidic biomass aqueous solution will be described with reference to FIG.

  A biomass water-soluble liquid collecting / separating system 1 shown in FIG. 1 is roughly composed of an electric furnace 2 having a furnace core tube 3, a first container 4, and a second container 5. The core tube 3 and the first container 4 are connected by a pipe 7, and the first container 4 and the second container 5 are connected by a pipe 8.

  In the electric furnace 2 having the furnace core tube 3, the biomass raw material is carbonized. A biomass raw material is thermally decomposed (carbonized) when heated to 300 ° C. or higher in an oxygen-free condition, for example, in an inert gas atmosphere. At this time, an acidic biomass water-soluble component gas is generated.

As the inert gas, a rare gas such as Ar or nitrogen gas (N ₂ ) can be used, but it is preferable to use nitrogen gas in view of cost.

  Here, about the upper limit of the heating temperature in the carbonization treatment of the biomass raw material, if it is set to 500 ° C., the thermal decomposition of the biomass raw material is completely completed, but the thermal decomposition of the biomass raw material in the temperature range of 400 ° C. to 450 ° C. Is almost completed, it is sufficient to heat to a temperature range of 400 ° C. to 450 ° C. for the purpose of obtaining an acidic biomass aqueous solution. About a heating time, it can select suitably by the quantity of the biomass raw material charged in a furnace. As for the heating method, the temperature of the electric furnace may be gradually raised after the temperature of the electric furnace is set to room temperature, and then the temperature in the furnace is kept at 400 ° C. to 450 ° C. for heating. More preferably. In this case, productivity can be improved by shortening the time required to raise the temperature of the electric furnace.

  In the present embodiment, the biomass raw material pyrolysis apparatus has a vertical shape as the shape of the core tube 3, and is generated from the biomass material without passing the biomass material charged into the core tube 3 into the core tube 3. The perforated plate 12 having a through hole through which a gas to be sufficiently passed can be provided. Then, while the inside of the core tube 3 is heated by the electric furnace 2, the inert gas is supplied from the upper part of the core tube 3, so that the gas generated during the pyrolysis is directed from the pipe 7 toward the first container 4. It is forced to exhaust.

  As described above, the furnace tube 3 is a vertical type, and the pipe 7 is disposed downward with respect to the first container 4, so that the components such as the gas generated during the thermal decomposition are discharged before the pipe 7 is discharged. 7 and can be prevented from agglomerating, and even if it adheres to the pipe 7 and agglomerates, the agglomerate can be dropped into the first container 4 by gravity and collected. Therefore, the components generated by carbonizing the biomass raw material can be recovered without waste, and the yield of the acidic biomass aqueous solution can be increased.

  However, the biomass raw material pyrolysis apparatus is not limited to the above form, a horizontal electric furnace having a horizontal shape of the furnace core tube, a general drying apparatus that can be used at 300 to 500 ° C., a carbonizer, etc. Even in the case where is used, it is possible to obtain an acidic biomass water-soluble liquid although the yield of the acidic biomass water-soluble liquid is slightly reduced as compared with the above-described embodiment. Further, the heating method is not limited to heating by an electric furnace, and exhaust heat from the coal gasification power generation system may be supplied to secure a heat source for the thermal decomposition process. Further, in the biomass water-soluble liquid collection / separation system 1, a heat source may be secured by using a gas exhausted from the second container 5 as a fuel.

  Exhaust from the pipe 7 is introduced into the first container 4. The first container 4 is kept warm by a warming heater 14. The temperature of the heat retaining heater 14 is controlled by a thermocouple 16. Specifically, heavy components such as tars and solids contained in the discharge from the pipe 7 can be captured, and the temperature at which moisture evaporates, for example, the temperature in the vicinity of the introduction portion of the pipe 8 is 100 ° C. to Set to 110 ° C. As a result, heavy components such as tars and solids contained in the discharge from the pipe 7 are collected in the first container 4, and the gaseous discharge that has not been collected in the first container 4, Of the components once collected in one container 4, the component that evaporates at the set temperature of the heat retaining heater 14 is introduced into the pipe 8.

  In addition, the energy density as a fuel of heavy components, such as tars, and solid matter is raised by fully removing moisture from heavy components, such as tars, and solid matter collected by the first container 4 in this way. be able to. Therefore, it can be suitable for use as a fuel for combustion power generation and boilers, and it is also possible to reduce transportation costs and improve handling.

  Exhaust from the pipe 8 is introduced into the second container 5. The pipe 8 is provided with a water circulation type cooling device 15 (for example, a Liebig cooler), which keeps the temperature of the gaseous effluent not recovered in the first container 4 and the components once recovered in the first container 4. Aggregates are collected in the second container 5 by cooling the component that evaporates at the set temperature of the heater 14. This aggregate is an acidic biomass aqueous solution. In the present embodiment, the pipe 8 is provided with a cooling device, but the present invention is not limited to this configuration, and the second container 5 itself is cooled to capture and collect aggregates. It may be. Moreover, the cooling temperature for recovering the gaseous emission from the pipe 8 may be 0 ° C. to room temperature, but the cooling temperature is lower than this range to recover the discharge from the pipe 8. You may do it.

  The gas that has not been collected in the second container 5 may be used as fuel gas for coal gasification power generation. Further, as described above, it may be used as a fuel for a heat source for carbonization treatment of a biomass raw material. In this case, the cost for carbonization treatment of the biomass raw material can be reduced, and the cost for manufacturing the biomass water-soluble liquid can be reduced.

  In this embodiment, the first container 4 and the second container 5 are provided, heavy components such as solids and tars are collected in the first container 4, and acidic biomass water-soluble in the second container 5. Although the liquid is collected, the present invention is not limited to this form. For example, only the first container 4 is provided, and the first container 4 is cooled to 0 ° C. to room temperature, so that an acidic biomass aqueous solution is recovered in the first container 4 together with heavy components such as solids and tars. Then, the recovered product may be subjected to a solid-liquid separation process and a liquid-liquid extraction process to separate and recover an acidic biomass aqueous solution.

  In addition, the collection method of biomass water-soluble liquid is not limited to the said method, The water-soluble by-product of the vinegars collect | recovered in the manufacturing process of charcoal or bio-oil can also be used.

Calcium hydroxide (Ca (OH) ₂ ) can be dissolved in a high concentration in the collected biomass water-soluble liquid. As an example of the solubility of calcium hydroxide, the solubility of calcium hydroxide in water is 1.6 g / L (20 ° C.), whereas the aqueous biomass solution with a pH of 2-3 obtained from bamboo and rice husks. The solubility in was at least 20 g / L (20 ° C.). In other words, it has a calcium hydroxide solubility of at least 10 times the solubility in water. By utilizing this characteristic of the biomass water-soluble liquid, the gasification catalyst element can be uniformly supported on the coal at a high concentration.

  As for the acidity of the aqueous biomass solution, if the pH is less than 7, the solubility of sodium, potassium and calcium, which are gasification catalyst elements, is higher than that of water, so dissolve calcium hydroxide in an amount exceeding 1.6 g / L. Calcium can be supported on coal at a high concentration. And by further lowering the pH, the solubility of calcium can be further increased, and calcium can be supported on coal at a higher concentration. Therefore, it can be said that it is preferable to use a biomass water-soluble liquid having a pH lower than 7 and a pH as low as possible, but by using a biomass water-soluble liquid of calcium hydroxide having a pH of 2 to 3 obtained from bamboo and rice husk, Since it has been confirmed by experiments of the inventor that the gasification reaction rate can be sufficiently improved, the effect of the present invention can be sufficiently obtained by using a biomass water-soluble liquid having a pH of 2 to 3.

  The biomass ash used in the present invention includes a gasification catalyst element of at least one of sodium, potassium, and calcium that functions as a coal gasification catalyst. Then, the biomass ash is brought into contact with an acidic biomass aqueous solution to dissolve the gasification catalyst element contained in the biomass ash, and this is supported on coal as a gasification catalyst.

  As the biomass ash, ash obtained when gasifying the biomass raw material, for example, one obtained in a fluidized bed or fixed bed gasification furnace can be used, but is not limited thereto. Biomass ash obtained by incineration can also be used. However, if the heat applied to the biomass raw material is too high, the gasification catalyst element volatilizes and decreases. Therefore, it is preferable to use biomass ash heated within a range in which the gasification catalyst element does not volatilize and decrease.

  The inventors of the present application have examined five types of biomass ash α1 to α5 (see Table 1) having different compositions. As a result, in all the biomass ash, an improvement in the gasification reaction rate was observed. It was the largest in ash α5, and decreased in the order of α4, α3, α2, and α1. In Table 1, nd means unquantified.

  From this, if the biomass ash contains gasification catalyst elements such as sodium, potassium, and calcium, an effect of improving the gasification reaction rate can be expected by extracting with an acidic biomass aqueous solution and supporting it on coal. . And, it is considered that the effect can be improved by increasing the content of the gasification catalyst element. Among them, particularly, the effect of improving the gasification reaction rate can be obtained by increasing the content of potassium. It turns out that it is easy. For example, when focusing on the potassium content of biomass ash, in order to increase the gasification reaction rate, it is preferably 2.7 wt% or more, more preferably 13 wt% or more, and 18 wt% or more. Is more preferably 27 wt% or more, and still more preferably 59 wt% or more.

  The biomass ash that can be used as the gasification catalyst extraction source is not limited to the above composition, and various biomass ash that can dissolve the gasification catalyst element in an acidic biomass water-soluble liquid can be used. Biomass ash that can be used as an acidic gasification catalyst extraction source has the effect of increasing the pH of an acidic biomass aqueous solution when dissolved in the biomass aqueous solution. Therefore, the biomass ash is dissolved in an acidic biomass aqueous solution and the change in the pH value of the acidic biomass aqueous solution before and after the dissolution of the biomass ash is measured. It can be determined whether or not. In other words, by grasping the biomass ash having various composition ratios in an acidic biomass aqueous solution and measuring the change in pH value, the tendency of the composition ratio of biomass ash that can be used as a gasification catalyst extraction source is grasped. It becomes possible. Biomass ash includes coal ash. That is, coal ash having a high gasification catalyst element compound content can also be used as a gasification catalyst extraction source.

Here, when coal in which calcium is supported as a gasification catalyst is burned or gasified, calcium oxide (CaO) and calcium carbonate (CaCO ₃ ) are generated from the calcium supported in the coal. According to the experiments of the present inventors, it was confirmed that this calcium can be recovered by contacting the ash after combustion or after gasification of coal in which calcium is supported as a gasification catalyst with a biomass aqueous solution. Therefore, calcium-supporting coal can be obtained by dissolving calcium oxide or calcium carbonate in a biomass water-soluble liquid. That is, even if the calcium contained in the biomass ash is in the form of calcium oxide or calcium carbonate, it is possible to obtain calcium-supporting coal by dissolving calcium in the biomass water-soluble liquid. Further, sodium compounds and potassium compounds can be sufficiently dissolved in an acidic biomass aqueous solution and reused as a gasification catalyst.

  As raw material coal for carrying | supporting a gasification catalyst element, the general pulverized coal with which coal gasification power generation is used can be used, and coal type is not specifically limited. Although it is preferable to use pulverized coal having an average particle size of 100 μm or less in order to disperse and carry the gasification catalyst element at a high concentration, the pulverized coal is not limited to pulverized coal having this average particle size range.

  The gasification catalyst element can be supported on the coal by bringing the coal into contact with the gasification catalyst-containing solution of the present invention. The gasification catalyst-containing solution contains at least one of the gasification catalyst elements of sodium, potassium, and calcium that functions as a coal gasification catalyst, and inhibits the dissolution of the gasification catalyst element in the biomass aqueous solution. It is a biomass water-soluble liquid in which the gasification catalyst element of biomass ash not containing silica is dissolved. This contact can be performed, for example, by immersing coal in the impregnating liquid using the gasification catalyst-containing solution of the present invention as the impregnating liquid.

  It is preferable to immerse the coal in the impregnation liquid with respect to the total amount of coal to be subjected to the gasification treatment. In this case, the gasification catalyst element is supported at a high concentration and the total amount of coal to be subjected to the gasification treatment, so that the operating conditions of the gasification furnace can be kept stable. It is also possible to immerse only a part of the coal subjected to the coal gasification treatment in the impregnating liquid so as to increase the average value of the amount of gasification catalyst element supported relative to the total amount of coal. However, in this case, it is preferable to uniformly mix the gasification catalyst-supported coal and the gasification catalyst-unsupported coal from the viewpoint of stably maintaining the operating conditions of the gasification furnace. It is also possible to dilute the stock solution of the biomass water-soluble liquid with water and then immerse the entire amount of coal in the impregnating solution to carry the gasification catalyst element on the entire amount of coal.

  By setting the impregnating liquid to a volume amount substantially equal to the total amount of coal, the amount of heat required in the subsequent drying step can be suppressed. In addition, a large amount of impregnation liquid with respect to the total amount of coal is subjected to immersion treatment, and the entire amount of impregnation liquid is dried to increase the amount of heat required for the drying process. It is possible to increase the amount of catalytic element.

  In addition, the wettability of coal is fully ensured by using a biomass water-soluble liquid as an impregnation liquid. Therefore, the impregnation liquid can be brought into contact with the entire surface of the coal to fully support the gasification catalyst element.

  Here, the method of bringing coal into contact with the impregnating liquid is not limited to the method of immersing coal in the impregnating liquid. For example, you may employ | adopt the method of making an impregnation liquid contact-flow-contact with coal.

  After impregnating the impregnating liquid into the coal, a drying process is performed. This treatment is performed, for example, by heating at a temperature of 100 ° C. or higher. In order to maximize the catalyst performance and lower the coal gasification process, it is preferable to remove moisture contained in the coal as much as possible by the drying process. As long as the effect is achieved, moisture may remain in the coal.

  The gasification catalyst element is supported on the coal when the gasification catalyst element is bonded to a carboxyl group (—COOH group), a hydroxyl group (—OH group), or the like, which is an ion-exchange functional group in coal. Therefore, before these ion-exchange functional groups disappear, that is, before the coal is heated at 250 ° C. or higher, the gasification catalyst element is supported on the coal. When these ion-exchange functional groups disappear, it becomes difficult for the gasification catalyst element to be supported on the coal, and it becomes difficult to improve the catalytic activity.

  The effect of the present invention is not achieved only by using a liquid with high acidity as a dissolution medium for the gasification catalyst element. It is not a woody biomass raw material, a herbaceous biomass raw material, or a plant-derived food residue. This is a unique effect produced by using an acidic biomass aqueous solution generated when carbonizing at least one of them. That is, the present inventor considered that the gasification catalyst element can be dissolved at a high concentration by using a liquid having a higher acidity than water as a dissolution medium for the gasification catalyst element. However, when an inorganic acid such as sulfuric acid or nitric acid is used, when the gasification catalyst-supporting coal is subjected to coal gasification, sulfur oxide or nitrogen oxide may be generated. Means are needed. Then, when it considered and examined using acetic acid of pH 4-5 whose acidity is higher than water as a dissolution medium of a gasification catalyst element, the result contrary to expectation was obtained. That is, it was confirmed that the catalytic activity is lower when acetic acid is used than when water is used as a dissolution medium for calcium which is a gasification catalyst element.

  From this, the effect of the present invention is not only due to the high solubility of the gasification catalyst element of the biomass water-soluble liquid, but the components contained in the biomass water-soluble liquid are converted from the gasification catalyst element to coal. It is considered that this effect is combined with the action that can be stably supported. That is, it is considered that one or more components other than acetic acid contained in the biomass water-soluble liquid have some influence on stably supporting the gasification catalyst element on coal. Moreover, by using an acidic biomass aqueous solution generated when carbonizing at least one of a woody biomass raw material, a herbaceous biomass raw material and a plant-derived food residue, an industrial acidic reagent or the like is used. Compared to the case, the cost can be greatly reduced.

  In addition, the biomass water-soluble liquid has a function of dissolving the catalyst component (ash component) of the coal itself and re-supporting the catalyst component on the coal surface. It is considered that an excellent gasification reaction rate improvement effect is obtained.

  The above-described embodiment is an example of a preferred embodiment of the present invention, but is not limited thereto, and various modifications can be made without departing from the scope of the present invention. For example, a water-soluble component obtained by liquid-liquid separation of a reaction product liquid obtained by subjecting a woody biomass raw material, a herbaceous biomass raw material and a plant-derived food residue to a batch-type hydrothermal reaction using an autoclave Can also be used as a dissolution medium for the calcium source material.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1
Various studies were conducted on the production of coal with gasification catalyst using an impregnating solution obtained by dissolving calcium hydroxide in an aqueous biomass solution obtained from a herbaceous biomass raw material.

(1) Collection and separation of biomass water-soluble liquid from herbaceous biomass raw material Collection and separation of biomass water-soluble liquid from herbaceous biomass raw material were performed by a biomass water-soluble liquid collection and separation system 1a shown in FIG.

  The biomass water-soluble liquid collecting / separating system 1a shown in FIG. 10 is composed of a horizontal electric furnace 2 having a horizontal furnace core tube 3, a first container 4, a second container 5, and a third container 6. The first container 4 captures the gas generated from the furnace core tube 3 as agglomerates and was installed in the ice bath 4 '. The second container 5 captures the gas that has passed through the first container 4 as an agglomerate, and was installed in the dry ice methanol tank 5 '. The third container 6 captures the gas that has passed through the second container 5 by bubbling it into ice water contained in the third container 6. The core tube 3 and the first container 4, the first container 4 and the second container 5, and the second container 5 and the third container 6 were connected by pipes 7, 8, and 9, respectively.

  In this example, bamboo-derived biomass water-soluble liquid and rice husk-derived biomass water-soluble liquid were generated using powders of bamboo (produced in Japan) and rice husk (produced in Japan), which are herbaceous plant-derived biomass raw materials. 10 g of bamboo powder as a raw material was charged into the core tube 3 of the electric furnace 2. The temperature increase rate of the electric furnace 2 was 6 ° C./min, the initial temperature was room temperature, and the temperature was increased to 500 ° C. The biomass raw material powder was carbonized by setting the furnace tube 3 to an argon atmosphere (flow rate 1000 cc / min). The gas generated during the carbonization process is captured in the first container 4 installed in the ice tank 4 ′ and the second container 5 installed in the dry ice-methanol tank 5 ′, and is heavy such as solid components and tar. Except for the components, it was subjected to the experiment as a biomass-derived aqueous solution derived from bamboo. Further, a gas was bubbled into the ice water in the third container 6 to capture low boiling point organic components not captured by the first container 4 and the second container 5, and this was used as a bubbling liquid for the experiment. Similarly, a biomass water-soluble liquid was obtained using 10 g of rice husk powder as a raw material, and this was subjected to experiments as a biomass water-soluble liquid derived from rice husk.

  The pH of these biomass aqueous solutions was 2-3. Moreover, it was confirmed that the solubility of calcium hydroxide in these biomass aqueous solutions is at least 20 g / L or more. Since the solubility of calcium hydroxide in water is 1.6 g / L (20 ° C.), it becomes clear that the solubility of calcium hydroxide in the biomass water-soluble liquid is 10 times or more the solubility in water. It was. From this, it became clear that sodium, potassium, and calcium, which are elements that function as a gasification catalyst, can be dissolved at a high concentration.

(2) Calcium loading and char preparation on coal Char was prepared from coal carrying calcium by impregnation method, and chars A to H for use in subsequent experiments were obtained. Table 2 shows the coal type of the pulverized coal used in this example and the composition of the impregnation liquid. Here, “calcium dissolution medium” in Table 2 means a solution for dissolving calcium hydroxide. The amount of calcium dissolution medium was all 1 ml. In this example, about 10% by volume of methanol was added in order to improve the wettability of pulverized coal. The amount of pulverized coal immersed in the impregnation liquid was 100 mg. The pulverized coal after the impregnation treatment is dried at 107 ° C., and then charged into an infrared electric furnace, heated in an argon atmosphere (flow rate 200 cc / min) at a heating rate of 600 ° C./min to 900 ° C., A gasification agent is prepared by carrying out char preparation by holding for 1 minute and subjecting to dry distillation, and preliminarily performing a gas phase-gas phase reaction, which is a thermal decomposition reaction that occurs in the early stage of the gasification reaction, to be a rate-limiting reaction in the entire gasification reaction Only gas phase-solid phase reaction with char could be measured in subsequent experiments. Further, as a reference sample, char was prepared from pulverized coal β1 and pulverized coal β3 which were not impregnated, and Char I and Char J were obtained, respectively. In this example, methanol was added to improve the wettability of pulverized coal, but the inventors of the present application later examined, and a process for increasing the wettability of pulverized coal by adding an organic solvent such as methanol. Even if it does not perform, it became clear that wettability of pulverized coal can be sufficiently secured with the biomass water-soluble liquid alone. Therefore, it is not necessary to add an organic solvent such as methanol in order to increase the wettability of coal.

  Table 3 shows the ash composition of pulverized coal β1 and pulverized coal β3. Table 3 also shows the ash content of pulverized coal β2 used in the following examples.

(3) Char gasification reaction rate measurement The char gasification reaction rate was measured by a constant temperature measurement method using a pan-type thermobalance (device name: TGA-DTA2000S, manufactured by Mac Science). 5 mg of char was charged into a 5 mmφ cell, and the temperature was raised to 850 ° C. at an increase rate of 15 ° C./min in an argon atmosphere (450 cc / min). Then, while maintaining the temperature at 850 ° C., the supply of argon is stopped, the carbon dioxide gas is supplied at 450 cc / min, and the gasification of the char is progressed at a gasifying agent concentration of 100%. The amount was monitored.

The gasification reaction rate x and the gasification reaction rate r were defined by the TG curve shown in FIG. That is, the weight reduction amount from the time T1 when the weight reduction started to the time T2 when the weight reduction was no longer observed was set as W0, and the weight reduction amount at each time T was set as W. And the gasification reaction rate x was calculated | required by Numerical formula 1. The gasification reaction rate r was determined from the time derivative of the reaction rate shown in Equation 2.
[Formula 1] x = W / W ₀
[Formula 2] r = dx / dt = (dW / dt) / W ₀

(4) Examination of influence on gasification performance by calcium dissolution medium The gasification reaction rate of char A, F, G, H and I was measured, and the influence on the gasification performance by the calcium dissolution medium was examined. The results are shown in FIG. a is char I (no impregnation treatment), b is char F (calcium dissolution medium: acetic acid), c is char G (calcium dissolution medium: bubbling solution), d is char H (calcium dissolution medium: water), e is char The measurement result of A (calcium dissolution medium: bamboo-derived biomass aqueous solution) is shown. Further, in order to facilitate comparison of the gasification reaction rate r, FIG. 4 shows the gasification reaction rate x with respect to the reaction time T. E took the shortest time to complete the reaction, followed by c, d, b and a. From this result, it was confirmed that when bamboo-derived biomass water-soluble liquid was used as a calcium dissolution medium, the gasification reaction rate was about 3 to 4 times faster than raw coal. In addition, it was confirmed that the gasification reaction rate was about twice as fast as when water was used as the calcium dissolution medium. Furthermore, it was confirmed that when acetic acid was used as the calcium dissolution medium, the gasification reaction rate was slower than when water was used as the calcium dissolution medium. One possible cause is as follows. That is, when calcium-supporting coal was produced using acetic acid as a calcium dissolution medium, white deposits were confirmed on the inner wall of the container used for the drying treatment. This is because the solubility of calcium acetate produced by the reaction of calcium hydroxide and acetic acid in the calcium dissolution medium decreases as the temperature rises during the drying process. It is considered that this is due to the fact that the amount of calcium supported on the coal after drying was lower than when water was used as the calcium dissolution medium due to precipitation of calcium caused by the reaction. From the above results, it was shown that when the bamboo-derived biomass aqueous solution is used as the calcium dissolution medium, the catalytic activity can be improved most. In addition, when acetic acid was used as the calcium dissolution medium, it was confirmed that the gasification reaction rate was slower than when water was used as the calcium dissolution medium. It has been clarified that the catalytic activity of coal cannot be increased only by using. That is, by using an acidic biomass aqueous solution as a gasification catalyst element dissolution medium, sodium, potassium and calcium contained in biomass ash are stably supported on coal at a high concentration, and the catalytic activity of coal is enhanced. It became clear.

(5) Examination of the influence on the gasification performance by the amount of calcium loaded on the coal Measure the gasification reaction rate of Char B, C, D and J and examine the influence on the gasification performance by the amount of calcium hydroxide added. went. The results are shown in FIG. a is char J (no calcium hydroxide added), b is char B (calcium hydroxide 5 mg added), c is char C (calcium hydroxide 10 mg added), d is char D (calcium hydroxide 20 mg added). Is shown. As the amount of calcium hydroxide added increases, the gasification reaction rate of char also improves, and when 20 mg of calcium hydroxide is added, the gasification reaction rate is about four times faster than that of raw coal. Was confirmed. Therefore, if the gasification catalyst element contained in the biomass ash is large, it becomes easier to increase the catalytic activity, and the amount of biomass ash to be used can be increased to increase the biomass water-soluble liquid of the gasification catalyst element. It has been clarified that the catalytic activity can be increased by increasing the amount dissolved in the catalyst.

(6) Examination of the effect of biomass raw material species on gasification performance The gasification reaction rates of Char A and E were measured, and the influence of biomass raw material species on gasification performance was examined. The results are shown in FIG. a shows the measurement result of char A (calcium dissolution medium: bamboo-derived biomass water-soluble liquid), and b shows the measurement result of char E (calcium dissolution medium: rice husk-derived biomass water-soluble liquid). From the results of a and b, it was confirmed that no difference was observed in the gasification reaction rate between either the herbaceous biomass raw material bamboo or rice husk.

(7) Examination of recovery and recycling of calcium from generated ash of calcium-supporting coal 10 mg of calcium hydroxide was dissolved in 1 ml of bamboo-derived biomass aqueous solution, and 100 mg of pulverized coal β3 was added to this solution and impregnated. Thereafter, it was dried at 107 ° C. and burned in air. The total amount of the generated ash after combustion was added to 1 ml of bamboo-derived biomass aqueous solution, and further impregnated with 100 mg of pulverized coal β3, dried at 107 ° C., and then char was prepared. Char preparation was performed under the same conditions as in (2) above. The gasification reactivity of this secondary calcium-supported char was compared with the gasification reactivity of char C. The results are shown in FIG. a is char J, b is a secondary calcium-supporting char, and c is the char C measurement result. Comparing the measurement results of b and c, since there was almost no difference in gasification reactivity, it was clear that the total amount of calcium supported as a gasification catalyst could be recovered and reused from coal combustion ash It became.

  The form of calcium supported on coal as a gasification catalyst changes into calcium oxide and calcium carbonate by a combustion reaction or a gasification reaction. Therefore, it is considered that calcium supported on coal as a gasification catalyst was dissolved in bamboo-derived biomass aqueous solution as a calcium dissolution medium in the form of calcium oxide and calcium carbonate. From this, it is clear that even if calcium is present in biomass ash in the form of calcium oxide or calcium carbonate, it can be dissolved in biomass water-soluble liquid and supported on coal as a gasification catalyst. It became. In addition, since sodium compounds and potassium compounds are generally readily soluble in water, no matter what form sodium or potassium is in the biomass ash, it is sufficiently soluble in acidic biomass solutions. Thus, it can be used as a gasification catalyst.

(Example 2)
Various studies were conducted on the production of coal with gasification catalyst using an impregnation solution in which calcium hydroxide was dissolved in a biomass water-soluble solution obtained from a woody biomass raw material.

(1) Collection and separation of biomass water-soluble liquid from woody biomass raw material and plant-derived food residue Collection and separation of biomass water-soluble liquid from woody biomass raw material is performed by biomass water-soluble liquid collection and separation system 1b shown in FIG. It was.

  The biomass water-soluble liquid collection / separation system 1b shown in FIG. 11 has substantially the same configuration as the biomass water-soluble liquid collection / separation system shown in FIG. The configuration differs from the biomass water-soluble liquid collection and separation system shown in FIG. That is, the electric furnace 2 having the core tube 3, the first container 4, the second container 5, and the third container 6 are configured, and the core tube 3, the first container 4, the first container 4, and the second container are formed. 5, The 2nd container 5 and the 3rd container 6 are connected by piping 7,8,9, respectively.

  The shape of the core tube 3 is a vertical type, and inside the core tube 3, a porous plate (eye plate) 12 having a plurality of through holes and quartz wool 13 are arranged, and the biomass raw material to be fed into the core tube 3 Was held in the core tube 3. Then, by supplying an inert gas from the upper part of the furnace core tube 3, the gas generated during the carbonization treatment is forcibly exhausted from the pipe 7 toward the first container 4.

  The discharge from the pipe 7 was introduced into the first container 4, and the first container 4 was kept warm by the heat retaining heater 14. The temperature of the heat retaining heater 14 was controlled by the thermocouple 16, and the temperature in the vicinity of the introduction portion of the pipe 8 was set to 100 ° C. to 110 ° C. As a result, heavy components such as tars and solids contained in the discharge from the pipe 7 are collected in the first container 4, and the gaseous discharge that has not been collected in the first container 4 and the first Among the components once collected in the container 4, the components that evaporate at the set temperature of the heat retaining heater 14 are introduced into the pipe 8.

  The discharge from the pipe 8 was introduced into the second container 5. The pipe 8 is provided with a Liebig cooler 15 that is a water circulation type cooling device, and the heat-retaining heater 14 among the gaseous effluents not recovered in the first container 4 and the components once recovered in the first container 4. The components that evaporate at the set temperature were cooled, and aggregates were collected in the second container 5.

  A low boiling point organic component that was not recovered in the second container 5 was introduced into the pipe 9. Water was put in the third container 6 and the low-boiling organic components were recovered by bubbling the gas discharged from the pipe 9.

  In this example, cedar chips (produced in Japan), cedar bark (produced in Japan), which are woody biomass materials, and orange peel are used as a biomass water-soluble liquid derived from cedar chips, a biomass water-soluble liquid derived from cedar bark and orange Each of the peel-derived biomass water-soluble liquids was produced. 10 g of cedar chips as a raw material was put into the furnace core tube 3 of the electric furnace 2. The cedar chips were charged in a state where the furnace temperature of the electric furnace 2 was set to 500 ° C. The biomass raw material powder was carbonized by setting the furnace tube 3 to a nitrogen atmosphere (flow rate 1000 cc / min). The gas generated during the carbonization treatment was collected in the first container 4, the second container 5, and the third container 6, and the aggregate collected in the second container 5 was used as a biomass water-soluble liquid derived from cedar chips.

  Similarly, a cedar bark-derived biomass water-soluble liquid was obtained using 10 g of cedar bark as a raw material, and an orange peel-derived biomass water-soluble liquid was obtained using 10 g of orange peel. The pH of these biomass aqueous solutions was 2-3. Moreover, it was confirmed that the solubility of calcium hydroxide in these biomass aqueous solutions is at least 20 g / L or more. Since the solubility of calcium hydroxide in water is 1.6 g / L (20 ° C.), it becomes clear that the solubility of calcium hydroxide in the biomass water-soluble liquid is 10 times or more the solubility in water. It was. In other words, even when using woody biomass raw materials or using plant-derived food residues, a biomass water-soluble liquid having the same properties as when using herbaceous biomass raw materials can be obtained. Was confirmed.

(2) Calcium loading and char preparation on coal Char was prepared from coal carrying calcium by an impregnation method to obtain chars K to M for use in subsequent experiments. Table 4 shows the coal type of the pulverized coal used in this example and the composition of the impregnation liquid. The amount of calcium dissolution medium was all 1 ml. Further, in this example, the wettability of the pulverized coal was sufficiently secured, so methanol was not added to improve the wettability of the pulverized coal. The amount of pulverized coal immersed in the impregnation liquid was 100 mg. The pulverized coal after the impregnation treatment is dried at 107 ° C., and then charged into an infrared electric furnace, heated in an argon atmosphere (flow rate 200 cc / min) at a heating rate of 600 ° C./min to 900 ° C., A gasification agent is prepared by carrying out char preparation by holding for 1 minute and subjecting to dry distillation, and preliminarily performing a gas phase-gas phase reaction, which is a thermal decomposition reaction that occurs in the early stage of the gasification reaction, to be a rate-limiting reaction in the entire gasification reaction Only gas phase-solid phase reaction with char could be measured in subsequent experiments.

(3) Measurement of char gasification reaction rate The same method as in Example 1 was used.

(4) Examination of the influence on the gasification performance by the biomass raw material species The gasification reaction rate was measured for the chars K to M, and the influence on the gasification performance by the biomass raw material species was examined. The results are shown in FIG. In FIG. 8, a is char K (calcium dissolution medium: cedar chip-derived biomass water-soluble liquid), b is char L (calcium dissolution medium: cedar bark-derived biomass water-soluble liquid), and c is char M (calcium dissolution medium: orange). The measurement result of the skin-derived biomass aqueous solution) is shown. D to f are the results obtained in Example 1 and are shown in FIG. 8 for comparison with the measurement results of a to c. That is, d is a measurement result of char A (calcium dissolution medium: bamboo-derived biomass water-soluble liquid), e is char E (calcium dissolution medium: rice husk-derived biomass water-soluble liquid), and f is a measurement result of char I (no impregnation treatment). .

  From the results shown in FIG. 8, from the cedar chip-derived biomass aqueous solution, the cedar bark-derived biomass aqueous solution and the orange peel-derived biomass aqueous solution, the bamboo-derived biomass aqueous solution and the rice husk-derived biomass aqueous solution. There was almost no difference in the gasification reaction rate. Therefore, even when using a biomass water-soluble liquid obtained from a woody biomass raw material and a plant-derived food residue such as fruit skin, the same effect as when using a biomass water-soluble liquid obtained from a herbaceous biomass raw material is obtained. It became clear that it was obtained.

(Example 3)
As biomass ash, α4 ash and α1 ash in Table 1 were used, and a production test of gasification catalyst-supported coal was conducted to evaluate its performance.

  The biomass ash used in the experiment was ashed at 820 ° C., and the biomass ash obtained by the same treatment was used in the subsequent experiments.

  To 20 mg of α4 ash, 1 ml of the biomass water-soluble liquid derived from cedar chips obtained in Example 2 was added and subjected to ultrasonic irradiation for 5 minutes, followed by solid-liquid separation with a filter having a pore size of 0.2 μm. The filtrate was impregnated by adding pulverized coal β1 or pulverized coal β2, and then dried at 107 ° C. to adjust the char. Char adjustment was performed in the same manner as in Example 1.

  The gasification reaction rate of the char-adjusted sample was measured, and the influence on the gasification performance when α4 ash was used as the gasification catalyst extraction source was examined. The results are shown in FIG. a shows the measurement result of the pulverized coal β1 char carrying the gasification catalyst using α4 ash, b shows the measurement result of the pulverized coal β2 char carrying the gasification catalyst using α4 ash, c The measurement result of the pulverized coal β1 char not supporting the gasification catalyst is shown, and d shows the measurement result of the pulverized coal β2 char not supporting the gasification catalyst. Further, in order to facilitate comparison of the gasification reaction rate r, FIG. 13 shows the gasification reaction rate x with respect to the reaction time T.

  From this result, the gasification reaction rates of pulverized coal β1 char carrying a gasification catalyst using α4 ash and pulverized coal β2 char carrying a gasification catalyst using α4 ash are compared with those of raw coal. It was confirmed that it was improved 8 to 10 times.

  Moreover, when the same experiment was conducted using α1 ash as biomass ash, an effect of improving the gasification reaction rate was obtained, but it was confirmed that the effect was smaller than when α4 ash was used. It was done.

  When the α4 ash was added to the biomass water-soluble liquid, the pH value of the biomass water-soluble liquid was greatly increased. However, when the α1 ash was added to the biomass water-soluble liquid, the pH value of the biomass water-soluble liquid was not so high. It did not fluctuate greatly. From this, it was found that the fluctuation of the pH value of the biomass water-soluble liquid can be a criterion for determining whether or not the effect as a gasification catalyst extraction source is excellent.

  The results of analysis of inorganic components contained in various biomass ash are as shown in Table 1. This analysis was performed by atomic absorption method and ICP emission analysis method.

  As shown in Table 1, since α4 ash contained more gasification catalyst elements than α1 ash, Na, K, and Ca that function as gasification catalysts were eluted into the biomass water-soluble liquid. As a result, it is considered that the effect of improving the gasification reaction rate was high.

Example 4
Using the rice husk-derived biomass water-soluble liquid and the cedar chip-derived biomass water-soluble liquid, the influence of the biomass water-soluble liquid itself on coal was examined.

  The cedar chip-derived biomass aqueous solution used was obtained in Example 2. The rice husk-derived biomass water-soluble liquid was obtained by using the biomass water-soluble liquid collection and separation system 1b shown in FIG.

  100 mg of pulverized coal is added to 0.5 ml of the rice husk-derived biomass aqueous solution, impregnated overnight (12 hours), dried at 107 ° C., and prepared in the same manner as (2) of Example 1 Went. The same treatment was performed for the cedar chip-derived biomass aqueous solution. Char obtained using the rice husk-derived biomass water-soluble liquid is referred to as sample X, and char obtained using the cedar chip-derived biomass water-soluble liquid is referred to as sample Y. Note that β1 was used as pulverized coal.

  Moreover, the rice husk is used as a biomass raw material, and all the aggregates collected in the first container 4 to the third container 6 are collected using the biomass water-soluble liquid collecting / separating system 1 ′ shown in FIG. 11 and dried at 107 ° C. Then, char was prepared in the same manner as in Example 1 (2). This char is called Sample Z.

  For samples X to Z, the gasification reaction rate was measured by the same method as in Example 1. The measurement results are shown in FIG. In FIG. 9, the result of measuring the gasification reaction rate of untreated pulverized coal β1 char as a comparative sample is shown as sample A.

  From the results shown in FIG. 9, it has been clarified that the gasification reaction rate is improved about twice as much as that of the untreated pulverized coal char only by impregnating the pulverized coal with the aqueous biomass solution. Here, for sample Z, which is char prepared from rice husks alone, the gasification reaction rate was slower than that of untreated pulverized coal char, so the components themselves contained in the biomass water-soluble liquid increase the gasification reaction rate. It was thought that it was not a factor.

  Therefore, the factors that increase the gasification reaction rate by the biomass aqueous solution can be considered as follows. That is, when the biomass water-soluble liquid is impregnated with pulverized coal, the catalyst component contained in the pulverized coal itself is dissolved in the biomass water-soluble liquid, and this catalyst component is re-supported on the surface of the pulverized coal, thereby causing a gasification reaction. It is thought that the speed has increased. That is, acidic biomass is brought into contact with coal by contacting an acidic biomass aqueous solution generated when carbonizing at least one of a woody biomass raw material, a herbaceous biomass raw material, and a plant-derived food residue. It is also possible to produce a gasification catalyst-supporting coal by dissolving a gasification catalyst element contained in the coal itself in an aqueous solution and supporting it.

  As described above, according to the present invention, the gasification catalyst element is dissolved in the biomass water-soluble liquid at a high concentration so that the gasification catalyst element is supported at a high concentration on the pulverized coal, and the catalyst component possessed by the pulverized coal itself. In combination with the effect that the catalyst component is re-supported on the surface of the pulverized coal by dissolving in the biomass water-soluble liquid, an excellent gasification reaction rate improvement effect is obtained.

  Here, as shown in Table 3, the composition of the ash component of the pulverized coal β1 used in the present example was found to be mainly composed of calcium oxide. Further, from the results of X-ray diffraction, it was found that the calcium compound contained in the raw coal was calcium carbonate. From this, it is considered that by bringing the biomass water-soluble liquid into contact with coal, calcium carbonate in the coal is dissolved, and calcium is highly dispersed on the surface of the pulverized coal, thereby obtaining a catalytic effect.

(Example 5)
As the biomass ash, α4 ash of Table 1 was used, and the influence of the time for impregnating pulverized coal in the biomass water-soluble liquid brought into contact with α4 ash on the gasification reaction rate was examined.

  1 ml of the biomass water solution derived from cedar chips obtained in Example 2 was added to 40 mg of α4 ash, and after ultrasonic irradiation for 5 minutes, solid-liquid separation was performed with a filter having a pore size of 0.2 μm. Next, 200 mg of pulverized coal β2 was impregnated with 0.2 ml of the filtrate, and Sample 1 dried at 107 ° C. immediately after the start of impregnation and Sample 2 dried at 107 ° C. 5 hours after impregnation were prepared. Samples 1 and 2 were subjected to char adjustment in the same manner as in Example 1.

  The gasification rate of the char-adjusted sample was measured, and the influence of the gasification rate on the impregnation time was investigated. The results are shown in FIG. From this result, it is clear that the effect of increasing the gasification reaction rate does not depend on the impregnation time, and by drying the pulverized coal immediately after impregnation, a sufficient gasification reaction rate improvement effect can be obtained, It became clear that catalyst-supporting coal could be produced quickly.

(Example 6)
Using the ash of α1 to α5 in Table 1 as biomass ash, a production test of gasification catalyst-carrying coal was conducted to evaluate its performance.

  To 20 mg of various biomass ash, 1 ml of the biomass water-soluble liquid derived from cedar chips obtained in Example 2 was added and subjected to ultrasonic irradiation for 5 minutes, followed by solid-liquid separation with a filter having a pore size of 0.2 μm. The filtrate was impregnated with pulverized coal β2 and dried at 107 ° C., and then char was adjusted. Char adjustment was performed in the same manner as in Example 1.

The gasification rate of the char-adjusted sample was measured, and the effect on the gasification performance when using various biomass ash as the gasification catalyst extraction source was investigated. The results are shown in FIG. In FIG. 15, “R” is the gasification reaction rate (r _ash = dx / dt _{x = 0.5} ) when the solution obtained by bringing biomass ash into contact with the biomass aqueous solution is impregnated with pulverized coal β2. The ratio of the gasification reaction rate (r _raw = dx / dt _{x = 0.5} ) when impregnating pulverized coal β2 into a solution in which the biomass ash and the biomass water-soluble liquid are not in contact with each other.

  From this result, it became clear that any ash of α1 to α5 has an effect of increasing the gasification reaction rate as compared with the case of using raw coal. And it became clear that the effect is the highest in α5 and decreases in the order of α4, α3, α2, and α1.

  Here, for calcium, sodium and potassium, which are gasification catalyst elements contained in the ash of α1 to α5, the total content of the oxides was calculated, α1 was 3.92 wt%, α2 was 71.66 wt%, α3 was 41.59 wt%, α4 was 43.07 wt%, and α5 was 61.56 wt%, which did not match the results of FIG.

  This result can be considered as follows. That is, calcium has a lower catalytic effect than sodium and potassium, and among the gasification catalyst elements, α2 having a large proportion of calcium, although the total content of gasification catalyst elements is the highest, It is thought that the effect of improving the gasification reaction rate was smaller than α3, α4, and α5.

  In addition, regarding α3 and α4, although there is no significant difference in the total content of gasification catalyst elements, there is a clear difference in the effect of improving the gasification reaction rate in α3. This is considered to be due to the large proportion of calcium.

(Example 7)
About the extraction effect of the catalyst component from the ash of α4 and α5, a comparative experiment was conducted using water and an aqueous biomass solution.

  To 20 mg of α4 or α5 ash, 1 ml of the biomass water-soluble liquid derived from cedar chips or water obtained in Example 2 was added and subjected to ultrasonic irradiation for 5 minutes, followed by solid-liquid separation with a filter having a pore size of 0.2 μm. The filtrate was impregnated with pulverized coal β2 and dried at 107 ° C., and then char was adjusted. Char adjustment was performed in the same manner as in Example 1.

  The gasification reaction rate of the char-adjusted sample was measured, and the extraction effect of catalyst components in the case of using water and biomass aqueous solution was investigated. The results are shown in FIG. When water was used, the effect of improving the gasification reaction rate was not sufficient, and the difference in gasification reaction rate when using α4 and α5 ash was not obtained. That is, water has a low ability to dissolve the gasification catalyst component, the water is saturated and the gasification catalyst component does not dissolve, and as a result, the gasification catalyst component contained in the ash of α4 and α5 remains. It is considered that the effect of improving the gasification reaction rate was not sufficiently obtained.

  On the other hand, when the biomass water-soluble liquid is used, the gasification catalyst component contained in the ash of α4 and α5 can be sufficiently dissolved and extracted, resulting in an excellent gasification reaction rate improvement effect. It is thought that it was obtained.

  In addition, since the α5 ash contained 26.7 wt% of silica, a compound of silica and a gasification catalyst element was generated in the ash adjustment process, and thereby the gasification catalyst element was contained in water. However, when the biomass water-soluble liquid was used as the dissolution medium, a higher gasification reaction rate improvement effect was obtained compared to the case where α4 ash was used. . From this, even if a compound of silica and a gasification catalyst element is generated in the ash adjustment process, the gasification catalyst element can be reliably extracted from the biomass ash by using the biomass water-soluble liquid as a dissolution medium. Became clear.

It is a figure which shows an example of a structure of the apparatus which collects and isolate | separates biomass water-soluble liquid from biomass raw material. It is a figure explaining the definition of weight reduction W and total weight reduction W0. It is a figure which shows the measurement result of the gasification reaction rate at the time of using various calcium dissolution media. FIG. 4 is a diagram showing the result of FIG. 3 as a gasification reaction rate x with respect to a reaction time T. It is a figure which shows the difference in the gasification reaction rate at the time of changing the amount of calcium carrying to coal. It is a figure which shows the measurement result of the gasification reaction rate at the time of using various herbaceous biomass raw materials. It is a figure which shows the measurement result of the gasification reaction rate at the time of carrying | supporting the calcium collect | recovered from the production | generation ash of calcium carrying coal on pulverized coal again. It is a figure which shows the measurement result of the gasification reaction rate at the time of using various biomass raw materials. It is a figure which shows the result of having investigated the influence which biomass aqueous solution itself has on gasification reaction rate. It is a figure which shows the structure of the collection separation apparatus of the biomass aqueous solution used in Example 1. FIG. It is a figure which shows the structure of the collection separation apparatus of the biomass aqueous solution used in Example 2. FIG. It is a figure which shows the measurement result of the gasification reaction rate at the time of using (alpha) 4 ash as a gasification catalyst extraction source. It is the figure which showed the result of FIG. 12 as the gasification reaction rate x with respect to reaction time T. FIG. It is a figure which shows the result of having examined about the influence which the impregnation time of pulverized coal to biomass water-soluble liquid has on the gasification reaction rate. It is a figure which shows the result of having examined about the gasification reaction rate improvement effect at the time of using various biomass ash. It is a figure which shows the result of having examined about the catalyst component extraction effect at the time of using water and biomass water-soluble liquid.

Claims (2)

Acidic biomass water-soluble liquid generated when carbonizing at least one of woody biomass raw material, herbaceous biomass raw material and plant-derived food residue, and sodium, potassium and calcium that function as coal gasification catalysts A biomass ash containing a gasification catalyst element of at least one of
The biomass water-soluble liquid is brought into contact with the biomass ash to dissolve the gasification catalyst element contained in the biomass ash in the biomass water-soluble liquid, and the biomass water-soluble liquid is brought into contact with coal to the coal. A process for producing a gasification catalyst-supporting coal, characterized by supporting a gasification catalyst element. Sodium, potassium and calcium that function as a coal gasification catalyst in an acidic biomass aqueous solution generated when carbonizing at least one of a woody biomass raw material, a herbaceous biomass raw material and a plant-derived food residue A gasification catalyst-containing solution in which the gasification catalyst element of biomass ash containing at least one of the gasification catalyst elements is dissolved.