JP2004137144A - Porous carbon material, porous carbon material powder using the same, method of manufacturing the same, and method of manufacturing porous carbon material product using the porous carbon material powder - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porous carbon material and porous carbon material powder prepared to turn various kinds of bran conventionally treated like an useless material to a highly functional product and having a novel structure, a manufacturing method of the porous carbon material powder by which the porous carbon material powder is efficiently and stably fired to be carbonized and which is composed of a novel constitution and a manufacturing method of a porous carbon mbaterial product which uses the porous carbon material powder and is compposed of a novel constitution using the porous carbon material power in the effective utilization of the bran. <P>SOLUTION: The porous carbon material is prepared by adding a thermosetting resin and the proper quantity of a glue-containing aqueous solution or water into the particle size adjusted bran of rice, wheat or the like, drying the kneaded mixed bran, granulating to form a bran granular base material and firing the bran granular base material under an inert gas atmosphere or vacuum to carbonize. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention aims to widely apply as a material for high-performance products, by converting fu-bran, which had been regarded as having a low utility value, into a porous carbon material which is a promising industrial resource. In particular, the technical field is not specified, and any field is the technical field, and therefore, the technical field related to agriculture producing fu bran or people consuming fu bran In addition to the technical field of refining oily content from rice bran, etc., the field of manufacturing and selling various machines such as manufacturing machines, testing machines, facility equipment necessary for the field, and providing the necessary materials and parts for them The field, providing machinery and tools necessary for the processing of these materials and parts, and providing the materials, machinery, equipment and components necessary for such materials, such as wood, plywood, plastic, and various metal materials Field of electronic components incorporated in them, the field of control equipment that integrates them, the field of various measuring instruments, the field of power machinery that moves the equipment and instruments, the power that is the energy and the electricity and oil that is the energy source. Fields generally referred to as industrial machines, such as fields, furthermore, those facilities and instruments are tested and researched, and repair, display, sale, import / export, and use of them, and fields in which they are used, All fields of application of the new material of the present invention obtained from bran as a raw material and powders using the same, agriculture, machinery, electricity, chemistry, etc. necessary to implement the manufacturing method included in the present invention All technical fields, collecting and transporting garbage generated in the process of carrying out the manufacturing method of the present invention, collecting and transporting, recycling, recycling garbage efficiently, and It can not be assumed at the time but, and to the ends of the unknown in the art to which the coming new addition, it is enough not the technical field that is not related.

(point of view)
Rice, a major grain in Japan, produces large amounts of rice husks and bran as by-products. Similarly, cereals such as wheat, buckwheat, and soybeans also produce a large amount of husks and fus (husma), and many of the by-products from cereals, such as husks and fusi, are incinerated as obstructions. Either the rice bran is crushed to produce rice bran oil, or a very small part of the husk (particularly rice husk) is used as culvert material or smoked charcoal, and is distilled during the coal making process. Dry distillate vapors are sometimes condensed and used as insect repellents, animal repellents, soil conditioners, athlete's foot remedies, and the like.

However, most of the bran containing defatted bran has been used only for agricultural purposes, such as being converted into feed or mushroom culture medium, or converted into fertilizer. There is a continuing search for the effective use of such materials as industrial materials. One of them is a technology to carbonize fusi bran. The carbonization of this bran is, on a small scale, carried out by a method of steaming in a batch system, and on a large scale, is carried out by a method of continuously burning in a rotary kiln or a multi-stage fluidized bed furnace or the like. However, the rice bran is a very fine powder, has poor air permeability and thermal conductivity, and even contains a small amount of fats and oils. The ratio is large, and it is difficult to efficiently and completely carbonize it, which is a great disadvantage in terms of economic efficiency.In addition, the produced carbide becomes fine and easily scattered, resulting in inconvenient handling. Due to such problems, there has been no record of aggressive commercialization. Therefore, charcoal (so-called “charcoal”) formed from wheat bran cannot be used for agricultural purposes in terms of quality and quantity. Although it is used as a soil conditioner, Is the reality of never be effectively used as a use material.

(Conventional technology)
As he was involved in the rice bran oil manufacturing industry, he was very interested in the effective use of defatted bran, so he quickly worked on the technology development and research and obtained guidance from both the Faculty of Engineering and the Yamagata Prefecture Industrial Technology Center. As already described in Japanese Patent Application Laid-Open No. 10-101453, as a "production method of a porous carbon material product", when defatted bran and the like, finally crushed rice hulls and wheat are ground to powder. The raw material is fu (bran) that comes out as shavings and, in some cases, fu brans, including buckwheat husks, soy husks, etc., for example, very familiar materials such as building materials such as outer wall materials, furniture, and packing materials. Technology related to the effective use of rice bran, which is used to form high-performance products such as conductive materials, heating elements, and electronic components by electrolytic refining into bearing parts and other mechanical parts. The has been completed.

Then, according to the completed “Production method of porous carbon material product”, the production of various high-performance products was started, and from the viewpoint of effective use of resources, as well as quality and function, it was too useful. While reconfirming the characteristics, in the case of using this manufacturing method, it is only after a high-performance product has been identified because of the characteristics of the manufacturing process that it begins to make a mold that matches the high-performance product. The production of a predetermined high-performance product must be started according to the process of the present invention, and the procedure of providing the product must be followed.
(1) JP-A-10-101453

(Awareness of problems)
Under the circumstances described above, unless the product is determined, in other words, unless an order is received for a high-performance product having a specified shape and structure, the present invention cannot be naturally carried out. The product will remain stopped, causing inconvenience in terms of profitability.In addition, after receiving an order, all processes will be performed sequentially from the beginning. For the first time, it was recognized that there was a problem that it was almost impossible to shorten the time required until the response could be promptly made, and there was a possibility that it might not be possible to meet the demands of customers. Was.

(Object of the invention)
The present invention has been continuously developed and researched to address these new problems, and finally, a novel porous carbon that can be an effective means for quickly and reliably obtaining such high-performance products. A material powder and a method for producing the same, and a method for producing a porous carbon material product using the porous carbon material powder, have been successfully completed. I will explain along with it.

(Structure of the invention)
First, the porous carbon material forming the basis of the present invention basically has the following configuration. That is, kneaded rice bran obtained by adding a thermosetting resin, and an appropriate amount of aqueous solution or water containing a paste to rice bran such as rice bran or wheat glue whose particle size has been adjusted, dried, granulated, and granulated into rice bran It is a porous carbon material that has a constitution in which, after being made into a raw material, the granular material of the rice bran is baked and carbonized in an inert gas atmosphere or in a vacuum.

If this basic configuration is shown as a more specific example, a kneaded state obtained by adding a thermosetting resin and an appropriate amount of aqueous solution or water containing a paste to a bran such as rice bran or fu having a mesh under 20 mesh. After drying and granulating the bran, sieving it to 4 mesh under, sorting to form a granulated bran material, and baking and carbonizing the granulated bran material in an inert gas atmosphere or vacuum. It becomes a porous carbon material.

(Related invention 1)
In relation to the above-described porous carbon material of the present invention, the present invention includes a porous carbon material powder having the following constitution using the porous carbon material as a raw material. That is, kneaded rice bran obtained by adding a thermosetting resin, and an appropriate amount of aqueous solution or water containing a paste to rice bran such as rice bran or wheat glue whose particle size has been adjusted, dried, granulated, and granulated into rice bran After making the raw material, the granular material of the rice bran is baked and carbonized in an inert gas atmosphere or vacuum to form a porous carbon material, and the porous carbon material is pulverized and powdered to have a desired particle size. A porous carbon material powder using the porous carbon material according to any one of claims 1 and 2 as a raw material.

(Related invention 2)
On the other hand, the present invention relates to a porous carbon material that forms the basis of the present invention, and the present invention includes a method for producing a porous carbon material that can surely produce the porous carbon material. It basically consists of the following configuration. That is, a step of adding and kneading a thermosetting resin and an appropriate amount of an aqueous solution or water containing a paste to kneaded rice bran such as rice bran or grated rice whose particle size is adjusted, and drying and granulating the kneaded kneaded rice bran. Above, a step of sieving to a predetermined particle size or less, sorting and forming into a granular rice bran material, firing and carbonizing the granular rice bran material in an inert gas atmosphere or in a vacuum, carbonizing the granular rice bran material A step of cooling the final firing temperature from the final firing temperature to a normal temperature at a predetermined temperature lowering rate to form a porous carbon material, and the above-described steps are sequentially performed to manufacture the porous carbon material of the present invention. Is the way.

More specifically, more specifically, a step of adding a thermosetting resin and an appropriate amount of an aqueous solution or water containing a paste to kneading rice bran such as rice bran or gluten having a mesh size of 20 mesh, and kneading the mixture; Is dried to remove volatile substances by heating to about 60 to 80 ° C., granulated, sieved to 4 mesh under, and sorted to obtain a granular material of fusi bran. The step of firing and carbonizing the granular material in an inert gas atmosphere or in a vacuum, the step of cooling the carbonized granular rice bran from the final firing temperature to a normal temperature at a predetermined cooling rate to obtain a porous carbon material, It can be said that this is a method for producing a porous carbon material in which the steps are sequentially performed.

More specifically, a step of adding a thermosetting resin and an appropriate amount of aqueous solution or water containing a paste to kneaded bran such as rice bran or grated bran with a mesh size of 20 mesh, and kneading the mixture. Or drying and granulating while heating to about 80 ° C. to remove volatile substances, sieving into 4 mesh under, sorting to obtain fusiform granular materials, A step of raising the temperature in an inert gas atmosphere or vacuum in accordance with a predetermined temperature raising rate, firing at a final firing temperature of about 700 ° C. or more, and carbonizing, and removing the carbonized granular rice bran from the final firing temperature. This is a method of manufacturing a porous carbon material having a configuration in which the steps of cooling to a normal temperature at a predetermined cooling rate and the above steps are sequentially performed.

(Related invention 3)
In addition, the present invention relates to the porous carbon material powder included in the present invention described above, and the porous carbon material powder based on the following configuration, which is capable of reliably manufacturing the porous carbon material powder. Is included in the present invention.
That is, following the final step in the above-described method for producing a porous carbon material, a step of pulverizing the cooled porous carbon material obtained in the final step and pulverizing the cooled porous carbon material to a desired particle size, and sequentially performing the above steps This is a method for producing a porous carbon material powder.

(Related invention 4)
On the other hand, the present invention also includes a method of manufacturing a porous carbon material product manufactured using the porous carbon material powder of the present invention, and has the following configuration. That is, following the respective steps in the production method of the related invention 3, the appropriate amount of thermosetting resin is added to the porous carbon material powder obtained through the steps, and the mixture is kneaded to obtain a kneaded product. Filling into a desired mold, molding by pressurizing, firing the molded product released from the mold to a desired final firing temperature according to a predetermined heating rate in an inert gas atmosphere or vacuum. And a step of carbonizing, and a step of cooling from a final firing temperature to a normal temperature at a predetermined temperature lowering rate. The method for manufacturing a porous carbon material product has a configuration in which the above steps are sequentially performed.

According to the porous carbon material and the porous carbon material powder of the present invention and the method for producing the same, and the method for producing a porous carbon material product using the porous carbon material powder, which is realized as the gist of the configuration as described above. For example, a porous carbon material powder of a size suitable for the properties of a high-performance product expected to be required by consumers can be efficiently produced from the porous carbon material in each case, or a sufficient amount can be prepared in advance. After the high-performance products are specified by the customer, simply select the porous carbon material powder of the present invention having the optimal particle size suitable for the properties of the specified high-performance products, and then select those porous carbon materials. The production of a porous carbon material product can be started immediately from the process of mixing a thermosetting resin into a kneaded product so that the optimum ratio takes into account the properties of the target high-performance product and the material powder. become As in previous cases, unless a high-performance product is specified, it is not possible to manufacture a specific high-performance product.In the meantime, the production line remains stopped, reducing profitability, and increasing the time it takes to supply the product. The inconvenience of necessity is completely eliminated, and it is possible to promptly respond to the demands of the customers to improve the convenience for the users, and to add the rice bran that has been treated as waste. A wide variety of high valued functions (in addition to physical functions such as structural strength, friction coefficient, expansion coefficient, etc., as well as functions such as adsorptivity, heat insulation, heat resistance, chemical resistance, weather resistance, electrical conductivity, electromagnetic shielding, etc.) ) That can be efficiently and reliably commercialized into a highly functional product having the above-mentioned function.

最 良 In implementing the present invention having the above-described configuration, the best mode or desirable mode will be described. First of all, as the bran, such as defatted bran that remains in large quantities after pressing the rice bran oil, and the wheat flour that comes out as shavings when the wheat is ground into flour, as well as chaff, buckwheat hull, soybean hull, gluten Such as feed (corn husks and slag, ie residues from the production of corn starch), such as powdered or pulverized crusts generated during the processing of cereals; Is sieved so that the grain size is equal to or less than a certain value (for example, in the case of bran after defatting, it is 12 mesh-under, optimally 20 mesh-under in order to remove large particles solidified or solidified in the degreasing process). Should be adopted, which is advantageous for the subsequent homogeneity of formability and material structure.

As the thermosetting resin, a typical phenolic resin, for example, by adopting one diluted to about 10 to 60% by weight, the mixing with the bran can be performed smoothly. Desirably, the mixing ratio varies depending on the type of fusi bran. For example, in the case of defatted bran, about 5 to 80% by weight, and for fu (bran) about 5 to 70% by weight About 5 to 60% by weight in the case of gluten feed (however, in any case, it is changed depending on conditions such as the particle size, moisture content, material temperature, etc.). It is adopted at the optimal ratio corresponding to the rice bran, and if it is necessary to adjust the penetration rate into the rice bran, various conditions such as mixing, stirring work environment and setting of the mixing and the standing time after stirring etc. Is considered It is so. In addition, the thermosetting resin, aqueous solution containing paste, or water, when mixed with rice bran, functions as a paste for rice bran, as paste for the aqueous solution containing paste, Seaweed paste, collagen, starch, lignin and the like can be used.

It is necessary to reduce the variation in quality after baking and carbonizing, so that the kneaded bran after drying and granulation is sieved in advance to 4 mesh under, and the bran selected Granular material should be adopted, and the grain size-adjusted wheat bran granular material should be fired and carbonized so as not to cause variation in quality, and ultimately required by consumers. It is possible to respond freely to the properties of various high-performance products that are expected to be different, that is, the differences in the complexity of the product shape, the difficulty in filling the mold, the structural strength, the fineness of the appearance, etc. Particle sizes such as 250 to 100 μm, 150 to 100 μm, 150 μm or less, 100 μm or less, 50 to 10 μm, 10 μm or less, etc. After once crushed Yichun by grinder (atomizer), and screened by shaking sieve is to a porous carbon material powder of the present invention.

As described above, the thermosetting resin in the related inventions 2 and 3 is, for example, a typical phenolic resin is reduced to about 10 to 60% by weight in order to smoothly mix and stir the rice bran. The mixing ratio, such as using a diluted one, differs depending on the type of fu bran. For example, in the case of bran after defatting, about 5 to 80% by weight, and in the case of fu (bran) About 5 to 70% by weight, and about 5 to 60% by weight in the case of gluten feed (however, it is changed depending on conditions such as the particle size, moisture content, material temperature, etc. of the bran). )), It is adopted at the optimal ratio corresponding to the rice bran, and when it is necessary to adjust the permeability to the rice bran, the mixing and stirring work environment and the mixing and stirring time Each setting Conditions are to be considered.

In the mixing and impregnation step of the thermosetting resin, the penetration rate of the thermosetting resin into the bran is examined, and in parallel with the mixing of the thermosetting resin of a predetermined concentration, an appropriate amount of water is added, or An appropriate amount of a binder for various animal and plant pastes (eg, seaweed paste, collagen, starch, lignin, etc.), starch, and various sugar solutions (eg, about 5 to 30% by weight in the case of bran after defatting) To be carried out by adding a mixed aqueous solution, or beforehand, water and a binder mixed solution for improving the moldability are mixed with a predetermined concentration of thermosetting resin, Should be mixed and stirred to obtain kneaded rice bran.

The kneaded rice bran obtained by mixing the thermosetting resin to a predetermined ratio is, for example, granulated using a known granulator such as a flat granulator or a cylindrical granulator, and is subjected to 60 to 80 granulation. After heating to about ℃ to remove volatile matter and drying, the granulated material is sieved in order to smooth out gas in the sintering step and to realize as uniform carbonization as possible. In this case, a step of preparing a granular material of rice bran, which is adjusted to a predetermined size, preferably about 4 mesh under, more preferably about 5 mesh under, is required.

The thus prepared granular rice bran material, especially the granular rice bran material of 4 mesh under, is then transferred to a step of firing and carbonizing in an inert gas atmosphere or vacuum. Must be carried out in an atmosphere of an inert gas such as nitrogen gas or in an oxygen-free state such as under a vacuum so that the granular material containing cereal bran does not burn. Care should be taken to avoid a sudden rise in temperature so that the granular material does not collapse. In particular, at around 200 to 400 ° C., a large amount of gas is generated due to decomposition. Therefore, sufficient consideration should be given to the heating rate during this period. Then, up to around 500 ° C., the temperature should be raised at a rate of about 1.0 to 5.0 ° C. per minute (determined according to conditions such as the proportion of resin and particle size).

The firing temperature may vary from about 200 ° C. to 1000 ° C. depending on the characteristics required for the porous carbon material powder of the present invention, such as hardness, purity, porosity and insulation, workability and structural strength. The optimum temperature within the range of several hundred degrees will be selected, and firing will be carried out for the optimum time, taking into account various factors that affect the firing condition that affects the strength and density of the porous carbon material powder. You have to make sure.

In the subsequent cooling step of the carbonized granular rice bran, the carbonized granular rice bran is cooled from the final baking temperature to a predetermined temperature reduction rate, for example, at a rate of about 1.5 ° C./min. Is appropriately crushed using a crusher (atomizer) and then subjected to a particle size of each stage by a shaking sieve, for example, 250 to 100 μm, 150 to 100 μm, 150 μm or less, 100 μm or less, 50 to 10 μm, 10 μm or less And so on, so that it can be sorted out by stage, and the properties of various high-performance products that are expected to be demanded by consumers, that is, the complexity of the product shape, the difficulty of mold packing due to it, A porous carbon material powder according to the present invention which can freely respond to differences in structural strength, fineness of appearance, etc.

Further, the thermosetting resin in the production method in the case of the related invention 4 is the same as that used in producing the porous carbon material powder, but the mixing ratio is different from the previous one, and mainly the The porous carbon material powder having a predetermined particle size selected to be a high-performance product is made to function as a binding material that imparts moldability with a mold, and is carbonized in the firing step to form the porous carbon material of the present invention. It is incorporated into a part of the composition of the carbon material, and the ratio of the thermosetting resin is 10 to 40 w% to the porous carbon material powder 90 to 40 w%. It is selected as one having an optimum mixing ratio corresponding to conditions such as water content and material temperature, and is a kneaded product of a porous carbon material powder and a thermosetting resin.

When the kneaded product is obtained in the mixing step of the thermosetting resin, the permeability into the porous carbon material powder is examined, and an appropriate amount of water is added in parallel with the mixing of the thermosetting resin at a predetermined concentration. Or by adding an aqueous solution obtained by mixing an appropriate amount of a binder such as various animal and plant pastes, starch, and various sugar solutions, or in advance, a water and binder mixture liquid for improving the formability. Is mixed with a predetermined concentration of the thermosetting resin, and then mixed and stirred to carry out a kneaded product. It is needless to say that the same means as described above is not excluded, and can be appropriately adopted as needed.

The kneaded material filled in the mold should be pressurized and molded at a pressure of 40 to 450 kg / cm2 per unit area of the molded product. Unlike the baking and carbonizing processes for the bran granular material, there is no need to consider the burning of the bran, so it is not limited to an inert gas atmosphere or vacuum, but to air. It will be possible.

When the final baking temperature is 500 ° C. or lower, the rate of temperature rise in this step is 1.2 ° C./min from room temperature to 250 ° C., 1 ° C./min from 250 ° C. to 350 ° C., and 1.degree. C. from 350 ° C. to 500 ° C. After the holding at the final baking temperature for 3 hours, the cooling step is carried out at a cooling rate of 1.5 ° C./min to room temperature, and the final baking temperature is 500 ° C. When the temperature exceeds 250 ° C., the temperature is maintained at 1.2 ° C./min from room temperature to 250 ° C., 1 ° C./min from 250 ° C. to 350 ° C., 1.2 ° C./min from 350 ° C. to 500 ° C., and held at 500 ° C. for 1 hour. The temperature is raised at a rate of 2 ° C./min from the temperature of 500 ° C. to the final final baking temperature. The temperature is maintained at the final baking temperature for 2 hours. It is desirable to be cooled down to the temperature. Hereinafter, the porous carbon material powder of the present invention described above, a method for producing the same, and a method for producing a porous carbon material product using the porous carbon material powder will be described in more detail. This embodiment will be described.

This example is a typical example of a method for producing defatted porous carbon material powder by using defatted bran, which is one of the most typical raw materials among rice bran.
"Mixing process"
The defatted bran from which the oil was extracted was passed through a 50-mesh sieve, and 75% by weight of the defatted bran was added to a phenol resin [Honenko-Poration, Ltd. Name)] as a thermosetting resin so as to be 25% by weight, and sufficiently mixed.
`` Granulation process ''
In order to remove volatile components, the mixture is granulated while being heated to 80 ° C., and passed through a 4-mesh sieve is used as a granulated rice bran material.

"Baking process"
Firing is performed in a firing furnace while flowing nitrogen gas. The rate of temperature rise at that time is 1.2 ° C / min from room temperature to 250 ° C, 1 ° C / min from 250 ° C to 350 ° C, 1.2 ° C / min from 350 ° C to 500 ° C, and 1 hour at 500 ° C. Hold, 2 ° C./min from 500 ° C. to target temperature, hold at target temperature for 2 hours. Cooling is performed at a rate of 1.5 ° C./min.
`` Pulverization process ''
The carbonized granular rice bran material returned to room temperature is once crushed by a crusher (atomizer) and then sorted by a shaking sieve to obtain a porous carbon material powder of 100 μm or less according to the present invention.

The following is a typical production method for producing a plate-like porous carbon material product using the porous carbon material powder obtained by the production method of Example 1 described above.
"Mixing process"
To a porous carbon material powder 75 w%, a phenol resin [Honenko-Polyation Co., Ltd., Hosunen Resingle-px-1600 (trade name)] is added as a thermosetting resin to 25 w%. And kneaded well.

"Mold forming process"
After filling 100 g of the kneaded material in a mold (75 × 150 × 6 mm) for a flat product set at a temperature range of 140 to 170 ° C., the mixture was pressed at a gauge pressure of 50 kg / cm 2 for 2 minutes, and then decompressed. Degas. After degassing, pressure was applied again at a gauge pressure of 50 kg / cm2 for 3 minutes to obtain a flat molded product. In addition, in order to strengthen the physical properties of the molded article, air heating treatment was further performed with a heater in a temperature range of 150 to 250 ° C.

"Baking process"
Nitrogen gas was flown in the firing furnace to make it oxygen-free, and 1.2 ° C / min from room temperature to 250 ° C, 1 ° C / min from 250 ° C to 350 ° C, 1.2 ° C / min from 350 ° C to 500 ° C. After sintering at a rate of temperature increase at a rate of 1 minute, the temperature was kept at 500 ° C. for 1 hour, then the temperature was raised again from 500 ° C. to 900 ° C. at 2 ° C./minute, and when the temperature reached 900 ° C. The temperature is maintained for 2 hours and then cooled to room temperature at a rate of 1.5 ° C./min.
By sequentially performing the above steps, the porous carbon material product of the present invention can be manufactured.

This is a typical production method for producing a plate-shaped porous carbon material product using the porous carbon material powder obtained by the production method of Example 1 above.
"Mixing process"
A kneaded product is obtained by sufficiently mixing 75 parts by weight of the porous carbon material powder obtained in Example 1 and 25 parts by weight of a novolak type powder phenol resin [Phenolite 5510 (trade name) manufactured by DIK]. .

"Mold compression molding process"
100 g of the kneaded material is filled in a mold for a flat plate product (thickness can be varied depending on the amount of material and pressure; 75 × 150 × tmm) set to a temperature range of 140 to 170 ° C. A pressure of 50 kg / cm2 is applied for 2 minutes, then the pressure is released to release the gas, and then a pressure is applied again at a gauge pressure of 50 kg / cm2 for 3 minutes to obtain a flat molded product.

"Baking process"
Nitrogen gas is flown in a firing furnace (external heat type, manufactured by Tokai High Heat Co., Ltd.) to make it oxygen-free, and 1.2 ° C./min. From room temperature to 250 ° C., 1 ° C./min. After firing at a rate of 1.2 ° C./minute from 500 ° C. to 500 ° C. and maintaining the state of 500 ° C. for 1 hour, the temperature is again increased from 500 ° C. to 900 ° C. at a rate of 2 ° C./minute. After calcination, when the temperature reaches 900 ° C., the temperature is maintained for 2 hours, and thereafter, at a rate of 1.2 ° C./min up to 600 ° C., and at a rate of 1.5 ° C./min. Cool down to room temperature. By sequentially performing the above steps, the porous carbon material product of the present invention can be manufactured.

This is a manufacturing method according to another example of the present invention in which a porous (60 × 15 × 2 mm) porous carbon material product is manufactured using the porous carbon material powder obtained by the manufacturing method of Example 1 described above. .
"Mixing process"
75 parts by weight of the porous carbon material powder obtained in Example 1 and 25 parts by weight of a novolak type powder phenol resin [Phenolite 5510 (trade name) manufactured by DIK] were heated and kneaded with a mixing hot roll, The obtained kneaded material is pulverized with a power mill to produce a granular molding material of 4 mm × 4 mm × 4 mm or less.

"Injection molding process"
Using a screw-type injection molding machine (Matsuda Seisakusho, 75F-36K type), the injection temperature was set at 80 ° C at the inlet, 100 ° C in the middle, and 120 ° C at the outlet nozzle. The mold temperature was set at 180 ° C and 110kg / Injection molding is performed with a pressure of cm2.
The production cycle of the injection molded product is 90 seconds / one time, and a flat molded product (13 × 64 × 3t) is obtained.

"Baking process"
The molded product obtained above was used in a batch-type firing furnace in a nitrogen gas atmosphere at room temperature to 250 ° C at 1.2 ° C / min, at 250 ° C to 350 ° C at 1 ° C / min, and at 350 ° C to 500 ° C. After baking at a temperature rising rate of 1.2 ° C./min and maintaining the state of 500 ° C. for 1 hour, baking again from 500 ° C. to 900 ° C. at a heating rate of 2 ° C./min. Was reached and the temperature was maintained for 2 hours. Thereafter, the temperature is lowered at a rate of 1.2 ° C./min up to 600 ° C. and at a rate of 1.5 ° C./min from 600 ° C. to room temperature, and cooled to room temperature. By sequentially performing the above steps, the porous carbon material product of the present invention can be manufactured.

This embodiment is a manufacturing method according to still another example using the porous carbon material powder obtained by the manufacturing method of the first embodiment.
"Mixing process"
55 parts by weight of the porous carbon material powder obtained in Example 1, 25 parts by weight of a novolak-type powder phenol resin [manufactured by DIK, Phenolite 5510 (trade name)], and carbon fibers (Donacarbo S-242; And 20 parts by weight (manufactured by Donac Co., Ltd.) with a mixer to obtain a molding material.

"Press molding process"
A mold (75 × 150 × tmm) set at a mold temperature of 150 ° C. is filled with 100 g of the above molding material, pressurized at a gauge pressure of 40 kg / cm 2 for 2 minutes, depressurized, and degassed. Thereafter, pressurization is performed at a gauge pressure of 40 kg / cm2 for 2 minutes, and thereafter, the molded product is formed by pressurizing at 1 decomposition pressure and again at a gauge pressure of 60 kg / cm2 for 2 minutes, and the molded product is left in a 200 ° C. heater for 5 hours. The heat treatment (after-cure) is performed to produce the porous carbon material product of the present invention.

In Example 1, except that the phenolic resin was changed to an aqueous solution containing collagen as described below to produce a granular material of rice bran, a porous carbon material powder was obtained through the same steps as in Example 1. Then, 5 parts by weight of a 1% by weight collagen-containing aqueous solution was sprayed and stirred against 95 parts by weight of the bran, and then pelletized with a desk pelletizer (Dalton F-20 / 12-330 type). A pellet having a diameter of φ5 × L10 is manufactured.

(Operation of the embodiment)
The porous carbon material of the present invention constituted by the steps as described above functions as a raw material of the porous carbon material powder. In order to obtain a porous carbon material powder, a predetermined amount is stocked in advance, and regardless of the properties of high-performance products that are expected to be required by consumers, the granulated rice bran is appropriately ground in advance in advance. It is crushed by a machine (atomizer), and is classified and prepared by a shaking sieve into particles having a particle size of each stage, for example, 250 to 100 μm, 150 to 100 μm, 150 μm or less, 100 μm or less, 50 to 10 μm, 10 μm or less. As soon as a high-performance product is identified, its properties, that is, the complexity of the product shape, the difficulty of mold packing, the structural strength, and the appearance In addition to selecting the porous carbon material powder of the present invention having an optimum particle size suitable for adjustment, etc., the mixing ratio of the thermosetting resin to the porous carbon material powder (90 to 40 w%): (10 to 60 w%) From the range, the thermosetting resin is mixed into a kneaded product so as to have an optimal ratio in consideration of the properties of the target high-performance product, and a molded product is obtained through a mold forming process, followed by firing and carbonizing processes. To manufacture the porous carbon material product according to the present invention, or to purchase the porous carbon material of the present invention as a raw material, It can also be used to make a porous carbon material powder having the optimal particle size for a functional product.

In the method for producing a porous carbon material, kneaded glutinous bran obtained by adding a thermosetting resin and an appropriate amount of an aqueous solution or a water containing a paste to the bran as a main raw material and kneading the mixture is used for smooth degassing in the firing step. In order to realize the above, a process of adjusting the particle size to 5 mesh under and granulating in advance is indispensable, and in order to prevent burning during the baking process, etc., in an inert gas atmosphere or in a vacuum, according to a predetermined heating rate, A firing step of reaching the firing temperature and firing, carbonizing, and a step of cooling from the final firing temperature to a normal temperature at a predetermined temperature lowering rate are indispensable constituent requirements, and how to produce a porous carbon material powder, And a powdering process that enables the production of high-performance products with various properties are indispensable components, and as a result, porous carbon material powders of various sizes are sufficiently manufactured and stocked in advance The invention proceeds to encompass the porous carbon material product manufacturing is assumed to be made smoothly.

In the following, the physical properties of the porous carbon material product obtained by the above-described embodiment based on the technical idea of the present invention will be shown by comparing with those of the following reference example, and thereby, the present invention described below. Make the effect clearer.
<< Reference Example 1 >>
75 parts by weight of the defatted bran passed through a 50-mesh sieve and 25 parts by weight of a phenolic resin [Honenko-Polyration Co., Ltd., Hojunen Resingle-px-1600 (trade name)] were sufficiently mixed. In order to remove the volatile matter, the mixture was granulated while heating to 80 ° C., and the mixture passed through a 12-mesh sieve was used as a raw material. 15 g of the raw material was used as a mold with a heater (inner diameter: 42 mm, (Length: 60 mm) and then molded and manufactured while heating to a pressure of 300 kg / cm 2 and a temperature of 180 ° C. with a high pressure jackie (cylinder inner diameter: 21 mm). In order to degas several times during the process, the pressure is reduced to a gauge pressure of about 70 kg / cm2 to remove moisture and decomposed gas.
Firing at 1.2 ° C / min from room temperature to 250 ° C, 1 ° C / min from 250 ° C to 350 ° C, and 1.2 ° C / min from 350 ° C to 500 ° C while flowing nitrogen gas into the firing furnace After maintaining the state at 500 ° C. for 1 hour, the mixture was fired again from 500 ° C. to 900 ° C. at a rate of 2 ° C./min, and when the temperature reached 900 ° C., the temperature was maintained for 2 hours. After that, the porous carbon material was cooled to 600 ° C. at a temperature lowering rate of 1.5 ° C./min and then naturally cooled to room temperature.

<< Test Example 1 >>
The results of evaluating the physical properties of the porous carbon material products of Examples 3 and 4 and Reference Example 1 obtained above are shown in Table 1, and the results of evaluating the physical properties of the molded article of Example 5 are also shown in Table 1. It is shown in Table 2. In the table, each item is evaluated as follows.
Bulk specific gravity: A sample of a constant weight (100 g) is taken in a measuring cylinder, and the volume is read to calculate the weight / volume.
True specific gravity: Measured according to JIS R1620 (pycnometer method).
Bending stress: Measured in an environment of 20 ° C. and 65% RH using an Instron type material testing machine in accordance with JIS R1601 (three-point method).
Compressive stress: Measured according to JIS R1608.
Thermal expansion coefficient: Measured according to JIS P1618.
Firing shrinkage ratio: Measure the molded product before and after firing on a scale and calculate the ratio after firing / before firing.
Friction coefficient: Measurement using a reciprocating friction tester (Shin Toyo Kagaku Co., Ltd., Pin-on-Desk HEIDO N-22 type).
Abrasion resistance: Using a reciprocating friction tester (Shin Toyo Kagaku Co., Ltd., pin-on-desk HEIDO N-22 type), use a stylus type surface roughness meter to measure the cross-sectional curve of the wear mark perpendicular to the friction direction. After measuring at five locations and calculating the wear volume based on these, the specific wear amount was calculated according to the following equation (1). Here, Ws is the specific wear amount, V is the wear volume, W is the vertical load, and L is the slip distance.

The pore area ratio is calculated according to the following formula (2) based on a photograph output to a printer by observing the sample surface with a scanning laser microscope (manufactured by Lasertec) 1LM21. Here, Ap indicates the pore area, and Aa indicates the total area.

Next, the workability was evaluated based on the results of expert judgment on the ease of processing the sample on each processing surface of drilling, milling, turning, and grinding, and the results are shown in Table 1 below. Is shown.

The data obtained by comparing the electric resistance value and the volume specific resistance value are as shown in Table 2 below.
The electric resistance value was measured by a digital multimeter custom (CDM-27D) by preparing a 1 × 1 × 1t test piece, and the volume specific resistance was determined by Toa Denpa Kogyo (SM-8001). It was measured by preparing a test piece of 100 × 100 × 2t.

(Effects of the embodiment)
As described above, as is clear from the results of each experiment, the porous carbon material product of the present invention obtained in Example 2 and the like has improved firing shrinkage, bending stress, compressive stress, wear resistance, etc. It was confirmed that the porous carbon material obtained in Example 1 could be effectively used as a raw material of a porous carbon material powder that forms a basis for manufacturing a porous carbon material product. Therefore, as already described as the effect of the present invention, the properties of the final product (high-performance product) requested by the customer, for example, the complexity of the product shape, the difficulty of the mold packing due to the property, and the structural strength It is supported that the porous carbon material powder having the optimal particle size for the production of the final product can be appropriately selected and adopted according to the fineness of the appearance, and even this raw material is prepared in advance. What kind of high machine A porous carbon material powder is obtained, which enables the production of products to be appropriately supported.In addition, using the optimal porous carbon material powder, the next step is to mix the porous carbon material powder with the resin, mold, By going through the firing step, the production of the final product can be started, and the porous carbon material product can be produced promptly.

(Conclusion)
As described above, the present invention completely compensates for the weaknesses of the method for producing a porous carbon material powder that has already been developed and put into practical use, including defatted bran, and when wheat is ground into powder. Until now, mainly agricultural materials such as fu, which is produced as shavings, and finely powdered or crushed husks generated during the processing of grains, such as rice hulls, buckwheat husks, soybean husks, gluten feed, etc. It is a method of using rice bran, which had been used only as an industrial material, in an extremely wide range of applications, especially as a high-performance product, efficiently and economically. It is expected that the spread and expansion will be achieved, assuring advancement into a wide range of fields that are needed. Rather, various industrial products manufacturers and general users, is expected to be in but also its usefulness is highly appreciated from agricultural producers, which has been struggling in the handling of the thus Fusumanukarui.

Claims (13)

Dried kneaded rice bran obtained by adding a thermosetting resin and an aqueous solution or water containing an appropriate amount of paste to rice bran such as rice bran or glue whose grain size has been adjusted, dried and granulated to give a granular material for rice bran In addition, a porous carbon material characterized by being obtained by firing and carbonizing the granular material of rice bran in an inert gas atmosphere or vacuum. Dried kneaded rice bran obtained by adding a thermosetting resin and an aqueous solution or water containing an appropriate amount of paste to rice bran such as rice bran and gluten, etc. of 20 mesh under, dried, granulated, and sieved to 4 mesh under A porous carbon material characterized in that it is selected and made into granular rice bran material, and the granular rice bran material is baked and carbonized in an inert gas atmosphere or vacuum. Dried kneaded rice bran obtained by adding a thermosetting resin and an aqueous solution or water containing an appropriate amount of paste to rice bran such as rice bran or glue whose grain size has been adjusted, dried and granulated to give a granular material for rice bran After that, the granulated rice bran material was fired and carbonized in an inert gas atmosphere or vacuum to form a porous carbon material, and the porous carbon material was pulverized and powdered to obtain a desired particle size. Item 4. A porous carbon material powder comprising the porous carbon material according to any one of Items 1 or 2 as a raw material. To a rice bran such as rice bran or fu with adjusted particle size, a thermosetting resin, and a step of kneading by adding an appropriate amount of an aqueous solution or water containing a paste, and drying and granulating the kneaded fu brans, A step of sieving to a predetermined particle size or less, sorting to form a granulated rice bran, a step of firing and carbonizing the granulated rice bran in an inert gas atmosphere or in a vacuum, and finalizing the carbonized granulated rice bran 3. The process according to claim 1, wherein the step of cooling the porous carbon material from the firing temperature to a normal temperature at a predetermined temperature lowering rate is performed, and the above steps are sequentially performed. Manufacturing method of carbon material. A step of adding a thermosetting resin and an appropriate amount of aqueous solution or water containing a paste to kneaded rice bran such as rice bran and grated rice bran with a 20 mesh under, and kneading the mixture. A process of drying and granulating while removing volatile substances by heating and sieving into 4 mesh under, sorting and forming into a granular rice bran material, in a gas atmosphere of an inert gas Or a step of baking and carbonizing in a vacuum, a step of cooling the carbonized granular rice bran from the final baking temperature to a normal temperature at a predetermined temperature lowering rate to form a porous carbon material, so that the above steps are sequentially performed. The method for producing a porous carbon material according to claim 1, wherein: A step of adding a thermosetting resin and an appropriate amount of aqueous solution or water containing a paste to kneaded rice bran such as rice bran and grated rice bran with a 20 mesh under, and kneading the mixture. A process of drying and granulating while removing volatile substances by heating and sieving into 4 mesh under, sorting and forming into a granular rice bran material, in a gas atmosphere of an inert gas Or raising the temperature in vacuum according to a predetermined heating rate, firing and carbonizing at a temperature of about 700 ° C. or more at the final firing temperature, and heating the carbonized granular rice bran from the final firing temperature to a normal temperature at a predetermined cooling rate. The method for producing a porous carbon material according to claim 1, wherein the cooling step and the above steps are sequentially performed. The method for producing a porous carbon material according to any one of claims 4 to 6, wherein the firing and carbonizing steps are performed at a temperature of 600 to 1100 ° C for about 1 to 3 hours. 8. A step of pulverizing the cooled porous carbon material obtained in the final step and pulverizing it to a desired particle size, following the final step in the method for producing a porous carbon material according to any one of claims 4 to 7. 8. A method for producing a porous carbon material powder incorporating the method for producing a porous carbon material according to any one of claims 4 to 7, wherein each of the steps is sequentially performed. An appropriate amount of a thermosetting resin is added to the porous carbon material powder obtained through each of the steps following the steps in the manufacturing method according to claim 8, and the mixture is kneaded to obtain a kneaded product. Filling into a mold, molding by pressurizing, and firing and carbonizing the molded product demolded from the mold by reaching a desired final firing temperature according to a predetermined heating rate in an inert gas atmosphere or vacuum. The method for producing a porous carbon material powder according to claim 8, wherein the steps, and a step of cooling from a final firing temperature to a normal temperature at a predetermined temperature-lowering rate, are arranged so that each of the above steps is sequentially performed. Manufacturing method of the incorporated porous carbon material product. 10. The porous carbon according to claim 9, wherein the ratio of the porous carbon material powder to the thermosetting resin is 10 to 60 w% with respect to the porous carbon material powder of 90 to 40 w%. Method of manufacturing raw material products. The method for producing a porous carbon material product according to claim 9, wherein the kneaded material filled in the mold is pressed and molded at a pressure of 40 to 450 kg / cm 2 per unit area of the molded product. The firing and carbonization processes in an inert gas atmosphere or in a vacuum are performed at 1.2 ° C./minute from room temperature to 250 ° C., 1 ° C./minute from 250 ° C. to 350 ° C., and 1.2 ° C. from 350 ° C. to 500 ° C. If the final firing temperature is 500 ° C. or lower, the temperature is maintained at the final firing temperature for 3 hours, and then, in the cooling step, the temperature is lowered at a temperature lowering rate of 1.5 ° C./minute to room temperature. The method for producing a porous carbon material product according to claim 9, wherein the product is cooled. The firing and carbonization processes in an inert gas atmosphere or in a vacuum are performed at 1.2 ° C./minute from room temperature to 250 ° C., 1 ° C./minute from 250 ° C. to 350 ° C., and 1.2 ° C. from 350 ° C. to 500 ° C. / Minute, at 500 ° C. for 1 hour, and then the temperature is raised from 500 ° C. to a target final firing temperature at a rate of 2 ° C./minute. The method for producing a hard porous carbon material product according to any one of claims 9 to 11, wherein the product is cooled to a normal temperature at a cooling rate of 0.5 ° C / min.