JP4529471B2 - Method and apparatus for producing hydrophilic coal slurry - Google Patents

Description

  The present invention relates to a method and an apparatus for producing a hydrophilic coal slurry, and more specifically, a hydrophilic coal slurry capable of obtaining a hydrophilic coal slurry having excellent fluidity by modifying coal to be hydrophilic by a simple method. The present invention relates to a manufacturing method and apparatus.

  In recent years, the development of alternative energy has been desired due to the problem of exhaustion of petroleum resources, and the use of coal has been studied as one of alternative energy. Coal has difficulties in handling such as transportation compared to liquid fuels such as petroleum and heavy oil, and various reforming techniques for liquefying or gasifying coal have been proposed for this purpose.

  As one of such coal reforming technologies, carbonaceous materials such as coal, coke, char, pitch, coal tar, heavy oil and asphalt are pyrolyzed under normal pressure, reduced pressure or high pressure to form a gaseous state. When producing hydrocarbons and / or liquid hydrocarbons, there is one that thermally decomposes the carbonaceous material in a gas atmosphere while irradiating the carbonaceous material with beta rays or gamma rays (see, for example, Patent Document 1). ).

A. Providing a carbonaceous material containing sulfur; Contacting the carbonaceous material with a source of active oxygen in the presence of a base, and using an amount of the active oxygen and the base effective to reduce the sulfur content of the carbonaceous material; and C . Removing sulfur from a sulfur-containing carbonaceous material comprising exposing the carbonaceous material to an energy source such as radiation and subjecting the carbonaceous material to conditions effective to further reduce the sulfur content of the carbonaceous material; There is a process (for example, see Patent Document 2).
JP 05-059371 A JP 2002-524651 A

  In Patent Document 1, in order to control the quantity and quality of coal pyrolysis products, the pyrolysis temperature, radiation dose, and pyrolysis gas atmosphere are controlled. When carbon is subjected to thermal decomposition (change in molecular structure) while irradiating with radiation in a hydrogen gas atmosphere at a temperature of 700 ° C., the amount of the solid product is reduced within a range of 10 to 80%. Only the amount of liquid product and gas product is said to have increased. In addition, regarding coal liquefaction, 55% liquid hydrocarbon was obtained by using an iron sulfide + sulfur catalyst in a hydrogen atmosphere at 450 ° C. and 170 atm. It is assumed that 70 to 75% of liquid hydrocarbon was obtained using the same catalyst under atmospheric hydrogen atmosphere. Furthermore, when a hydrogen-donating organic solvent such as tetralin is added, a large amount of coal liquid product is generated.

  However, in the method disclosed in Patent Document 1, it is necessary to maintain a hydrogen gas atmosphere at 700 ° C. to vaporize coal, and to maintain a high temperature and high pressure of 450 ° C. and 10 atm even when liquefying coal. As described above, in Patent Document 1, since it is necessary to maintain a high temperature and a high pressure, there is a problem that the structure of the apparatus becomes complicated and handling control becomes troublesome. Further, since gas and solid are generated in addition to the liquid by pyrolysis, it is necessary to store each product separately, and for example, control for taking out a desired amount of the desired liquid product. Is also troublesome. Further, in order to take out a large amount of liquid product, it is necessary to add a large amount of a hydrogen-donating organic solvent. Therefore, a material and an apparatus for adding the organic solvent are also required, which increases the cost.

  On the other hand, Patent Document 2 relates to a method for removing sulfur from a carbonaceous material, and is a peroxide (active oxygen source) such as hydrogen peroxide and a hydroxide (active oxygen generating action) such as sodium hydroxide. And the like, and heat generation by generation of heat and generation of active oxygen, and a mixture of a solvent such as ether and a carbonaceous material is added to this and exposed to radiation to change the molecular structure. And release of sulfur.

  Therefore, in Patent Document 2, it is essential to use a peroxide material (active oxygen source) and a hydroxide (active oxygen generating agent). Therefore, an apparatus for mixing and supplying these, a solvent such as ether, An apparatus for mixing and supplying the carbonaceous material and a reaction apparatus for containing these mixtures are required, and there is a problem that the equipment becomes very complicated and large, and costs increase. In addition, since the peroxide substance (active oxygen source) and hydroxide (active oxygen generating agent) are mixed and heated by heat generation, there is a problem that control is difficult.

  Furthermore, also in the said patent document 2, since sulfur gas, a light oil product, a desulfurized crude oil product, and water + salt will be taken out as a reaction product, it is necessary to store each product separately, For example, the control for taking out a desired amount of the desired liquid product is also troublesome.

  As shown in Patent Documents 1 and 2, when pyrolyzing a carbonaceous material containing coal, a method of changing the molecular structure of the coal by radiation exposure, separating it into a gas, a liquid, a solid, and the like, and At the same time, a method for removing sulfur is disclosed, but there is currently no technique for obtaining coal as a hydrophilic coal slurry having fluidity as it is.

  The present invention has been made in view of the above circumstances, and a method and apparatus for producing a hydrophilic coal slurry capable of obtaining a hydrophilic coal slurry excellent in fluidity by reforming coal to be hydrophilic by a simple method. The purpose is to provide.

  The present invention creates a coal water slurry by mixing coal with water and irradiates the coal water slurry with radiation to dissociate carbon double bonds and generate hydrophilic groups in the water. The present invention relates to a method for producing a hydrophilic coal slurry, characterized by producing a modified hydrophilic coal slurry by being combined with carbon.

  Further, it is preferable to add a modification accelerator to the coal water slurry, and it is preferable to use at least one of Fe, Ni, Co, Cu, or at least one of these compounds as the modification accelerator. .

  Moreover, it is preferable to add an alkali agent to the coal water slurry, and sodium hydroxide is preferably used as the alkali agent.

  Moreover, it is preferable to add a desulfurization agent to the coal water slurry, and it is preferable to use at least one of Ca, Ba, Sr, and Ra, or at least one of these compounds as the desulfurization agent.

  The present invention relates to an irradiation chamber surrounded by a shielding wall, a radiation source disposed in the irradiation chamber, a coal water slurry production apparatus that mixes coal with water, and a coal water slurry produced by the coal water slurry production apparatus. An apparatus for producing a hydrophilic coal slurry, comprising: a slurry transporting device that is made to approach the radiation source in the irradiation chamber and then separate from the irradiation chamber to be taken out from the irradiation chamber.

  The slurry transporting device may be a pipeline that transports coal water slurry, and may be a transport device that transports a container containing coal water slurry.

  In the present invention, a coal water slurry is prepared by mixing coal with water, and a simple method and apparatus for irradiating the coal water slurry with radiation. The effect which can manufacture a property coal slurry can be produced.

  Since the hydrophilic coal slurry is excellent in fluidity, handling properties such as transportation and storage are improved, so that the use of coal can be greatly expanded.

  Embodiments of the present invention will be described below with reference to the accompanying drawings.

  FIG. 1 is an overall schematic plan view showing an example of the form of the apparatus for producing a hydrophilic coal slurry of the present invention. In the figure, reference numeral 1 denotes an irradiation chamber surrounded by a shielding wall 2, and the central portion of the irradiation chamber 1 is shown. The radiation source 3 is arranged in the. 4 is a coal water slurry production apparatus provided outside the shielding wall 2, and the coal water slurry production apparatus 4 mixes coal 5 and water 6 to create a coal water slurry 7.

  And between the said coal water slurry manufacturing apparatus 4 and the inside of the shielding wall 2, the coal water slurry 7 manufactured with the coal water slurry manufacturing apparatus 4 consists of the pump with which the coal water slurry manufacturing apparatus 4 was equipped, etc. By means (not shown), there is provided a slurry transporting device 9 comprising a pipeline 8 that is detoured around the outer periphery of the radiation source 3. At this time, the coal water slurry 7 flowing inside the slurry transporting device 9 is transported at room temperature.

  The coal 5 mixed with the water 6 by the coal water slurry production apparatus 4 can use finely pulverized coal (pulverized coal having a particle size of about 70 μm, which is usually used as pulverized coal), if possible. The coal water slurry 7 solution may be neutral, acidic or alkaline.

  Further, a reforming accelerator 10, an alkali agent 11, a desulfurizing agent 12, and the like can be added to the coal water slurry 7 created by the coal water slurry production apparatus 4.

  As the modification accelerator 10, at least one of metals such as Fe, Ni, Co, and Cu, or at least one of these compounds can be used. By adding the modification accelerator 10, radiation can be emitted. The modification effect when irradiated can be enhanced.

  Moreover, sodium hydroxide can be used for the alkali agent 11, and by adding the alkali agent 11 to keep the coal water slurry 7 alkaline, the OH radicals when the coal water slurry 7 is irradiated with radiation are added. Generation can be increased.

  The desulfurizing agent 12 may be at least one of Ca, Ba, Sr, Ra, etc., or at least one of these compounds. The desulfurizing agent 12 is ionized when added to the coal water slurry 7, Thus, a sulfate precipitate is generated in the coal water slurry 7, so that sulfur can be separated and taken out.

Various radiation generators and radiation generators can be used for the radiation source 3. For example, when using a vitrified material obtained by vitrifying high-level radioactive waste, 0.66 MeV gamma rays emitted from ¹³⁷ Cs are obtained, but 1.33 MeV gamma rays emitted from ⁶⁰ Co are obtained. Other γ rays, X-rays, electron beams, or the like can be used. In the case of using X-rays, an X-ray source may be used directly, but indirect due to a physical phenomenon such as bremsstrahlung by irradiating a third object such as lead with radiation such as gamma rays or electron beams. X-rays generated automatically can also be used. At this time, the intensity of the radiation from the radiation source 3 applied to the coal water slurry 7 is preferably a large dose in order to effectively reform the coal.

  The operation of the above embodiment will be described below.

  In the coal water slurry manufacturing apparatus 4 of FIG. 1, for example, coal water slurry 7 is created by mixing coal 5 and water 6 having a particle diameter of about 70 μm. At this time, a metal such as Fe, Ni, Co, Cu or at least one of these compounds can be added to the coal water slurry 7 as the reforming accelerator 10, and the alkali agent 11 can be hydroxylated. Sodium can be added, and Ca, Ba, Sr, Ra or at least one of these compounds can be added as the desulfurizing agent 12.

  Further, the radiation source 3 may be, for example, a vitrified body obtained by vitrifying high-level radioactive waste, another γ-ray source, or an X-ray or electron beam.

  The coal water slurry 7 produced by the coal water slurry production apparatus 4 is a slurry transportation apparatus comprising a pipeline 8 at room temperature by a transportation means (not shown) comprising a pump or the like provided in the coal water slurry production apparatus 4. 9 is supplied to the irradiation chamber 1 so as to bypass the outer periphery of the radiation source 3. At this time, as shown in FIG. 2, the coal water slurry 7 is modified by receiving radiation from the radiation source 3 to be hydrophilic. The coal slurry 7a is taken out.

That is, when the coal water slurry 7 is irradiated with radiation, as shown in [Chemical Formula 1], the double bond of carbon C is dissociated by radiation to generate C, COOH, etc. having unpaired electrons. On the other hand, the hydroxyl group OH ⁻ receives the action of radiation to generate OH radicals in water.

  This OH radical is very reactive. For this reason, the OH radical binds to the carbon C dissociated from the coal, whereby the coal is modified to have a hydrophilic group OH, and the hydrophilic coal slurry. 7a is generated.

  The reforming reaction by the OH radical is considered to be more reactive than the reforming reaction by hydrogenation that has been used in the conventional coal reforming method, and for this reason, a high temperature atmosphere is required as in the past. Without modification, it is possible to modify coal by radiation even at room temperature.

  When the reforming accelerator 10 made of at least one of metals such as Fe, Ni, Co, and Cu or these compounds is added to the coal water slurry 7 created in the coal water slurry manufacturing apparatus 4, the coal water slurry 7 can increase the radiation irradiation effect when radiating radiation, thereby further enhancing the modification reaction. Further, by adding Fe or the like to the coal water slurry 7 as described above, the combustion effect as a fuel when the hydrophilic coal slurry 7a is used as a fuel can be improved.

  Further, when an alkali agent 11 such as sodium hydroxide is added to the coal water slurry 7 created in the coal water slurry manufacturing apparatus 4, the coal water slurry 7 is kept alkaline, thereby irradiating the coal water slurry 7 with radiation. The generation of OH radicals when irradiated is increased, and thus the reforming reaction is further enhanced.

  Further, when a desulfurization agent 12 made of at least one of Ca, Ba, Sr, Ra or these compounds is added to the coal water slurry 7 created in the coal water slurry production apparatus 4, the desulfurization agent 12 is ionized, Thereby, since a sulfate precipitate is generated in the coal water slurry 7, sulfur can be separated and taken out.

  That is, when the coal water slurry 7 is irradiated with radiation, as shown in [Chemical Formula 2], the double bond of carbon C and sulfur S is dissociated by radiation to generate sulfur S having unpaired electrons, On the other hand, since OH radicals are generated in water by the action of radiation, the OH radicals combine with the dissociated sulfur S to form sulfates.

  Since the sulfate can be settled and separated, it can be separated and removed by the sulfur separation device 13 provided downstream of the pipeline 8.

  Therefore, the hydrophilic coal slurry 7a manufactured by the apparatus of FIG. 1 can be transported as it is to the destination by the slurry transporting device 9 by the pipeline 8.

  FIG. 3 is an overall schematic plan view showing another example of the form of the hydrophilic coal slurry production apparatus of the present invention, the basic structure of which is the same as that of FIG. 1, and the coal water slurry production apparatus 4 and the slurry transport apparatus. Since only the configuration of 9 is different, only this different configuration will be described.

  As shown in FIG. 4, the slurry transporting device 9 of FIG. 3 can circulate and convey the container 14 in which the coal water slurry 7 is accommodated between the radiation source 3 and the outside of the shielding wall 2. It has a conveying device 15 such as a belt conveyor installed at the endless.

  The coal water slurry production apparatus 4 mixes coal 5 with water 6 and further adds coal water slurry 7 to which the reforming accelerator 10, alkali agent 11, desulfurization agent 12 and the like are added as necessary. The container 14 in which the hydrophilic coal slurry 7a is generated by irradiation with radiation and the container 14 in which the hydrophilic coal slurry 7a is generated by being irradiated with radiation is taken out from the transport device 15 and supplied to the storage tank 16 for storing the hydrophilic coal slurry 7a. It has a function. The slurry transporting device 9 only needs to have a function of taking the coal water slurry 7 close to the radiation source 3 and irradiating it with radiation. A scheme can be used.

  The hydrophilic coal slurry 7 a stored in the storage tank 16 can be transported to a destination by a transport pipe 17.

  As described above, the hydrophilic coal slurry 7a, which is modified by irradiating the coal water slurry 7 in which the coal 5 and the water 6 are mixed with each other, is difficult to separate from water because it is hydrophilic, and is also fluid. Therefore, for example, the apparatus of the present invention is installed at a coal mining site, and the manufactured hydrophilic coal slurry 7a is easily and stably supplied in large quantities to a remote place such as a port by a pipeline 8 or a transport pipe 17 as it is. Therefore, it is possible to greatly expand the use of coal.

  In addition, the manufacturing method and apparatus of the hydrophilic coal slurry of this invention are not limited to an above-described form, Of course, various changes can be added within the range which does not deviate from the summary of this invention.

It is a whole schematic plan view which shows an example of the form of the manufacturing apparatus of the hydrophilic coal slurry of this invention. It is the front view which looked at FIG. 1 from the II direction. It is a whole schematic plan view which shows the other example of the form of the manufacturing apparatus of the hydrophilic coal slurry of this invention. It is the front view which looked at FIG. 3 from IV direction.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Irradiation chamber 2 Shielding wall 3 Radiation source 4 Coal water slurry production apparatus 5 Coal 6 Water 7 Coal water slurry 7a Hydrophilic coal slurry 8 Pipeline 9 Slurry transport apparatus 10 Modification accelerator 11 Alkaline agent 12 Desulfurization agent 14 Container 15 Conveyance apparatus

Claims (10)

  Coal is mixed with water to create a coal water slurry, and this coal water slurry is irradiated with radiation to dissociate double bonds of carbon and generate hydrophilic groups in the water, and the hydrophilic groups are combined with the dissociated carbon. A method for producing a hydrophilic coal slurry, characterized by producing a modified hydrophilic coal slurry.   The method for producing a hydrophilic coal slurry according to claim 1, wherein a reforming accelerator is added to the coal water slurry.   The method for producing a hydrophilic coal slurry according to claim 2, wherein at least one of Fe, Ni, Co, Cu, or at least one of these compounds is used as the modification accelerator.   The method for producing a hydrophilic coal slurry according to claim 1, wherein an alkaline agent is added to the coal water slurry.   The method for producing a hydrophilic coal slurry according to claim 4, wherein sodium hydroxide is used as the alkali agent.   The method for producing a hydrophilic coal slurry according to claim 1, wherein a desulfurizing agent is added to the coal water slurry.   The method for producing a hydrophilic coal slurry according to claim 6, wherein at least one of Ca, Ba, Sr, and Ra, or at least one of these compounds is used as the desulfurizing agent.   An irradiation chamber surrounded by a shielding wall, a radiation source disposed in the irradiation chamber, a coal water slurry production apparatus that mixes coal with water, and a coal water slurry produced by the coal water slurry production apparatus An apparatus for producing a hydrophilic coal slurry, comprising: a slurry transport device that is made to approach a radiation source and then separate from the radiation chamber to be taken out from the irradiation chamber.   The said slurry transport apparatus is a pipeline which conveys coal water slurry, The manufacturing apparatus of the hydrophilic coal slurry of Claim 8 characterized by the above-mentioned.   The said slurry transport apparatus is a conveying apparatus which conveys the container which accommodated the coal water slurry, The manufacturing apparatus of the hydrophilic coal slurry of Claim 8 characterized by the above-mentioned.

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