WO2021166612A1 - Porous substance regeneration apparatus - Google Patents

Porous substance regeneration apparatus Download PDF

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Publication number
WO2021166612A1
WO2021166612A1 PCT/JP2021/003470 JP2021003470W WO2021166612A1 WO 2021166612 A1 WO2021166612 A1 WO 2021166612A1 JP 2021003470 W JP2021003470 W JP 2021003470W WO 2021166612 A1 WO2021166612 A1 WO 2021166612A1
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Prior art keywords
porous substance
adsorbed
substance
porous
temperature
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PCT/JP2021/003470
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French (fr)
Japanese (ja)
Inventor
柴田　健司
東　隆行
亮 田中
笙 根本
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株式会社シバタ
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Publication of WO2021166612A1 publication Critical patent/WO2021166612A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • C01B32/36—Reactivation or regeneration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
    • G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder

Definitions

  • the present invention relates to a porous substance regenerating device.
  • a water treatment device that purifies the water to be treated by adsorbing the pollutants with an adsorbent such as a porous substance on the water to be treated containing a pollutant such as an organic compound.
  • the adsorbent on which pollutants and the like are adsorbed as the adsorbed material is regenerated by desorbing the adsorbed material by heating, for example.
  • a water treatment device capable of alternately adsorbing and desorbing such an object to be adsorbed is known (for example, Patent Document 1 described later).
  • Patent Document 1 describes that air at 180 ° C. is used as a heating gas in the desorption step of the water treatment apparatus.
  • the adsorbed material may not be desorbed at the above temperature.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a porous substance regenerating device capable of regenerating a porous substance at an appropriate temperature and reducing equipment cost and installation space. ..
  • the present invention is a porous substance regenerating device that heats and regenerates a porous substance on which an object to be adsorbed is adsorbed, and comprises a porous substance tank filled with the porous substance and the porous substance. It has a heating device that heats the first gas flowing in the porous substance tank so as to be in contact with the porous substance, and a combustion device that burns the adsorbed substance desorbed during regeneration of the porous substance.
  • the temperature at the time of regeneration of the sex substance is in the range of 300 ° C. to 800 ° C., and the porous substance is heated by using the second gas generated at the time of burning the object to be adsorbed in the combustion device.
  • playback equipment Regarding playback equipment.
  • the temperature at the time of regeneration of the porous substance is a temperature equal to or higher than the temperature at which the object to be adsorbed on the porous substance starts at least one of evaporation and decomposition, and the porous substance is said to be porous.
  • the porous substance regenerating apparatus according to any one of (1) to (7), wherein the temperature is lower than the temperature at which the substance starts to decompose by heating.
  • the temperature at which the adsorbed substance adsorbed on the porous substance starts at least one of evaporation and decomposition and the temperature at which the porous substance starts decomposition by heating are such that the adsorbed substance is adsorbed.
  • a porous substance regenerating device capable of regenerating a porous substance at an appropriate temperature and reducing equipment cost and installation space.
  • FIG. 7 is a cross-sectional view taken along the line AA'in the porous substance tank of FIG. It is a graph which shows the constant temperature analysis result of the activated carbon on which the adsorbed substance was adsorbed. It is a graph which shows the constant temperature analysis result of the activated carbon on which the adsorbed substance was adsorbed. It is a graph which shows the temperature-heating analysis result of the activated carbon on which the adsorbed substance was adsorbed.
  • the porous substance regenerating device 1 As shown in FIG. 1, the porous substance regenerating device 1 according to the embodiment of the present invention includes a porous substance tank 10, heating devices 11 and 16, a combustion device 12, a steam generator 13, and a water softener 14. And the pump device 15, and the lines L1, L2, L3, L4, L5 through which the fluid flows.
  • the porous substance regenerating device 1 can be used as a water treatment device capable of regenerating the porous substance used for adsorbing the object to be treated and also capable of on-site water treatment by using the regenerated porous substance. ..
  • the porous substance tank 10 is a tank filled with a porous substance.
  • the porous substance filled in the porous substance tank 10 is used for water treatment in which an object to be adsorbed such as an organic compound is adsorbed from the water to be treated and treated, and the object to be adsorbed is adsorbed.
  • an object to be adsorbed such as an organic compound
  • the object to be adsorbed is adsorbed.
  • By passing the first gas through the porous substance tank 10, at least one of evaporation and decomposition of the adsorbed substance is carried out to be desorbed from the porous substance, and the porous substance can be regenerated.
  • “desorption” shows the opposite concept to "adsorption”, and means that an object is detached from the surface of an object by a phenomenon such as evaporation or decomposition.
  • Water to be treated can flow through the porous substance tank 10, and after the porous substance is regenerated, it can also be used as an adsorption tank in water treatment.
  • porous substance examples include carbonic materials such as activated carbon and inorganic materials such as zeolite, alumina, titania, zirconia, silica and alumina.
  • Activated carbon is preferably used as the porous substance.
  • the activated carbon is not particularly limited, but activated carbon derived from coal, petroleum, biomass, etc. is used.
  • the shape is not particularly limited, and powdery, granular, molded products, fibers and the like are used.
  • the porous substance a mixture of two or more kinds may be used.
  • the porous substance regenerating device 1 can desorb an adsorbed substance having a boiling point of less than 100 ° C. from the porous substance.
  • the substance to be adsorbed is not particularly limited, and examples thereof include benzene (boiling point of about 80 ° C.) and trichlorethylene (boiling point of about 87 ° C.).
  • the porous substance regenerating device 1 according to the present embodiment can regenerate the porous substance filled in the porous substance tank 10 at an appropriate temperature.
  • the substance to be adsorbed contains, for example, an organic compound having a boiling point of 100 ° C. or higher or 200 ° C. or higher, the substance to be adsorbed can be desorbed.
  • the organic compound is not particularly limited, but is, for example, 1,4-dioxane (boiling point about 101 ° C.), triethylene glycol (boiling point about 285 ° C.), coalic acid (boiling point about 182 ° C.), p-tert-octylphenol (boiling point 280 ° C.). Degree), polyethylene glycol, sodium dodecylbenzenesulfonate, etc.
  • the first gas flows through the porous substance tank 10 so as to come into contact with the porous substance.
  • the first gas is, for example, at least one of water vapor, nitrogen, carbon dioxide, a rare gas such as helium and argon, and an inert gas such as freon, and the above two or more kinds of gases may be mixed. ..
  • the first gas preferably contains water vapor.
  • the first gas contains water vapor, desorption by decomposition of the substance to be adsorbed is promoted by the water vapor gasification reaction described later. In the following description, it is assumed that the first gas contains water vapor.
  • the first gas contains substantially no oxygen.
  • the oxygen contained in the first gas is preferably 0.01% by volume or less. From the above, a carbonaceous material such as activated carbon, which deteriorates by reacting with oxygen, can be used as the porous substance.
  • the temperature at the time of regeneration of the porous substance is 300 ° C. to 800 ° C. in the present embodiment.
  • the temperature at the time of regeneration is, for example, preferably 400 ° C. or higher, and more preferably 500 ° C. or higher. Further, it is preferably 700 ° C. or lower.
  • the temperature at the time of regeneration of the porous substance satisfies the above conditions, many substances to be adsorbed can be desorbed at the time of regeneration. Further, when the porous substance is activated carbon, weight loss due to activation of activated carbon can be suppressed.
  • the temperature at the time of regeneration of the porous substance filled in the porous substance tank 10 is preferably a temperature equal to or higher than the temperature at which the adsorbed substance desorbs by starting at least one of evaporation and decomposition.
  • the temperature at which the adsorbed substance adsorbed on the porous substance desorbs is a temperature equal to or higher than the boiling point of the adsorbed substance.
  • the adsorbed substance is adsorbed by forming an intermolecular force or, in some cases, a chemical bond in the micropores of a porous substance such as activated carbon.
  • the temperature at the time of regeneration of the porous substance is preferably a temperature lower than the temperature at which the porous substance starts decomposition by heating.
  • the porous substance is, for example, activated carbon
  • the temperature at which the activated carbon starts to decompose varies depending on the type of the substance to be adsorbed.
  • the temperature at which the adsorbed substance is desorbed and the temperature at which the porous substance starts to decompose are determined by thermogravimetric analysis.
  • Thermogravimetric analysis can be performed, for example, by measuring the weight change of a porous substance on which an adsorbed substance is adsorbed in a predetermined temperature range, for example, between room temperature and 1000 ° C.
  • the thermogravimetric analysis can be performed using, for example, a thermogravimetric analyzer (TGA) or a differential calorimetry simultaneous measurement device (TG-DTA).
  • TGA thermogravimetric analyzer
  • TG-DTA differential calorimetry simultaneous measurement device
  • the thermogravimetric analysis can be performed in an atmosphere of nitrogen, argon, air, water vapor or the like. Since the temperature at which the porous substance is decomposed by heating is measured, it is preferable to perform the analysis in a water vapor atmosphere.
  • the temperature at the time of regeneration of the porous substance is set to the temperature at which the object to be adsorbed starts at least one of evaporation and decomposition by the analysis by the thermogravimetric analyzer and the like, and the temperature at which the porous substance starts decomposition by heating. Determined based on.
  • the temperature of the first gas flowing through the porous substance tank 10 is determined based on the temperature at which the adsorbed substance starts at least one of evaporation and decomposition, which is determined by the thermogravimetric analysis.
  • the heating devices 11 and 16 are devices for heating the first gas.
  • the heating device 11 is not particularly limited, but is, for example, an electric heater device that is energized and heated.
  • the heating device 11 heats the steam to generate superheated steam at a predetermined temperature.
  • the heating device 16 is a heat exchange device and is provided on the upstream side of the heating device 11.
  • the heating device 16 heats the first gas by exchanging heat between the second gas and the first gas, which will be described later.
  • the heat exchange device used as the heating device 16 is not particularly limited, and examples thereof include heat exchange devices such as a double tube type, a jacket type, a shell & tube type, a spiral type, and a plate type.
  • the combustion device 12 burns the desorbed substance to be adsorbed during the regeneration of the porous substance.
  • the combustion device 12 is not particularly limited, but for example, a direct combustion device, a catalyst combustion device, or the like can be used.
  • the combustion device 12 includes a burner device, and mixes and burns air introduced from the outside and an object to be adsorbed such as an organic compound.
  • the combustion device 12 may include an air blower that introduces air.
  • the second gas which is the exhaust gas discharged from the combustion device 12, has a high temperature and is heat-exchanged with the first gas by the heating device 16 as a heat exchange device.
  • the steam generator 13 is a device that generates steam as a first gas.
  • the steam generator 13 is, for example, a boiler device, which generates heat by burning fuel.
  • the steam generator includes a heat exchange device, which exchanges heat between the generated heat and water, vaporizes the water, and generates steam.
  • the boiler device as the steam generator 13 may include a combustion chamber, a blower, and the like.
  • the boiler device is not particularly limited, and a known boiler device can be used.
  • the water softener 14 removes the hardness component of the raw water to soften the water.
  • the water softener 14 includes, for example, an ion exchange resin.
  • the ion exchange resin softens the raw water by adsorbing hardness components such as Ca ions and Mg ions contained in the raw water and releasing Na ions and the like possessed by the ion exchange resin instead. Thereby, the generation of scale with respect to the line L1 can be suppressed.
  • a water softener 14 a known one can be used.
  • the pump device 15 pumps the water to be treated to the porous substance tank 10 and distributes it.
  • the porous substance tank 10 is used as an adsorption tank in water treatment.
  • the pump device 15 is not particularly limited as long as it can pump a liquid, and examples thereof include a centrifugal pump such as a centrifugal pump and a volume transfer type pump such as a diaphragm pump.
  • the line L1 is a path through which the first gas flows.
  • the line L1 is provided with a water softener 14, a steam generator 13, a heating device 16, and a heating device 11 in this order from the upstream side.
  • Water such as tap water is circulated to the water softener 14 through the line L1.
  • the line L1 may be provided with a pump device (not shown) for pumping water to the water softener 14.
  • the water softened through the water softener 14 flows into the steam generator 13 and is vaporized to generate steam as the first gas.
  • the generated steam is heated to a boiling point or higher by the heating device 16 and the heating device 11, and becomes, for example, superheated steam of 300 ° C. or higher.
  • the superheated steam is circulated in the porous substance tank 10, and the adsorbed substance adsorbed on the porous substance is desorbed to regenerate the porous substance.
  • Line L2 is a path through which the gas discharged from the porous substance tank 10 flows.
  • the upstream side of the line L2 is connected to the porous material tank 10.
  • a combustion device 12 is provided on the line L2.
  • the gas discharged from the porous substance tank 10 includes water vapor and an adsorbed substance desorbed from the porous substance.
  • the substance to be adsorbed contains an organic compound or the like, and it is not preferable that the substance to be adsorbed is untreated and released to the outside. Therefore, the gas discharged from the porous substance tank 10 flows into the combustion device 12 through the line L2, is mixed with air, and is burned. As a result, the adsorbed material is deodorized and detoxified.
  • Line L3 is a path through which the second gas discharged from the combustion device 12 flows.
  • the upstream side of the line L3 is connected to the combustion device 12.
  • the line L3 is provided with a heating device 16 which is a heat exchange device.
  • the second gas is a high-temperature gas containing water vapor and a gas produced by decomposing the adsorbed substance by combustion.
  • the heating device 16 the first gas and the second gas having a temperature higher than that of the first gas exchange heat. That is, the porous substance is indirectly heated by using the second gas. Since the second gas after heat exchange in the line L3 still has a calorific value, it may be heat-accommodated with another system, and since it is deodorized and detoxified, it is released to the outside. You may.
  • the line L4 is a route through which the water to be treated flows.
  • a pump device 15 is provided on the line L4.
  • the water to be treated containing an organic compound is pumped by the pump device 15 and flows into the porous substance tank 10 used as the adsorption tank through the line L4.
  • Porous substance as an adsorption tank Water treatment is performed by adsorbing an object to be adsorbed such as an organic compound contained in the water to be treated to the porous substance filled in the tank 10.
  • the detoxified treated water after the adsorbed object is adsorbed is discharged to the outside, for example, through the line L5.
  • a porous substance regeneration device that regenerates a porous substance by allowing a heated first gas to flow through the porous substance tank 10 filled with the porous substance on which the adsorbed substance is adsorbed to desorb the adsorbed substance.
  • the first gas can be heated by using the heat energy of the second gas to indirectly heat the porous substance, the energy cost required for the regeneration of the porous substance can be reduced. Further, the device cost and installation space of the heating device 11 can be suppressed, and the temperature at the time of regeneration of the porous substance can be set to a temperature suitable for desorption of the adsorbed substance.
  • the porous substance regenerating device 1a has 11a and 11b as heating devices. Similar to the heating device 11, the heating devices 11a and 11b are, for example, electric heater devices that are energized and heated. Like the heating device 11, the heating device 11a is provided on the line L1 to heat the first gas. The heating device 11b is provided outside the porous substance tank 10 and heats the porous substance tank 10.
  • the heating device 11b that directly heats the porous substance tank in addition to the heating device 11a, the temperature of the first gas can be set to a high temperature gas suitable for desorption of the adsorbed object. Further, when heating the porous substance in a state where the moisture remains after using the porous substance tank 10 as the adsorption tank, a large amount of heat is required because the moisture is vaporized. Since the heating device 11b can directly apply the heat required for vaporizing the water from the heating device 11b, the energy cost can be reduced. Further, by vaporizing the water remaining in the porous substance, the desorption of the adsorbed substance is promoted.
  • the porous substance regenerating device 1b includes a combustion device 12a and a heating device 16a.
  • fuel is supplied to the combustion device 12a together with air.
  • a combustion device 12a is, for example, a direct combustion device.
  • the fuel is not particularly limited, and for example, liquid fuels such as kerosene, heavy oil, and light oil, and gaseous fuels such as liquefied natural gas (LNG) and liquefied petroleum gas (LPG) are used.
  • LNG liquefied natural gas
  • LPG liquefied petroleum gas
  • the fuel is burned together with the adsorbed material desorbed during the regeneration of the porous material.
  • the combustion device 12a can raise the temperature of the second gas discharged from the combustion device 12a to a higher temperature.
  • the heating device 16a is a heat exchange device, and the second gas discharged from the combustion device 12a can flow.
  • the second gas flowing through the heating device 16a has a higher temperature than that according to the first embodiment and the second embodiment. Therefore, the first gas can be sufficiently heated by heat exchange between the second gas and the first gas without providing another heating device in the line L1.
  • the porous substance regenerating device 1b is configured by providing a combustion device 12a in which fuel is supplied together with air and burned together with an adsorbed object. As a result, the temperature of the second gas generated from the combustion device 12a can be raised. Therefore, since the first gas can be heated using only the heating device 16a that exchanges heat between the second gas and the first gas, the installation space of the porous substance regeneration device can be reduced.
  • the porous substance regenerating device 1c As shown in FIG. 4, the porous substance regenerating device 1c according to the fourth embodiment has a porous substance tank 10a. Further, as in the third embodiment, it has a combustion device 12a and a heating device 16a.
  • FIG. 7 is a vertical cross-sectional view showing the configuration of the porous substance tank 10a. As shown in FIG. 7, the porous substance tank 10a has a filling portion 101, a heat transfer tube 102, and a jacket 103.
  • the filling part 101 is a place where, for example, activated carbon as a porous substance is filled.
  • the first gas and the water to be treated can flow into the filling portion 101 via the inlet portion 101a and can flow out through the outlet portion 101b.
  • the water vapor as the first gas flows through the filling portion 101 so as to be in direct contact with the activated carbon, thereby desorbing the adsorbed substance from the activated carbon.
  • the water to be treated is circulated to the filling portion 101 so as to be in direct contact with the activated carbon, so that the adsorbed substance contained therein is adsorbed by the activated carbon and purified, and is discharged to the outside as treated water.
  • the heat transfer tube 102 is a tube through which the second gas discharged from the combustion device 12a can flow. As shown in FIG. 7, the heat transfer tube 102 has a plurality of folded flow paths that circulate in the filling portion 101. The flow path may have a branch portion inside the filling portion 101.
  • FIG. 8 is a cross-sectional view taken along the line AA'in FIG. As shown in FIG. 8, the heat transfer tube 102 circulates throughout the filling portion 101.
  • the second gas flows into the heat transfer tube 102 via the heat transfer tube inlet 102a and flows out from the heat transfer tube 102 via the heat transfer tube outlet 102b. By flowing a second gas having a high temperature through the heat transfer tube 102, the porous substance filled in the filling portion 101 can be heated.
  • the material of the heat transfer tube 102 is not particularly limited, and for example, stainless steel (SUS), titanium, copper, or the like is used.
  • the jacket 103 is a flow path through which the second gas discharged from the combustion device 12a can flow. As shown in FIGS. 7 and 8, the jacket 103 is formed so as to cover the periphery of the filling portion 101.
  • the second gas flows into the jacket 103 through the jacket inlet 103a and flows out from the jacket 103 through the jacket outlet 103b.
  • a second gas By passing a second gas through the jacket 103 in addition to the heat transfer tube 102, a larger amount of heat can be given to the porous substance filled in the filling portion 101.
  • Line L31 and line L32 are routes through which the second gas flows.
  • Line L31 is a path connecting the combustion device 12a and the porous substance tank 10a.
  • the upstream side of the line L31 is connected to the combustion device 12a.
  • the downstream side of the line L31 is connected to the heat transfer tube inlet 102a and the jacket inlet 103a of the porous material tank 10a.
  • a second gas is circulated through the heat transfer tube 102 and the jacket 103.
  • the porous material can be heated. After the residual water is exhausted, the porous substance may be heated by passing a second gas through either the heat transfer tube 102 or the jacket 103.
  • Line L32 is a route on the downstream side of the porous substance tank 10a.
  • the upstream side of the line L32 is connected to the heat transfer tube outlet 102b and the jacket outlet 103b of the porous material tank 10a.
  • the line L32 is provided with a heating device 16a as a heat exchange device. Since the second gas discharged from the porous substance tank 10a still has a large amount of heat, the first gas can be heated by exchanging heat with the first gas in the heating device 16a.
  • the porous substance regenerating device 1d As shown in FIG. 5, the porous substance regenerating device 1d according to the fifth embodiment has a steam generating device 13a. Further, as in the fourth embodiment, it has a porous substance tank 10a, a combustion device 12a, and a heating device 16a.
  • a steam generator 13a is provided in addition to the heating device 16a on the line L32 which is a flow path on the downstream side of the porous substance tank 10a.
  • the second gas can flow, and by exchanging heat between the second gas and water, the water is vaporized to generate steam as the first gas.
  • the second gas flowing out of the heating device 16a has a sufficient amount of heat even after heat exchange with the first gas. Therefore, by providing the steam generator 13a on the downstream side of the heating device 16a, it is possible to further recover heat from the second gas. Therefore, the energy cost required for the regeneration of the porous substance can be further reduced.
  • the porous substance regenerating device 1e includes a porous substance tank 10a, a combustion device 12a, a steam generator 13a, and a heating device 16a, as in the fifth embodiment. Has.
  • a heating device 16a which is a heat exchange device, is provided in a line L31 which is a flow path on the upstream side of the porous substance tank 10a.
  • the upstream side of the line L31 is connected to the combustion device 12a.
  • the second gas discharged from the combustion device 12a may have a high temperature of, for example, 800 ° C. or higher. Therefore, the second gas is not directly circulated to the porous substance tank 10a, but is circulated to the porous substance tank 10a after heat exchange with the first gas in the heating device 16a which is a heat exchange device.
  • the temperature of the second gas flowing through the porous substance tank 10a can be controlled, and the temperature at the time of regeneration of the porous substance can be set to an appropriate temperature.
  • the porous substance regenerating device has been described as having a single porous substance tank 10 or 10a. However, it is not limited to the above.
  • the porous substance regenerating device may have a plurality of porous substance tanks. For example, two porous substance tanks can be provided. According to the above, while water treatment is performed using one porous substance tank, water treatment is continuously performed by using another porous substance tank for regeneration of the porous substance or performing maintenance. be able to. Further, when the load of the water to be treated temporarily increases, the water treatment capacity can be temporarily improved by circulating the water to be treated to a plurality of porous substance tanks and performing the water treatment in parallel. In addition to the above, the number of porous substance tanks may be three or more. As a result, the reserve capacity for water treatment can be secured, so that water treatment can be performed even when the load of the water to be treated fluctuates drastically.
  • ABS sodium dodecylbenzenesulfonate
  • PEG polyethylene glycol
  • the symbols in the formula indicate the following.
  • W t Sample weight (mg) at treatment time t A: Initial adsorption rate (wt%) of the object to be adsorbed
  • the regeneration rate R of activated carbon whose adsorbed material is ABS is shown in Table 1 and FIG. 9 below.
  • the regeneration rate R of activated carbon in which the adsorbed material is PEG is shown in Table 2 and FIG. 10 below.
  • the activated carbon on which ABS is adsorbed has a regeneration rate R of 83.5% when regenerated for 120 minutes under the condition of 450 ° C. Under the condition of 500 ° C., the regeneration rate R reached 100% after 120 minutes, and under the condition of 550 ° C., the regeneration rate R reached 100% after 30 minutes. Therefore, even when the temperature at the time of regeneration of the activated carbon is set to the boiling point of ABS (about 205 ° C.) or higher, the result shows that the activated carbon cannot be completely regenerated in a short time depending on the regeneration temperature.
  • the activated carbon on which PEG is adsorbed has a regeneration rate R of 86.5% when regenerated at 350 ° C. for 30 minutes, and a regeneration rate R after 60 minutes of regeneration. Is 100%. Under the condition of 400 ° C., the regeneration rate R reached 100% after 5 minutes. Therefore, by comparing with Table 1 and FIG. 9, it was shown that the preferable regeneration temperature differs depending on the type of the object to be adsorbed on the activated carbon.
  • Activated carbon crushed coal, standard particle size 8/32 mesh, specific surface area 965 m 2 / g was used as the porous material, and the above activated carbon in a state where the adsorbed material was adsorbed was prepared by practical use of water treatment.
  • a mixed gas of 20% water vapor and 80% nitrogen was used (water vapor partial pressure 20.2 kPa).
  • the temperature rising condition the temperature was raised from a temperature of about 70 to 80 ° C. to 1000 ° C. at a temperature rising rate of 10 ° C./min. The results are shown in FIG.
  • FIG. 11 is a graph showing the results of the above-mentioned temperature rise heat analysis test.
  • the horizontal axis represents temperature (° C.) and the vertical axis represents weight (mg).
  • the temperature change of the sample is shown by a solid line.
  • the weight loss was shown in the temperature range from about 80 ° C. to about 100 ° C. immediately after the start of temperature rise. This is considered to be due to the evaporation of water contained in the activated carbon.
  • the onset of weight loss was shown at temperature T1. It is considered that this is due to the desorption of the adsorbed material due to at least one of evaporation and decomposition of the adsorbed material adsorbed on the activated carbon.
  • the temperature at the time of regeneration of the activated carbon is T1 or higher, which is the temperature at which the adsorbed substance starts at least one of evaporation and decomposition, and is the temperature at which the activated carbon starts decomposition by activation. It was confirmed that by setting the temperature to less than T3, the adsorbed material was desorbed and the activated carbon could be regenerated without being decomposed by activation.
  • Porous substance regeneration device water treatment device
  • Porous substance tank adsorption tank
  • Heating device 12a Combustion device 13, 13a Steam generator
  • 16a Heat exchange device heat exchange device

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  • Treatment Of Liquids With Adsorbents In General (AREA)

Abstract

Provided is a porous substance regeneration apparatus with which it is possible to regenerate a porous substance at a suitable temperature and to reduce equipment costs and required installation space.　A porous substance regeneration apparatus 1 that regenerates a porous substance by which an adsorption material is adsorbed, the porous substance regeneration apparatus 1 having a porous substance tank 10 filled with the porous substance, heating devices 11 and 16 that heat a first gas channeled through the porous substance tank 10 so that the first gas comes into contact with the porous substance, and a combustion device 12 that combusts the desorbed adsorption material during regeneration of the porous substance, the porous substance regeneration apparatus 1 moreover being such that a second gas generated during combustion of the adsorption material in the combustion device 12 is used to heat the porous substance.

Description

多孔性物質再生装置Porous material regeneration device
　本発明は、多孔性物質再生装置に関する。 The present invention relates to a porous substance regenerating device.
　従来、有機化合物等の汚染物質を含有する被処理水に対し、多孔性物質等の吸着材により汚染物質を吸着させ、被処理水を清浄化する水処理装置が知られている。被吸着物として汚染物質等が吸着された吸着材は、例えば加熱されることで被吸着物が脱着され、再生される。このような被吸着物の吸着と脱着を交互に行える水処理装置が知られている（例えば、後述する特許文献１）。 Conventionally, there is known a water treatment device that purifies the water to be treated by adsorbing the pollutants with an adsorbent such as a porous substance on the water to be treated containing a pollutant such as an organic compound. The adsorbent on which pollutants and the like are adsorbed as the adsorbed material is regenerated by desorbing the adsorbed material by heating, for example. A water treatment device capable of alternately adsorbing and desorbing such an object to be adsorbed is known (for example, Patent Document 1 described later).
特開２００６－０５５７１３号公報Japanese Unexamined Patent Publication No. 2006-055713
　特許文献１には、水処理装置の脱着工程における加熱ガスとして１８０℃の空気を使用することが記載されている。しかし、多孔性物質等の吸着材に吸着される被吸着物の種類によっては、上記温度では被吸着物が脱着されない場合がある。他方で、加熱ガスの温度を高温化するには、加熱装置の容量を増大させる必要があり、装置コストや設置スペースの点で課題があった。 Patent Document 1 describes that air at 180 ° C. is used as a heating gas in the desorption step of the water treatment apparatus. However, depending on the type of the adsorbed material adsorbed on the adsorbent such as a porous substance, the adsorbed material may not be desorbed at the above temperature. On the other hand, in order to raise the temperature of the heating gas, it is necessary to increase the capacity of the heating device, which poses a problem in terms of device cost and installation space.
　本発明は、上記に鑑みてなされたものであり、多孔質物質の再生を適正温度で行うことができ、かつ設備コストや設置スペースを低減できる多孔性物質再生装置を提供することを目的とする。 The present invention has been made in view of the above, and an object of the present invention is to provide a porous substance regenerating device capable of regenerating a porous substance at an appropriate temperature and reducing equipment cost and installation space. ..
（１）本発明は、被吸着物が吸着された多孔性物質を加熱して再生する多孔性物質再生装置であって、前記多孔性物質が充填された多孔性物質槽と、前記多孔性物質に接触するように前記多孔性物質槽に流通する第１気体を加熱する加熱装置と、前記多孔性物質の再生時に脱着された前記被吸着物を燃焼させる燃焼装置と、を有し、前記多孔性物質の再生時の温度は３００℃～８００℃の範囲内であり、前記燃焼装置において前記被吸着物の燃焼時に発生する第２気体を用いて、前記多孔性物質を加熱する、多孔性物質再生装置に関する。 (1) The present invention is a porous substance regenerating device that heats and regenerates a porous substance on which an object to be adsorbed is adsorbed, and comprises a porous substance tank filled with the porous substance and the porous substance. It has a heating device that heats the first gas flowing in the porous substance tank so as to be in contact with the porous substance, and a combustion device that burns the adsorbed substance desorbed during regeneration of the porous substance. The temperature at the time of regeneration of the sex substance is in the range of 300 ° C. to 800 ° C., and the porous substance is heated by using the second gas generated at the time of burning the object to be adsorbed in the combustion device. Regarding playback equipment.
（２）前記第２気体を、前記多孔性物質槽に流通させて前記多孔性物質を加熱する（１）に記載の多孔性物質再生装置。 (2) The porous substance regenerating apparatus according to (1), wherein the second gas is circulated in the porous substance tank to heat the porous substance.
（３）前記加熱装置は、前記第２気体と前記第１気体との間で熱交換を行う熱交換装置を含む、（１）又は（２）に記載の多孔性物質再生装置。 (3) The porous substance regenerating device according to (1) or (2), wherein the heating device includes a heat exchange device that exchanges heat between the second gas and the first gas.
（４）前記第１気体は、水蒸気を含み、水蒸気を発生させる水蒸気発生装置を有する、（１）～（３）いずれかに記載の多孔性物質再生装置。 (4) The porous substance regenerating device according to any one of (1) to (3), wherein the first gas contains water vapor and has a water vapor generator for generating water vapor.
（５）前記第２気体は、前記水蒸気発生装置において熱交換を行う、（４）に記載の多孔性物質再生装置。 (5) The porous substance regeneration device according to (4), wherein the second gas exchanges heat in the steam generator.
（６）前記燃焼装置には、前記被吸着物と共に燃焼される燃料が供給される、（１）～（５）いずれかに記載の多孔性物質再生装置。 (6) The porous substance regenerating device according to any one of (1) to (5), wherein fuel to be burned together with the adsorbed substance is supplied to the combustion device.
（７）前記多孔性物質は、活性炭である、（１）～（６）いずれかに記載の多孔性物質再生装置。 (7) The porous substance regenerating device according to any one of (1) to (6), wherein the porous substance is activated carbon.
（８）前記多孔性物質の再生時の温度は、前記多孔性物質に吸着された前記被吸着物が蒸発及び分解のうち少なくともいずれかを開始する温度以上の温度であり、かつ、前記多孔性物質が加熱により分解を開始する温度未満の温度である、（１）～（７）いずれかに記載の多孔性物質再生装置。 (8) The temperature at the time of regeneration of the porous substance is a temperature equal to or higher than the temperature at which the object to be adsorbed on the porous substance starts at least one of evaporation and decomposition, and the porous substance is said to be porous. The porous substance regenerating apparatus according to any one of (1) to (7), wherein the temperature is lower than the temperature at which the substance starts to decompose by heating.
（９）前記多孔性物質に吸着された前記被吸着物が蒸発及び分解のうち少なくともいずれかを開始する温度と、前記多孔性物質が加熱により分解を開始する温度は、前記被吸着物が吸着された前記多孔性物質を熱重量分析し、前記被吸着物が吸着された前記多孔性物質が重量減少を開始する温度を測定することにより決定される、（８）に記載の多孔性物質再生装置。 (9) The temperature at which the adsorbed substance adsorbed on the porous substance starts at least one of evaporation and decomposition and the temperature at which the porous substance starts decomposition by heating are such that the adsorbed substance is adsorbed. The regeneration of the porous material according to (8), which is determined by thermogravimetric analysis of the porous material and the temperature at which the porous material on which the adsorbed object is adsorbed starts to lose weight. Device.
（１０）（１）～（９）いずれかに記載の多孔性物質再生装置を備える水処理装置であり、前記被吸着物が脱着された前記多孔性物質が充填された前記多孔性物質槽を、被処理水が流通可能な吸着層として用いる、水処理装置。 (10) A water treatment apparatus provided with the porous substance regenerating apparatus according to any one of (1) to (9), wherein the porous substance tank filled with the porous substance to which the adsorbed substance has been desorbed is provided. , A water treatment device used as an adsorption layer through which water to be treated can flow.
　本発明によれば、多孔質物質の再生を適正温度で行うことができ、かつ設備コストや設置スペースを低減できる多孔性物質再生装置を提供できる。 According to the present invention, it is possible to provide a porous substance regenerating device capable of regenerating a porous substance at an appropriate temperature and reducing equipment cost and installation space.
本発明の第１実施形態に係る多孔性物質再生装置の構成を示す図である。It is a figure which shows the structure of the porous substance regeneration apparatus which concerns on 1st Embodiment of this invention. 本発明の第２実施形態に係る多孔性物質再生装置の構成を示す図である。It is a figure which shows the structure of the porous substance regeneration apparatus which concerns on 2nd Embodiment of this invention. 本発明の第３実施形態に係る多孔性物質再生装置の構成を示す図である。It is a figure which shows the structure of the porous substance regeneration apparatus which concerns on 3rd Embodiment of this invention. 本発明の第４実施形態に係る多孔性物質再生装置の構成を示す図である。It is a figure which shows the structure of the porous substance regeneration apparatus which concerns on 4th Embodiment of this invention. 本発明の第５実施形態に係る多孔性物質再生装置の構成を示す図である。It is a figure which shows the structure of the porous substance regeneration apparatus which concerns on 5th Embodiment of this invention. 本発明の第６実施形態に係る多孔性物質再生装置の構成を示す図である。It is a figure which shows the structure of the porous substance regeneration apparatus which concerns on 6th Embodiment of this invention. 本発明の実施形態に係る多孔性物質槽を示す縦断面図である。It is a vertical sectional view which shows the porous substance tank which concerns on embodiment of this invention. 図７の多孔性物質槽におけるＡ－Ａ’線断面図である。FIG. 7 is a cross-sectional view taken along the line AA'in the porous substance tank of FIG. 被吸着物が吸着された活性炭の定温熱分析結果を示すグラフである。It is a graph which shows the constant temperature analysis result of the activated carbon on which the adsorbed substance was adsorbed. 被吸着物が吸着された活性炭の定温熱分析結果を示すグラフである。It is a graph which shows the constant temperature analysis result of the activated carbon on which the adsorbed substance was adsorbed. 被吸着物が吸着された活性炭の昇温熱分析結果を示すグラフである。It is a graph which shows the temperature-heating analysis result of the activated carbon on which the adsorbed substance was adsorbed.
　以下、本発明の実施形態について説明する。但し、以下に示す実施形態は、本発明を例示するものであって、本発明は以下の実施形態に限定されない。 Hereinafter, embodiments of the present invention will be described. However, the embodiments shown below exemplify the present invention, and the present invention is not limited to the following embodiments.
［第１実施形態］
　本発明の実施形態に係る多孔性物質再生装置１は、図１に示すように、多孔性物質槽１０と、加熱装置１１及び１６と、燃焼装置１２と、水蒸気発生装置１３と、軟水器１４と、ポンプ装置１５と、流体が流通するラインＬ１、Ｌ２、Ｌ３、Ｌ４、Ｌ５と、を有する。多孔性物質再生装置１は、被処理物の吸着に用いる多孔性物質の再生が可能であると共に、再生後の多孔性物質を用い、オンサイトでの水処理が可能な水処理装置として使用できる。 [First Embodiment]
As shown in FIG. 1, the porous substance regenerating device 1 according to the embodiment of the present invention includes a porous substance tank 10, heating devices 11 and 16, a combustion device 12, a steam generator 13, and a water softener 14. And the pump device 15, and the lines L1, L2, L3, L4, L5 through which the fluid flows. The porous substance regenerating device 1 can be used as a water treatment device capable of regenerating the porous substance used for adsorbing the object to be treated and also capable of on-site water treatment by using the regenerated porous substance. ..
　多孔性物質槽１０は、多孔性物質が充填される槽である。多孔性物質槽１０に充填される多孔性物質は、被処理水から有機化合物等の被吸着物を吸着して処理する水処理に用いられ、上記被吸着物が吸着されている。多孔性物質槽１０に第１気体を流通させることで、被吸着物の蒸発及び分解のうち少なくともいずれかが行われて多孔性物質から脱着され、多孔性物質を再生できる。なお、本明細書中において、「脱着」は、「吸着」とは反対の概念を示し、蒸発や分解等の現象により対象が物体表面から脱離することを意味する。多孔性物質槽１０には、被処理水が流通可能であり、多孔性物質の再生を行った後に、水処理における吸着槽としても使用できる。 The porous substance tank 10 is a tank filled with a porous substance. The porous substance filled in the porous substance tank 10 is used for water treatment in which an object to be adsorbed such as an organic compound is adsorbed from the water to be treated and treated, and the object to be adsorbed is adsorbed. By passing the first gas through the porous substance tank 10, at least one of evaporation and decomposition of the adsorbed substance is carried out to be desorbed from the porous substance, and the porous substance can be regenerated. In addition, in this specification, "desorption" shows the opposite concept to "adsorption", and means that an object is detached from the surface of an object by a phenomenon such as evaporation or decomposition. Water to be treated can flow through the porous substance tank 10, and after the porous substance is regenerated, it can also be used as an adsorption tank in water treatment.
　多孔性物質としては、例えば活性炭等の炭素質材料や、ゼオライト、アルミナ、チタニア、ジルコニア、シリカ、アルミナ等の無機質材料等が挙げられる。多孔性物質としては、活性炭が用いられることが好ましい。活性炭としては、特に制限されないが、石炭由来、石油由来、バイオマス由来等の活性炭が用いられる。形状としても特に制限されず、粉状、粒状、成形品、繊維等の形状を有するものが用いられる。上記多孔性物質としては、２種以上が混合されたものを用いてもよい。 Examples of the porous substance include carbonic materials such as activated carbon and inorganic materials such as zeolite, alumina, titania, zirconia, silica and alumina. Activated carbon is preferably used as the porous substance. The activated carbon is not particularly limited, but activated carbon derived from coal, petroleum, biomass, etc. is used. The shape is not particularly limited, and powdery, granular, molded products, fibers and the like are used. As the porous substance, a mixture of two or more kinds may be used.
　被吸着物としては、例えば、炭化水素化合物、含酸素化合物、含窒素化合物、含硫黄化合物、及びハロゲン化合物等の有機化合物が挙げられる。本実施形態に係る多孔性物質再生装置１は、１００℃未満の沸点を有する被吸着物を多孔性物質から脱着できる。上記被吸着物としては特に制限されないが、例えばベンゼン（沸点８０℃程度）、トリクロロエチレン（沸点８７℃程度）等が挙げられる。本実施形態に係る多孔性物質再生装置１は、多孔性物質槽１０に充填される多孔性物質の再生を適正温度で行うことができる。従って、被吸着物として例えば１００℃以上、或いは２００℃以上の沸点を有する有機化合物が含まれている場合であっても、被吸着物の脱着を行うことができる。上記有機化合物としては特に制限されないが、例えば１，４－ジオキサン（沸点１０１℃程度）、トリエチレングリコール（沸点２８５℃程度）、石炭酸（沸点１８２℃程度）、ｐ－ｔｅｒｔ－オクチルフェノール（沸点２８０℃程度）、ポリエチレングリコール、ドデシルベンゼンスルホン酸ナトリウム等が挙げられる。 Examples of the object to be adsorbed include organic compounds such as hydrocarbon compounds, oxygen-containing compounds, nitrogen-containing compounds, sulfur-containing compounds, and halogen compounds. The porous substance regenerating device 1 according to the present embodiment can desorb an adsorbed substance having a boiling point of less than 100 ° C. from the porous substance. The substance to be adsorbed is not particularly limited, and examples thereof include benzene (boiling point of about 80 ° C.) and trichlorethylene (boiling point of about 87 ° C.). The porous substance regenerating device 1 according to the present embodiment can regenerate the porous substance filled in the porous substance tank 10 at an appropriate temperature. Therefore, even when the substance to be adsorbed contains, for example, an organic compound having a boiling point of 100 ° C. or higher or 200 ° C. or higher, the substance to be adsorbed can be desorbed. The organic compound is not particularly limited, but is, for example, 1,4-dioxane (boiling point about 101 ° C.), triethylene glycol (boiling point about 285 ° C.), coalic acid (boiling point about 182 ° C.), p-tert-octylphenol (boiling point 280 ° C.). Degree), polyethylene glycol, sodium dodecylbenzenesulfonate, etc.
　多孔性物質槽１０には、多孔性物質に接触するように第１気体が流通する。
　第１気体は、例えば水蒸気、窒素、二酸化炭素、及びヘリウム、アルゴン等の希ガス、及びフロン等の不活性ガスのうち少なくともいずれかであり、上記２種以上の気体が混合されていてもよい。第１気体には、水蒸気が含まれることが好ましい。第１気体に水蒸気が含まれることで、後述する水蒸気ガス化反応により、被吸着物質の分解による脱着が促進される。以下の説明では、第１気体に水蒸気が含まれるものとして説明する。上記に加え、第１気体は酸素を実質的に含まないことが好ましい。例えば第１気体に含まれる酸素が０．０１体積％以下であることが好ましい。上記により、酸素と反応して劣化する活性炭等の炭素質材料を多孔性物質として用いることができる。 The first gas flows through the porous substance tank 10 so as to come into contact with the porous substance.
The first gas is, for example, at least one of water vapor, nitrogen, carbon dioxide, a rare gas such as helium and argon, and an inert gas such as freon, and the above two or more kinds of gases may be mixed. .. The first gas preferably contains water vapor. When the first gas contains water vapor, desorption by decomposition of the substance to be adsorbed is promoted by the water vapor gasification reaction described later. In the following description, it is assumed that the first gas contains water vapor. In addition to the above, it is preferable that the first gas contains substantially no oxygen. For example, the oxygen contained in the first gas is preferably 0.01% by volume or less. From the above, a carbonaceous material such as activated carbon, which deteriorates by reacting with oxygen, can be used as the porous substance.
　第１気体が加熱されて多孔性物質に接触することで、被吸着物が加熱され、多孔性物質から脱着される。第１気体に水蒸気が含まれる場合、水蒸気と多孔性物質に吸着された被吸着物とが以下の式（１）で示す水蒸気ガス化反応や、式（２）で示すシフト反応を起こすことで、被吸着物が分解されると考えられる。
　ＣｎＨｍ＋ｎＨ２Ｏ＝ｎＣＯ＋（ｎ＋ｍ／２）Ｈ２　　　　（１）
　ｎＣＯ＋ｎＨ２Ｏ＝ｎＣＯ２＋ｎＨ２　　　　　　　　　　（２） When the first gas is heated and comes into contact with the porous substance, the object to be adsorbed is heated and desorbed from the porous substance. When the first gas contains water vapor, the water vapor and the adsorbed substance adsorbed on the porous substance cause a water vapor gasification reaction represented by the following formula (1) or a shift reaction represented by the formula (2). , It is considered that the adsorbed material is decomposed.
C n H m + nH 2 O = nCO + (n + m / 2) H 2 (1)
nCO + nH 2 O = nCO 2 + nH 2 (2)
　多孔性物質の再生時の温度は、本実施形態において、３００℃～８００℃である。上記再生時の温度は、例えば４００℃以上であることが好ましく、５００℃以上であることがより好ましい。また、７００℃以下であることが好ましい。多孔性物質の再生時の温度が上記条件を満たすことで、再生時に多くの被吸着物を脱着することができる。また、多孔性物質が活性炭である場合、活性炭の賦活による重量減少を抑制することができる。 The temperature at the time of regeneration of the porous substance is 300 ° C. to 800 ° C. in the present embodiment. The temperature at the time of regeneration is, for example, preferably 400 ° C. or higher, and more preferably 500 ° C. or higher. Further, it is preferably 700 ° C. or lower. When the temperature at the time of regeneration of the porous substance satisfies the above conditions, many substances to be adsorbed can be desorbed at the time of regeneration. Further, when the porous substance is activated carbon, weight loss due to activation of activated carbon can be suppressed.
　多孔性物質槽１０に充填される多孔性物質の再生時の温度は、被吸着物が蒸発及び分解のうち少なくともいずれかを開始することで脱着する温度以上の温度であることが好ましい。多孔性物質に吸着された被吸着物が脱着する温度は、被吸着物の沸点以上の温度である。例えば、ｐ－ｔｅｒｔ－オクチルフェノール（沸点２８０℃程度）が被吸着物として吸着された多孔性物質としての活性炭を再生する場合、活性炭の再生時の温度を例えば２８０℃とした場合であっても、活性炭の再生を行うことができない。これは、被吸着物が活性炭等の多孔性物質における微細孔中で、分子間力や場合により化学結合を形成して吸着しているためと考えられる。また、多孔性物質の再生時の温度は、多孔性物質が加熱により分解を開始する温度未満の温度であることが好ましい。多孔性物質が例えば活性炭である場合、被吸着物質の種類により、活性炭が分解を開始する温度は変動する。 The temperature at the time of regeneration of the porous substance filled in the porous substance tank 10 is preferably a temperature equal to or higher than the temperature at which the adsorbed substance desorbs by starting at least one of evaporation and decomposition. The temperature at which the adsorbed substance adsorbed on the porous substance desorbs is a temperature equal to or higher than the boiling point of the adsorbed substance. For example, when regenerating activated carbon as a porous substance in which p-tert-octylphenol (boiling point of about 280 ° C.) is adsorbed as an adsorbed substance, even when the temperature at the time of regeneration of the activated carbon is set to, for example, 280 ° C. Activated carbon cannot be regenerated. It is considered that this is because the adsorbed substance is adsorbed by forming an intermolecular force or, in some cases, a chemical bond in the micropores of a porous substance such as activated carbon. Further, the temperature at the time of regeneration of the porous substance is preferably a temperature lower than the temperature at which the porous substance starts decomposition by heating. When the porous substance is, for example, activated carbon, the temperature at which the activated carbon starts to decompose varies depending on the type of the substance to be adsorbed.
　上記被吸着物が脱着する温度及び多孔性物質が分解を開始する温度は、熱重量分析によって決定することが好ましい。熱重量分析は、例えば所定の温度領域、例えば室温から１０００℃の間の被吸着物が吸着された多孔性物質の重量変化を測定することで行うことができる。熱重量分析は、例えば熱重量分析装置（ＴＧＡ）や示差熱量同時測定装置（ＴＧ－ＤＴＡ）を用いて行うことができる。なお、熱重量分析は窒素、アルゴン、空気、水蒸気等の雰囲気下で行うことができる。多孔性物質が加熱により分解される温度を測定するため、水蒸気雰囲気下で分析を行うことが好ましい。 It is preferable that the temperature at which the adsorbed substance is desorbed and the temperature at which the porous substance starts to decompose are determined by thermogravimetric analysis. Thermogravimetric analysis can be performed, for example, by measuring the weight change of a porous substance on which an adsorbed substance is adsorbed in a predetermined temperature range, for example, between room temperature and 1000 ° C. The thermogravimetric analysis can be performed using, for example, a thermogravimetric analyzer (TGA) or a differential calorimetry simultaneous measurement device (TG-DTA). The thermogravimetric analysis can be performed in an atmosphere of nitrogen, argon, air, water vapor or the like. Since the temperature at which the porous substance is decomposed by heating is measured, it is preferable to perform the analysis in a water vapor atmosphere.
　多孔性物質の再生時の温度は、上記熱重量分析装置等による分析により、被吸着物が蒸発及び分解のうち少なくともいずれかを開始する温度と、多孔性物質が加熱により分解を開始する温度に基づき決定される。例えば、多孔性物質槽１０に流通する第１気体の温度は、上記熱重量分析により求めた、被吸着物が蒸発及び分解のうち少なくともいずれかを開始する温度に基づき決定される。 The temperature at the time of regeneration of the porous substance is set to the temperature at which the object to be adsorbed starts at least one of evaporation and decomposition by the analysis by the thermogravimetric analyzer and the like, and the temperature at which the porous substance starts decomposition by heating. Determined based on. For example, the temperature of the first gas flowing through the porous substance tank 10 is determined based on the temperature at which the adsorbed substance starts at least one of evaporation and decomposition, which is determined by the thermogravimetric analysis.
　加熱装置１１及び１６は、第１気体を加熱する装置である。加熱装置１１は、特に制限されないが、例えば通電されて加熱される電気式のヒータ装置である。加熱装置１１は、第１気体が水蒸気である場合、水蒸気を加熱して所定温度の過熱水蒸気を生成する。加熱装置１６は、熱交換装置であり、加熱装置１１の上流側に設けられる。加熱装置１６は、後述する第２気体と第１気体とを熱交換することで、第１気体を加熱する。加熱装置１６として用いられる熱交換装置は、特に制限されず、二重管式、ジャケット式、シェル＆チューブ式、スパイラル式、プレート式等の熱交換装置が挙げられる。 The heating devices 11 and 16 are devices for heating the first gas. The heating device 11 is not particularly limited, but is, for example, an electric heater device that is energized and heated. When the first gas is steam, the heating device 11 heats the steam to generate superheated steam at a predetermined temperature. The heating device 16 is a heat exchange device and is provided on the upstream side of the heating device 11. The heating device 16 heats the first gas by exchanging heat between the second gas and the first gas, which will be described later. The heat exchange device used as the heating device 16 is not particularly limited, and examples thereof include heat exchange devices such as a double tube type, a jacket type, a shell & tube type, a spiral type, and a plate type.
　燃焼装置１２は、多孔性物質の再生時に脱着された被吸着物を燃焼させる。燃焼装置１２としては、特に限定されないが、例えば直接燃焼装置や触媒燃焼装置等を用いることができる。燃焼装置１２は、バーナ装置を備え、外部から導入した空気と有機化合物等の被吸着物とを混合して燃焼させる。燃焼装置１２は、空気を導入する空気ブロワを備えていてもよい。上記燃焼により、被吸着物がＣＯ２やＨ２Ｏ等に分解され、脱臭及び無害化される。上記燃焼装置１２から排出される排ガスである第２気体は高温であり、熱交換装置としての加熱装置１６で第１気体と熱交換される。 The combustion device 12 burns the desorbed substance to be adsorbed during the regeneration of the porous substance. The combustion device 12 is not particularly limited, but for example, a direct combustion device, a catalyst combustion device, or the like can be used. The combustion device 12 includes a burner device, and mixes and burns air introduced from the outside and an object to be adsorbed such as an organic compound. The combustion device 12 may include an air blower that introduces air. By the above combustion, the adsorbed substance is decomposed into CO 2 and H 2 O, etc., and deodorized and detoxified. The second gas, which is the exhaust gas discharged from the combustion device 12, has a high temperature and is heat-exchanged with the first gas by the heating device 16 as a heat exchange device.
　水蒸気発生装置１３は、第１気体としての水蒸気を発生させる装置である。水蒸気発生装置１３は、例えばボイラ装置であり、燃料を燃焼させることで熱を発生させる。水蒸気発生装置は、熱交換装置を備え、発生させた熱と水との間で熱交換を行い、水を気化させて水蒸気を発生させる。水蒸気発生装置１３としてのボイラ装置は、燃焼室や送風機等を含んでいてもよい。このようなボイラ装置としては、特に制限されず、公知のものを用いることができる。 The steam generator 13 is a device that generates steam as a first gas. The steam generator 13 is, for example, a boiler device, which generates heat by burning fuel. The steam generator includes a heat exchange device, which exchanges heat between the generated heat and water, vaporizes the water, and generates steam. The boiler device as the steam generator 13 may include a combustion chamber, a blower, and the like. The boiler device is not particularly limited, and a known boiler device can be used.
　軟水器１４は、原水中の硬度成分を除去し軟水化させる。軟水器１４は、例えばイオン交換樹脂を備える。イオン交換樹脂は、原水に含まれるＣａイオンやＭｇイオン等の硬度成分を吸着し、代わりに自身が有するＮａイオン等を放出することで原水を軟水化する。これにより、ラインＬ１に対するスケールの発生を抑制できる。このような軟水器１４としては、公知のものを用いることができる。 The water softener 14 removes the hardness component of the raw water to soften the water. The water softener 14 includes, for example, an ion exchange resin. The ion exchange resin softens the raw water by adsorbing hardness components such as Ca ions and Mg ions contained in the raw water and releasing Na ions and the like possessed by the ion exchange resin instead. Thereby, the generation of scale with respect to the line L1 can be suppressed. As such a water softener 14, a known one can be used.
　ポンプ装置１５は、被処理水を多孔性物質槽１０に圧送して流通させる。ポンプ装置１５により、被処理水が多孔性物質槽１０に流通される場合、多孔性物質槽１０は水処理における吸着槽として用いられる。ポンプ装置１５としては、液体を圧送できるものであれば特に制限されず、例えば渦巻式等の遠心ポンプ、ダイアフラムポンプ等の容積移送式ポンプ等が挙げられる。 The pump device 15 pumps the water to be treated to the porous substance tank 10 and distributes it. When the water to be treated is circulated to the porous substance tank 10 by the pump device 15, the porous substance tank 10 is used as an adsorption tank in water treatment. The pump device 15 is not particularly limited as long as it can pump a liquid, and examples thereof include a centrifugal pump such as a centrifugal pump and a volume transfer type pump such as a diaphragm pump.
　（多孔性物質再生装置１を用いた多孔性物質の再生方法）
　ラインＬ１は、図１に示すように、第１気体が流通する経路である。ラインＬ１には、上流側から順に軟水器１４、水蒸気発生装置１３、加熱装置１６、加熱装置１１が設けられる。ラインＬ１を通じ、水道水等の水が軟水器１４に流通される。ラインＬ１には、水を軟水器１４に圧送するポンプ装置（図示省略）が設けられていてもよい。軟水器１４を通じ軟水化された水は水蒸気発生装置１３に流入し、気化されて第１気体としての水蒸気が生成される。生成された水蒸気は、加熱装置１６及び加熱装置１１により沸点以上に加熱され、例えば３００℃以上の過熱水蒸気となる。上記過熱水蒸気は多孔性物質槽１０に流通され、多孔性物質に吸着された被吸着物が脱着されて多孔性物質が再生される。 (Method of regenerating a porous substance using the porous substance regenerating device 1)
As shown in FIG. 1, the line L1 is a path through which the first gas flows. The line L1 is provided with a water softener 14, a steam generator 13, a heating device 16, and a heating device 11 in this order from the upstream side. Water such as tap water is circulated to the water softener 14 through the line L1. The line L1 may be provided with a pump device (not shown) for pumping water to the water softener 14. The water softened through the water softener 14 flows into the steam generator 13 and is vaporized to generate steam as the first gas. The generated steam is heated to a boiling point or higher by the heating device 16 and the heating device 11, and becomes, for example, superheated steam of 300 ° C. or higher. The superheated steam is circulated in the porous substance tank 10, and the adsorbed substance adsorbed on the porous substance is desorbed to regenerate the porous substance.
　ラインＬ２は、多孔性物質槽１０から排出される気体が流通する経路である。ラインＬ２の上流側は多孔性物質槽１０と接続される。ラインＬ２には、燃焼装置１２が設けられる。多孔性物質槽１０から排出される気体には、水蒸気と、多孔性物質から脱着された被吸着物とが含まれる。被吸着物には有機化合物等が含まれ、未処理で外部へ放出されることは好ましくない。このため、多孔性物質槽１０から排出された気体は、ラインＬ２を通じ燃焼装置１２に流入し、空気と混合されて燃焼される。これにより、被吸着物が脱臭及び無害化される。 Line L2 is a path through which the gas discharged from the porous substance tank 10 flows. The upstream side of the line L2 is connected to the porous material tank 10. A combustion device 12 is provided on the line L2. The gas discharged from the porous substance tank 10 includes water vapor and an adsorbed substance desorbed from the porous substance. The substance to be adsorbed contains an organic compound or the like, and it is not preferable that the substance to be adsorbed is untreated and released to the outside. Therefore, the gas discharged from the porous substance tank 10 flows into the combustion device 12 through the line L2, is mixed with air, and is burned. As a result, the adsorbed material is deodorized and detoxified.
　ラインＬ３は、燃焼装置１２から排出される第２気体が流通する経路である。ラインＬ３の上流側は、燃焼装置１２と接続される。ラインＬ３には、熱交換装置である加熱装置１６が設けられる。第２気体は、被吸着物が燃焼により分解されて生成される気体と、水蒸気とを含む高温の気体である。加熱装置１６において、第１気体と、第１気体より高温の第２気体とが熱交換される。即ち、第２気体を用いて、間接的に多孔性物質が加熱される。ラインＬ３において熱交換を行った後の第２気体は、まだ熱量を有しているため、他の系統と熱融通を行ってもよいし、脱臭及び無害化されているため、外部に放出されてもよい。 Line L3 is a path through which the second gas discharged from the combustion device 12 flows. The upstream side of the line L3 is connected to the combustion device 12. The line L3 is provided with a heating device 16 which is a heat exchange device. The second gas is a high-temperature gas containing water vapor and a gas produced by decomposing the adsorbed substance by combustion. In the heating device 16, the first gas and the second gas having a temperature higher than that of the first gas exchange heat. That is, the porous substance is indirectly heated by using the second gas. Since the second gas after heat exchange in the line L3 still has a calorific value, it may be heat-accommodated with another system, and since it is deodorized and detoxified, it is released to the outside. You may.
　（排水処理方法）
　次に、上記再生方法により再生された多孔性物質が充填された多孔性物質槽１０を吸着槽として用い、排水処理を行う方法について説明する。
　ラインＬ４は、図１に示すように、被処理水が流通する経路である。ラインＬ４には、ポンプ装置１５が設けられる。例えば有機化合物を含む被処理水は、ポンプ装置１５により圧送され、ラインＬ４を通じ、吸着槽として用いられる多孔性物質槽１０に流入する。吸着槽としての多孔性物質槽１０に充填された多孔性物質に、上記被処理水に含まれる有機化合物等の被吸着物が吸着されることで水処理が行われる。被吸着物が吸着された後の無害化された処理水は、ラインＬ５を通じて例えば外部に放出される。 (Wastewater treatment method)
Next, a method of performing wastewater treatment using the porous substance tank 10 filled with the porous substance regenerated by the above regeneration method as an adsorption tank will be described.
As shown in FIG. 1, the line L4 is a route through which the water to be treated flows. A pump device 15 is provided on the line L4. For example, the water to be treated containing an organic compound is pumped by the pump device 15 and flows into the porous substance tank 10 used as the adsorption tank through the line L4. Porous substance as an adsorption tank Water treatment is performed by adsorbing an object to be adsorbed such as an organic compound contained in the water to be treated to the porous substance filled in the tank 10. The detoxified treated water after the adsorbed object is adsorbed is discharged to the outside, for example, through the line L5.
　上記第１実施形態に係る多孔性物質再生装置１によれば、以下の効果が奏される。被吸着物が吸着された多孔性物質が充填された多孔性物質槽１０に対し、加熱された第１気体を流通させて被吸着物を脱着させ、多孔性物質を再生する多孔性物質再生装置１において、脱着させた被吸着物の燃焼時に発生する第２気体を用いて、多孔性物質を加熱することとした。上記により、第２気体の有する熱エネルギーを利用して第１気体を加熱し、間接的に多孔性物質を加熱できるため、多孔性物質の再生に要するエネルギーコストを低減できる。また、加熱装置１１の装置コストや設置スペースを抑え、かつ多孔性物質の再生時の温度を、被吸着物の脱着に適した温度とすることができる。 According to the porous substance regenerating device 1 according to the first embodiment, the following effects are exhibited. A porous substance regeneration device that regenerates a porous substance by allowing a heated first gas to flow through the porous substance tank 10 filled with the porous substance on which the adsorbed substance is adsorbed to desorb the adsorbed substance. In No. 1, it was decided to heat the porous substance by using the second gas generated at the time of burning the desorbed adsorbed substance. As described above, since the first gas can be heated by using the heat energy of the second gas to indirectly heat the porous substance, the energy cost required for the regeneration of the porous substance can be reduced. Further, the device cost and installation space of the heating device 11 can be suppressed, and the temperature at the time of regeneration of the porous substance can be set to a temperature suitable for desorption of the adsorbed substance.
［第２実施形態］
　次に、本発明の第２実施形態に係る多孔性物質再生装置１ａについて説明する。以下の説明において、既に説明した実施形態と同様の構成については、記載を省略する場合がある。 [Second Embodiment]
Next, the porous substance regenerating device 1a according to the second embodiment of the present invention will be described. In the following description, the description may be omitted for the same configuration as the embodiment already described.
　多孔性物質再生装置１ａは、図２に示すように、加熱装置として１１ａ及び１１ｂを有する。加熱装置１１ａ及び１１ｂは、加熱装置１１と同様、例えば通電されて加熱される電気式のヒータ装置である。加熱装置１１ａは、加熱装置１１と同様、ラインＬ１に設けられて第１気体を加熱する。加熱装置１１ｂは、多孔性物質槽１０の外側に設けられ、多孔性物質槽１０を加熱する。 As shown in FIG. 2, the porous substance regenerating device 1a has 11a and 11b as heating devices. Similar to the heating device 11, the heating devices 11a and 11b are, for example, electric heater devices that are energized and heated. Like the heating device 11, the heating device 11a is provided on the line L1 to heat the first gas. The heating device 11b is provided outside the porous substance tank 10 and heats the porous substance tank 10.
　上記第２実施形態に係る多孔性物質再生装置１ａによれば、以下の効果が奏される。加熱装置１１ａに加え、多孔性物質槽を直接加熱する加熱装置１１ｂを設けることで、第１気体の温度を被吸着物の脱着に適した高温の気体とすることができる。また、多孔性物質槽１０を吸着槽として使用した後の水分が残存した状態の多孔性物質の加熱に際しては、水分の気化を行うため、大きな熱量が必要となる。加熱装置１１ｂにより、上記水分の気化に要する熱を直接加熱装置１１ｂから付与できるため、エネルギーコストを低減できる。また、多孔性物質に残存した水分を気化させることで、被吸着物の脱着が促進される。 According to the porous substance regenerating device 1a according to the second embodiment, the following effects are exhibited. By providing the heating device 11b that directly heats the porous substance tank in addition to the heating device 11a, the temperature of the first gas can be set to a high temperature gas suitable for desorption of the adsorbed object. Further, when heating the porous substance in a state where the moisture remains after using the porous substance tank 10 as the adsorption tank, a large amount of heat is required because the moisture is vaporized. Since the heating device 11b can directly apply the heat required for vaporizing the water from the heating device 11b, the energy cost can be reduced. Further, by vaporizing the water remaining in the porous substance, the desorption of the adsorbed substance is promoted.
［第３実施形態］
　第３実施形態に係る多孔性物質再生装置１ｂは、図３に示すように、燃焼装置１２ａと、加熱装置１６ａとを有する。
　燃焼装置１２ａには、図３に示すように、空気と共に燃料が供給される。このような燃焼装置１２ａは、例えば直接燃焼装置である。上記燃料としては、特に制限されず、例えば灯油、重油、軽油等の液体燃料や、液化天然ガス（ＬＮＧ）、液化石油ガス（ＬＰＧ）等の気体燃料が用いられる。上記燃料は、多孔性物質の再生時に脱着された被吸着物と共に燃焼される。燃焼装置１２ａにより、燃焼装置１２ａから排出される第２気体を、より高温にすることができる。 [Third Embodiment]
As shown in FIG. 3, the porous substance regenerating device 1b according to the third embodiment includes a combustion device 12a and a heating device 16a.
As shown in FIG. 3, fuel is supplied to the combustion device 12a together with air. Such a combustion device 12a is, for example, a direct combustion device. The fuel is not particularly limited, and for example, liquid fuels such as kerosene, heavy oil, and light oil, and gaseous fuels such as liquefied natural gas (LNG) and liquefied petroleum gas (LPG) are used. The fuel is burned together with the adsorbed material desorbed during the regeneration of the porous material. The combustion device 12a can raise the temperature of the second gas discharged from the combustion device 12a to a higher temperature.
　加熱装置１６ａは、熱交換装置であり、燃焼装置１２ａから排出される第２気体が流通可能である。加熱装置１６ａに流通する第２気体は、第１実施形態及び第２実施形態に係るものよりも高温である。従って、ラインＬ１に他の加熱装置を設けずとも、第２気体と第１気体との熱交換により、十分に第１気体を加熱できる。 The heating device 16a is a heat exchange device, and the second gas discharged from the combustion device 12a can flow. The second gas flowing through the heating device 16a has a higher temperature than that according to the first embodiment and the second embodiment. Therefore, the first gas can be sufficiently heated by heat exchange between the second gas and the first gas without providing another heating device in the line L1.
　上記第３実施形態に係る多孔性物質再生装置１ｂによれば、以下の効果が奏される。多孔性物質再生装置１ｂを、空気と共に燃料が供給されて被吸着物と共に燃焼させる燃焼装置１２ａを設けて構成した。これにより、燃焼装置１２ａから発生する第２気体を高温化できる。従って、第２気体と第１気体との熱交換を行う加熱装置１６ａのみを用いて第１気体を加熱できるため、多孔性物質再生装置の設置スペースを低減できる。 According to the porous substance regenerating device 1b according to the third embodiment, the following effects are exhibited. The porous substance regenerating device 1b is configured by providing a combustion device 12a in which fuel is supplied together with air and burned together with an adsorbed object. As a result, the temperature of the second gas generated from the combustion device 12a can be raised. Therefore, since the first gas can be heated using only the heating device 16a that exchanges heat between the second gas and the first gas, the installation space of the porous substance regeneration device can be reduced.
［第４実施形態］
　第４実施形態に係る多孔性物質再生装置１ｃは、図４に示すように、多孔性物質槽１０ａを有する。また、第３実施形態と同様、燃焼装置１２ａと、加熱装置１６ａとを有する。 [Fourth Embodiment]
As shown in FIG. 4, the porous substance regenerating device 1c according to the fourth embodiment has a porous substance tank 10a. Further, as in the third embodiment, it has a combustion device 12a and a heating device 16a.
　多孔性物質槽１０ａは、図４に示すように、第１気体及び被処理水が流通可能であると共に、第２気体が流通可能である。図７は、多孔性物質槽１０ａの構成を示す縦断面図である。図７に示すように、多孔性物質槽１０ａは、充填部１０１と、伝熱管１０２と、ジャケット１０３と、を有する。 As shown in FIG. 4, the porous substance tank 10a can circulate the first gas and the water to be treated, and can circulate the second gas. FIG. 7 is a vertical cross-sectional view showing the configuration of the porous substance tank 10a. As shown in FIG. 7, the porous substance tank 10a has a filling portion 101, a heat transfer tube 102, and a jacket 103.
　充填部１０１は、多孔性物質としての例えば活性炭が充填される箇所である。充填部１０１には、第１気体及び被処理水が入口部１０１ａを介して流入可能であり、出口部１０１ｂを介して流出可能である。第１気体としての水蒸気は、活性炭と直接接するように充填部１０１に流通することで、活性炭から被吸着物を脱着させる。被処理水は、活性炭と直接接するように充填部１０１に流通することで、含有する被吸着物が活性炭に吸着されて浄化され、処理水として外部に排出される。 The filling part 101 is a place where, for example, activated carbon as a porous substance is filled. The first gas and the water to be treated can flow into the filling portion 101 via the inlet portion 101a and can flow out through the outlet portion 101b. The water vapor as the first gas flows through the filling portion 101 so as to be in direct contact with the activated carbon, thereby desorbing the adsorbed substance from the activated carbon. The water to be treated is circulated to the filling portion 101 so as to be in direct contact with the activated carbon, so that the adsorbed substance contained therein is adsorbed by the activated carbon and purified, and is discharged to the outside as treated water.
　伝熱管１０２は、燃焼装置１２ａから排出される第２気体が流通可能な管である。図７に示すように、伝熱管１０２は充填部１０１内を流通する複数の折り返し流路を有する。上記流路は、充填部１０１の内部で分岐箇所を有していてもよい。図８は、図７におけるＡ－Ａ’断面図である。図８に示すように、充填部１０１の全体にわたり伝熱管１０２が流通している。第２気体は伝熱管入口１０２ａを介して伝熱管１０２に流入し、伝熱管出口１０２ｂを介して伝熱管１０２から流出する。伝熱管１０２に高温を有する第２気体が流通することで、充填部１０１に充填された多孔性物質を加熱できる。伝熱管１０２の材質としては特に制限されないが、例えばステンレス鋼材（ＳＵＳ）、チタン、銅等が用いられる。 The heat transfer tube 102 is a tube through which the second gas discharged from the combustion device 12a can flow. As shown in FIG. 7, the heat transfer tube 102 has a plurality of folded flow paths that circulate in the filling portion 101. The flow path may have a branch portion inside the filling portion 101. FIG. 8 is a cross-sectional view taken along the line AA'in FIG. As shown in FIG. 8, the heat transfer tube 102 circulates throughout the filling portion 101. The second gas flows into the heat transfer tube 102 via the heat transfer tube inlet 102a and flows out from the heat transfer tube 102 via the heat transfer tube outlet 102b. By flowing a second gas having a high temperature through the heat transfer tube 102, the porous substance filled in the filling portion 101 can be heated. The material of the heat transfer tube 102 is not particularly limited, and for example, stainless steel (SUS), titanium, copper, or the like is used.
　ジャケット１０３は、伝熱管１０２同様、燃焼装置１２ａから排出される第２気体が流通可能な流路である。図７及び図８に示すように、ジャケット１０３は充填部１０１の周囲を覆うように形成される。第２気体はジャケット入口１０３ａを介してジャケット１０３に流入し、ジャケット出口１０３ｂを介してジャケット１０３から流出する。伝熱管１０２に加え、ジャケット１０３に第２気体を流通させることで、充填部１０１に充填された多孔性物質に対し、より多くの熱量を与えることができる。 Like the heat transfer tube 102, the jacket 103 is a flow path through which the second gas discharged from the combustion device 12a can flow. As shown in FIGS. 7 and 8, the jacket 103 is formed so as to cover the periphery of the filling portion 101. The second gas flows into the jacket 103 through the jacket inlet 103a and flows out from the jacket 103 through the jacket outlet 103b. By passing a second gas through the jacket 103 in addition to the heat transfer tube 102, a larger amount of heat can be given to the porous substance filled in the filling portion 101.
　（多孔性物質再生装置１ｃを用いた多孔性物質の再生方法）
　多孔性物質再生装置１ｃのラインＬ１及びラインＬ２は、第１実施形態と同様の構成を有するため説明を省略する。ラインＬ３１及びラインＬ３２は、第２気体が流通する経路である。 (Method of regenerating a porous substance using the porous substance regenerating device 1c)
Since the line L1 and the line L2 of the porous substance regenerating device 1c have the same configuration as that of the first embodiment, the description thereof will be omitted. Line L31 and line L32 are routes through which the second gas flows.
　ラインＬ３１は、燃焼装置１２ａと多孔性物質槽１０ａとを接続する経路である。ラインＬ３１の上流側は、燃焼装置１２ａと接続される。ラインＬ３１の下流側は、多孔性物質槽１０ａの伝熱管入口１０２ａ及びジャケット入口１０３ａと接続される。例えば、多孔性物質槽１０ａを吸着槽として使用した後の、水分が残存した状態の多孔性物質の加熱の際は、多くの熱量を要するため、伝熱管１０２及びジャケット１０３に第２気体を流通させて多孔性物質を加熱できる。残存水がなくなった後は、伝熱管１０２及びジャケット１０３のうち、いずれかに第２気体を流通させて多孔性物質を加熱してもよい。 Line L31 is a path connecting the combustion device 12a and the porous substance tank 10a. The upstream side of the line L31 is connected to the combustion device 12a. The downstream side of the line L31 is connected to the heat transfer tube inlet 102a and the jacket inlet 103a of the porous material tank 10a. For example, after using the porous substance tank 10a as an adsorption tank, a large amount of heat is required to heat the porous substance in a state where water remains, so a second gas is circulated through the heat transfer tube 102 and the jacket 103. The porous material can be heated. After the residual water is exhausted, the porous substance may be heated by passing a second gas through either the heat transfer tube 102 or the jacket 103.
　ラインＬ３２は、多孔性物質槽１０ａの下流側の経路である。ラインＬ３２の上流側は、多孔性物質槽１０ａの伝熱管出口１０２ｂ及びジャケット出口１０３ｂと接続される。ラインＬ３２には、熱交換装置としての加熱装置１６ａが設けられる。多孔性物質槽１０ａから排出される第２気体はまだ多くの熱量を有しているため、加熱装置１６ａにおいて第１気体と熱交換を行うことで第１気体を加熱できる。 Line L32 is a route on the downstream side of the porous substance tank 10a. The upstream side of the line L32 is connected to the heat transfer tube outlet 102b and the jacket outlet 103b of the porous material tank 10a. The line L32 is provided with a heating device 16a as a heat exchange device. Since the second gas discharged from the porous substance tank 10a still has a large amount of heat, the first gas can be heated by exchanging heat with the first gas in the heating device 16a.
［第５実施形態］
　第５実施形態に係る多孔性物質再生装置１ｄは、図５に示すように、水蒸気発生装置１３ａを有する。また、第４実施形態と同様、多孔性物質槽１０ａと、燃焼装置１２ａと、加熱装置１６ａとを有する。 [Fifth Embodiment]
As shown in FIG. 5, the porous substance regenerating device 1d according to the fifth embodiment has a steam generating device 13a. Further, as in the fourth embodiment, it has a porous substance tank 10a, a combustion device 12a, and a heating device 16a.
　多孔性物質再生装置１ｄは、多孔性物質槽１０ａの下流側の流路であるラインＬ３２に、加熱装置１６ａに加え水蒸気発生装置１３ａが設けられる。
　水蒸気発生装置１３ａは、第２気体が流通可能であり、第２気体と水との熱交換を行うことで、水を気化させて第１気体としての水蒸気を発生させる。加熱装置１６ａから流出する第２気体は、第１気体と熱交換を行った後も十分な熱量を有している。このため、加熱装置１６ａの下流側に水蒸気発生装置１３ａを設けることで、第２気体から更に熱回収を行うことができる。従って、多孔性物質の再生に要するエネルギーコストを更に低減できる。 In the porous substance regeneration device 1d, a steam generator 13a is provided in addition to the heating device 16a on the line L32 which is a flow path on the downstream side of the porous substance tank 10a.
In the steam generator 13a, the second gas can flow, and by exchanging heat between the second gas and water, the water is vaporized to generate steam as the first gas. The second gas flowing out of the heating device 16a has a sufficient amount of heat even after heat exchange with the first gas. Therefore, by providing the steam generator 13a on the downstream side of the heating device 16a, it is possible to further recover heat from the second gas. Therefore, the energy cost required for the regeneration of the porous substance can be further reduced.
［第６実施形態］
　第６実施形態に係る多孔性物質再生装置１ｅは、図６に示すように、第５実施形態と同様、多孔性物質槽１０ａと、燃焼装置１２ａと、水蒸気発生装置１３ａと、加熱装置１６ａとを有する。 [Sixth Embodiment]
As shown in FIG. 6, the porous substance regenerating device 1e according to the sixth embodiment includes a porous substance tank 10a, a combustion device 12a, a steam generator 13a, and a heating device 16a, as in the fifth embodiment. Has.
　多孔性物質再生装置１ｅは、多孔性物質槽１０ａの上流側の流路であるラインＬ３１に、熱交換装置である加熱装置１６ａが設けられる。ラインＬ３１の上流側は燃焼装置１２ａと接続されている。燃焼装置１２ａから排出される第２気体は、例えば８００℃以上の高温である場合がある。従って、第２気体を多孔性物質槽１０ａに直接流通させず、熱交換装置である加熱装置１６ａで第１気体と熱交換を行った後に多孔性物質槽１０ａに流通させる。上記により、多孔性物質槽１０ａに流通する第２気体の温度を制御でき、多孔性物質の再生時の温度を適正な温度にすることができる。 In the porous substance regeneration device 1e, a heating device 16a, which is a heat exchange device, is provided in a line L31 which is a flow path on the upstream side of the porous substance tank 10a. The upstream side of the line L31 is connected to the combustion device 12a. The second gas discharged from the combustion device 12a may have a high temperature of, for example, 800 ° C. or higher. Therefore, the second gas is not directly circulated to the porous substance tank 10a, but is circulated to the porous substance tank 10a after heat exchange with the first gas in the heating device 16a which is a heat exchange device. As described above, the temperature of the second gas flowing through the porous substance tank 10a can be controlled, and the temperature at the time of regeneration of the porous substance can be set to an appropriate temperature.
　以上、本発明の好ましい実施形態について説明した。しかし、本発明は上記の実施形態に限定されず、本発明の効果を損なわない範囲内において適宜変更が可能である。 The preferred embodiment of the present invention has been described above. However, the present invention is not limited to the above-described embodiment, and can be appropriately modified as long as the effects of the present invention are not impaired.
　上記実施形態に係る多孔性物質再生装置を、単一の多孔性物質槽１０又は１０ａを有するものとして説明した。しかし、上記に限定されない。多孔性物質再生装置は、複数の多孔性物質槽を有していてもよい。例えば、多孔性物質槽を２つ設けることもできる。上記により、１つの多孔性物質槽を用いて水処理を行っている間に、他の多孔性物質槽を多孔性物質の再生に用い、或いはメンテナンスを行うことで、連続的に水処理を行うことができる。また、一時的に被処理水の負荷が増大した場合に、被処理水を複数の多孔性物質槽に流通させて水処理を並行して行うことで、一時的に水処理能力を向上できる。上記以外に、多孔性物質槽を３つ又はそれ以上の数とすることもできる。これにより、水処理における予備力を確保できるため、被処理水の負荷の変動が激しい場合であっても水処理を行うことができる。 The porous substance regenerating device according to the above embodiment has been described as having a single porous substance tank 10 or 10a. However, it is not limited to the above. The porous substance regenerating device may have a plurality of porous substance tanks. For example, two porous substance tanks can be provided. According to the above, while water treatment is performed using one porous substance tank, water treatment is continuously performed by using another porous substance tank for regeneration of the porous substance or performing maintenance. be able to. Further, when the load of the water to be treated temporarily increases, the water treatment capacity can be temporarily improved by circulating the water to be treated to a plurality of porous substance tanks and performing the water treatment in parallel. In addition to the above, the number of porous substance tanks may be three or more. As a result, the reserve capacity for water treatment can be secured, so that water treatment can be performed even when the load of the water to be treated fluctuates drastically.
［多孔性物質再生試験］
　上記実施形態に係る多孔性物質再生装置に使用される多孔性物質を用い、以下の方法で多孔性物質の再生試験を行った。 [Porosity material regeneration test]
Using the porous substance used in the porous substance regenerating device according to the above embodiment, the regeneration test of the porous substance was carried out by the following method.
　（定温熱分析試験）
　多孔性物質としての活性炭に対し、被吸着物としてドデシルベンゼンスルホン酸ナトリウム（以下、「ＡＢＳ」と記載）及びポリエチレングリコール（分子量４０００、以下、「ＰＥＧ」と記載）が所定量吸着されたものを試験用のサンプルとして用いた。第１気体としては２０％水蒸気、８０％窒素の混合気体を用いた（水蒸気分圧２０．２ｋＰａ）。温度条件は、７０～８０℃付近の温度からそれぞれ以下の表１に示す所定温度まで１０℃／ｍｉｎの昇温速度で昇温し、それぞれ所定温度で合計２時間保持を行った。 (Constant temperature analysis test)
A predetermined amount of sodium dodecylbenzenesulfonate (hereinafter referred to as "ABS") and polyethylene glycol (molecular weight 4000, hereinafter referred to as "PEG") adsorbed on activated carbon as a porous substance as objects to be adsorbed. It was used as a test sample. As the first gas, a mixed gas of 20% water vapor and 80% nitrogen was used (water vapor partial pressure 20.2 kPa). As for the temperature conditions, the temperature was raised from a temperature near 70 to 80 ° C. to a predetermined temperature shown in Table 1 below at a heating rate of 10 ° C./min, and the temperature was maintained at the predetermined temperature for a total of 2 hours.
　上記定温熱分析試験において、活性炭の再生率Ｒを、脱着された被吸着物の重量を被吸着物の初期重量で除したものとして定義した。具体的には、以下の式（３）により活性炭の再生率Ｒを求めた。なお、ＡＢＳが吸着された活性炭には、ＡＢＳに含有される硫酸ナトリウムが残存するものと仮定して再生率Ｒを求めた。
　再生率Ｒ＝（Ｗｄｒｙ－Ｗｔ）／（Ｗｄｒｙ×Ａ／１００）×１００　　　（３）
　ここで、式中の記号は以下を示す。
　Ｒ　　　：処理時間ｔにおける再生率（％）
　Ｗｄｒｙ　：乾燥試料重量（ｍｇ）
　Ｗｔ　　：処理時間ｔにおける試料重量（ｍｇ）
　Ａ　　　：被吸着物の初期吸着率（ｗｔ％） In the above constant temperature analysis test, the regeneration rate R of activated carbon was defined as the weight of the desorbed adsorbed material divided by the initial weight of the adsorbed material. Specifically, the regeneration rate R of activated carbon was determined by the following formula (3). The regeneration rate R was determined on the assumption that sodium sulfate contained in ABS remained in the activated carbon on which ABS was adsorbed.
Regeneration rate R = (W dry- W t ) / (W dry x A / 100) x 100 (3)
Here, the symbols in the formula indicate the following.
R: Regeneration rate (%) at processing time t
W dry : Dry sample weight (mg)
W t : Sample weight (mg) at treatment time t
A: Initial adsorption rate (wt%) of the object to be adsorbed
　被吸着物がＡＢＳである活性炭の再生率Ｒを、以下表１及び図９に示す。被吸着物がＰＥＧである活性炭の再生率Ｒを、以下表２及び図１０に示す。 The regeneration rate R of activated carbon whose adsorbed material is ABS is shown in Table 1 and FIG. 9 below. The regeneration rate R of activated carbon in which the adsorbed material is PEG is shown in Table 2 and FIG. 10 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び図９を参照すると、ＡＢＳが吸着された活性炭は、４５０℃の条件で１２０分再生を行った場合の再生率Ｒが８３．５％である。５００℃の条件では１２０分後の再生率Ｒが１００％に達し、５５０℃の条件では３０分後に再生率Ｒが１００％に達した。従って、活性炭の再生時の温度をＡＢＳの沸点（約２０５℃）以上とした場合であっても、再生温度によっては活性炭を短時間で完全に再生することができない結果が示された。 With reference to Table 1 and FIG. 9, the activated carbon on which ABS is adsorbed has a regeneration rate R of 83.5% when regenerated for 120 minutes under the condition of 450 ° C. Under the condition of 500 ° C., the regeneration rate R reached 100% after 120 minutes, and under the condition of 550 ° C., the regeneration rate R reached 100% after 30 minutes. Therefore, even when the temperature at the time of regeneration of the activated carbon is set to the boiling point of ABS (about 205 ° C.) or higher, the result shows that the activated carbon cannot be completely regenerated in a short time depending on the regeneration temperature.
　表２及び図１０を参照すると、ＰＥＧが吸着されている活性炭は、３５０℃の条件で３０分再生を行った場合の再生率Ｒが８６．５％であり、６０分再生後の再生率Ｒが１００％である。４００℃の条件では５分後に再生率Ｒが１００％に達した。従って、表１及び図９との比較により、活性炭の被吸着物の種類によって好ましい再生温度が異なる結果が示された。 With reference to Table 2 and FIG. 10, the activated carbon on which PEG is adsorbed has a regeneration rate R of 86.5% when regenerated at 350 ° C. for 30 minutes, and a regeneration rate R after 60 minutes of regeneration. Is 100%. Under the condition of 400 ° C., the regeneration rate R reached 100% after 5 minutes. Therefore, by comparing with Table 1 and FIG. 9, it was shown that the preferable regeneration temperature differs depending on the type of the object to be adsorbed on the activated carbon.
　（昇温熱分析試験）
　多孔性物質として活性炭（石炭破砕炭、標準粒度８／３２メッシュ、比表面積９６５ｍ２／ｇ）を用い、水処理の実地使用を行って被吸着物が吸着された状態の上記活性炭を準備した。第１気体としては２０％水蒸気、８０％窒素の混合気体を用いた（水蒸気分圧２０．２ｋＰａ）。昇温条件は、７０～８０℃付近の温度から１０００℃まで１０℃／ｍｉｎの昇温速度で昇温した。結果を図１１に示す。 (Heat temperature analysis test)
Activated carbon (crushed coal, standard particle size 8/32 mesh, specific surface area 965 m 2 / g) was used as the porous material, and the above activated carbon in a state where the adsorbed material was adsorbed was prepared by practical use of water treatment. As the first gas, a mixed gas of 20% water vapor and 80% nitrogen was used (water vapor partial pressure 20.2 kPa). As for the temperature rising condition, the temperature was raised from a temperature of about 70 to 80 ° C. to 1000 ° C. at a temperature rising rate of 10 ° C./min. The results are shown in FIG.
　図１１は、上記昇温熱分析試験の結果を示すグラフである。図１１中、横軸は温度（℃）を示し、縦軸は重量（ｍｇ）を示す。図１１中、サンプルの温度変化が実線で示される。図１１に示すように、まず昇温開始直後の８０℃付近から１００℃付近の温度帯で重量減少が示された。これは、活性炭に含有される水分の蒸発に起因するものと考えられる。次に、温度Ｔ１において重量減少の開始が示された。これは、活性炭に吸着された被吸着物の蒸発及び分解のうち少なくともいずれかによる、被吸着物の脱着に起因すると考えられる。上記重量減少は、温度Ｔ２になるまで継続し、それ以降の重量変化は一定値を示した。これは、活性炭に吸着された被吸着物が全て脱着したことに起因すると考えられる。次に、温度Ｔ３において重量減少の開始が示された。これは、活性炭の賦活による分解に起因すると考えられる。 FIG. 11 is a graph showing the results of the above-mentioned temperature rise heat analysis test. In FIG. 11, the horizontal axis represents temperature (° C.) and the vertical axis represents weight (mg). In FIG. 11, the temperature change of the sample is shown by a solid line. As shown in FIG. 11, first, the weight loss was shown in the temperature range from about 80 ° C. to about 100 ° C. immediately after the start of temperature rise. This is considered to be due to the evaporation of water contained in the activated carbon. Next, the onset of weight loss was shown at temperature T1. It is considered that this is due to the desorption of the adsorbed material due to at least one of evaporation and decomposition of the adsorbed material adsorbed on the activated carbon. The weight reduction continued until the temperature reached T2, and the weight change thereafter showed a constant value. It is considered that this is due to the desorption of all the adsorbed substances adsorbed on the activated carbon. Next, the onset of weight loss was indicated at temperature T3. This is considered to be due to the decomposition of activated carbon due to activation.
　上記の分析結果より、活性炭の再生時の温度を、被吸着物が蒸発及び分解のうち少なくともいずれかを開始する温度であるＴ１以上の温度であり、活性炭が賦活による分解を開始する温度であるＴ３未満の温度とすることで、被吸着物の脱着が行われ、かつ活性炭が賦活により分解することなく活性炭を再生できることが確認された。 From the above analysis results, the temperature at the time of regeneration of the activated carbon is T1 or higher, which is the temperature at which the adsorbed substance starts at least one of evaporation and decomposition, and is the temperature at which the activated carbon starts decomposition by activation. It was confirmed that by setting the temperature to less than T3, the adsorbed material was desorbed and the activated carbon could be regenerated without being decomposed by activation.
　１、１ａ、１ｂ、１ｃ、１ｄ　　多孔性物質再生装置（水処理装置）
　１０、１０ａ　　　　　　　　　多孔性物質槽（吸着槽）
　１１、１１ａ、１１ｂ　　　　　加熱装置
　１２、１２ａ　　　　　　　　　燃焼装置
　１３、１３ａ　　　　　　　　　水蒸気発生装置
　１６、１６ａ　　　　　　　　　熱交換装置（加熱装置） 1,1a, 1b, 1c, 1d Porous substance regeneration device (water treatment device)
10, 10a Porous substance tank (adsorption tank)
11, 11a, 11b Heating device 12, 12a Combustion device 13, 13a Steam generator 16, 16a Heat exchange device (heating device)

Claims (10)

  1. 　被吸着物が吸着された多孔性物質を加熱して再生する多孔性物質再生装置であって、
    　前記多孔性物質が充填された多孔性物質槽と、
    　前記多孔性物質に接触するように前記多孔性物質槽に流通する第１気体を加熱する加熱装置と、
    　前記多孔性物質の再生時に脱着された前記被吸着物を燃焼させる燃焼装置と、を有し、
    　前記多孔性物質の再生時の温度は３００℃～８００℃の範囲内であり、
    　前記燃焼装置において前記被吸着物の燃焼時に発生する第２気体を用いて、前記多孔性物質を加熱する、多孔性物質再生装置。     A porous substance regenerating device that heats and regenerates a porous substance on which an adsorbed substance is adsorbed.
    A porous substance tank filled with the porous substance and
    A heating device that heats the first gas that flows through the porous substance tank so as to come into contact with the porous substance.
    It has a combustion device that burns the adsorbed substance that has been desorbed during regeneration of the porous substance.
    The regenerating temperature of the porous substance is in the range of 300 ° C. to 800 ° C.
    A porous substance regeneration device that heats the porous substance by using a second gas generated at the time of combustion of the object to be adsorbed in the combustion device.
  2. 　前記第２気体を、前記多孔性物質槽に流通させて前記多孔性物質を加熱する、請求項１に記載の多孔性物質再生装置。 The porous substance regenerating device according to claim 1, wherein the second gas is circulated in the porous substance tank to heat the porous substance.
  3. 　前記加熱装置は、前記第２気体と前記第１気体との間で熱交換を行う熱交換装置を含む、請求項１又は２に記載の多孔性物質再生装置。 The porous substance regenerating device according to claim 1 or 2, wherein the heating device includes a heat exchange device that exchanges heat between the second gas and the first gas.
  4. 　前記第１気体は、水蒸気を含み、水蒸気を発生させる水蒸気発生装置を有する、請求項１～３いずれかに記載の多孔性物質再生装置。 The porous substance regenerating device according to any one of claims 1 to 3, wherein the first gas contains water vapor and has a water vapor generator for generating water vapor.
  5. 　前記第２気体は、前記水蒸気発生装置において熱交換を行う、請求項４に記載の多孔性物質再生装置。 The porous substance regeneration device according to claim 4, wherein the second gas exchanges heat in the steam generator.
  6. 　前記燃焼装置には、前記被吸着物と共に燃焼される燃料が供給される、請求項１～５いずれかに記載の多孔性物質再生装置。 The porous substance regenerating device according to any one of claims 1 to 5, wherein fuel to be burned together with the adsorbed substance is supplied to the combustion device.
  7. 　前記多孔性物質は、活性炭である、請求項１～６いずれかに記載の多孔性物質再生装置。 The porous substance regenerating device according to any one of claims 1 to 6, wherein the porous substance is activated carbon.
  8. 　前記多孔性物質の再生時の温度は、前記多孔性物質に吸着された前記被吸着物が蒸発及び分解のうち少なくともいずれかを開始する温度以上の温度であり、かつ、前記多孔性物質が加熱により分解を開始する温度未満の温度である、請求項１～７いずれかに記載の多孔性物質再生装置。 The temperature at the time of regeneration of the porous substance is a temperature equal to or higher than the temperature at which the object to be adsorbed on the porous substance starts at least one of evaporation and decomposition, and the porous substance is heated. The porous substance regenerating apparatus according to any one of claims 1 to 7, wherein the temperature is lower than the temperature at which decomposition is started.
  9. 　前記多孔性物質に吸着された前記被吸着物が蒸発及び分解のうち少なくともいずれかを開始する温度と、前記多孔性物質が加熱により分解を開始する温度は、前記被吸着物が吸着された前記多孔性物質を熱重量分析し、前記被吸着物が吸着された前記多孔性物質が重量減少を開始する温度を測定することにより決定される、請求項８に記載の多孔性物質再生装置。 The temperature at which the adsorbed material adsorbed on the porous material starts at least one of evaporation and decomposition and the temperature at which the porous material starts decomposition by heating are the temperatures at which the adsorbed material is adsorbed. The porous material regenerating apparatus according to claim 8, which is determined by thermogravimetric analysis of the porous material and measuring the temperature at which the porous material on which the adsorbed object is adsorbed starts to lose weight.
  10. 　請求項１～９いずれかに記載の多孔性物質再生装置を備える水処理装置であり、
    　前記被吸着物が脱着された前記多孔性物質が充填された前記多孔性物質槽を、被処理水が流通可能な吸着層として用いる、水処理装置。     A water treatment device including the porous substance regenerating device according to any one of claims 1 to 9.
    A water treatment apparatus that uses the porous substance tank filled with the porous substance to which the substance to be adsorbed has been desorbed as an adsorption layer through which water to be treated can flow.
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