Carbon dioxide adsorption device

Abstract

To provide a carbon dioxide adsorption device that is targeted at a carbon dioxide adsorbent of which adsorption performance deteriorates due to repeated adsorption / desorption, supports again the adsorbent by using the a simple method for regeneration and can maintain the adsorption performance for a long period.SOLUTION: In a continuous type carbon dioxide adsorption device having a rotor that supports a carbon dioxide adsorbent, when performance of the adsorbent deteriorates, the adsorption performance of the carbon dioxide adsorbent is regenerated by using a method of immersing the rotor in a solution for supporting again, a method of dropping liquid droplets of the solution for supporting again to the rotor, a method of causing mist for supporting again and gas for supporting again to flow in the rotor, a method of putting the rotor in a closed mechanism and being filled with fumigated mist for supporting again and the gas for supporting again and other methods.SELECTED DRAWING: Figure 4

Description

[Technical field]

[0001] The present invention relates to a carbon dioxide adsorption device that uses a rotor carrying a carbon dioxide adsorbing material, and a method for recovering the performance of the carbon dioxide adsorbing material (hereinafter referred to as a "regeneration method"). [Background technology]

[0002] In recent years, there is a high need for air purification in many areas. For example, there is a need to remove carbon dioxide and maintain clean air in living spaces. There is also a need to supply highly concentrated carbon dioxide to vinyl greenhouses, plant factories, and the like. Furthermore, there is a high need for carbon neutral systems that separate and capture carbon dioxide in combustion exhaust gases released into the atmosphere and reduce carbon dioxide emissions. To meet these societal needs, there is a demand for devices that remove, separate, and capture carbon dioxide.

[0003] For example, Patent Document 1 discloses a carbon dioxide absorption type removal and concentration device that uses a honeycomb rotor holding a carbon dioxide adsorbent material with carbon dioxide absorption function, divides this rotor into at least an adsorption (treatment) zone and a desorption (regeneration) zone, passes air to be adsorbed (treated) through the adsorption zone to separate and remove carbon dioxide from the air to be adsorbed, passes air for desorption (regeneration) through the desorption zone to desorb carbon dioxide, and provides enthalpy (temperature and humidity) adjustment means for either or both of the air to be adsorbed and the desorption air to control the enthalpy difference between the air to be adsorbed and the desorption air, thereby controlling the carbon dioxide removal and concentration performance.

[0004] In such a carbon dioxide adsorption device, zeolite, silica gel, activated carbon, etc. are used as the carbon dioxide adsorbent. Also, adsorbents in which a polymer or ion exchange resin having an amino group, an inorganic alkaline compound, or an amine compound is supported on a porous carrier (alumina, zeolite, activated carbon, ion exchange resin, polymer adsorbent, silica gel, mesoporous silica, etc.) are used.

[0005] A carbon dioxide adsorbent (hereinafter referred to as a "carbonate-based adsorbent") in which a carbonate, particularly an alkali metal carbonate, such as potassium carbonate or sodium carbonate, among inorganic alkaline compounds such as carbonates and hydroxides of alkali metals or alkaline earth metals is supported on a porous carrier has high carbon dioxide adsorption properties, is extremely stable even at high temperatures, and can be thermally regenerated at 100 to 200° C. Patent Document 2 discloses a carbonate-based adsorbent in which at least one carbonate selected from the group consisting of potassium carbonate, potassium hydrogen carbonate, sodium carbonate, and sodium hydrogen carbonate is impregnated on at least one porous carrier selected from the group consisting of alumina, silica gel, and zeolite.

[0006] Carbon dioxide adsorbents (hereinafter referred to as "amine-based adsorbents"), which are made by supporting a polymer or ion exchange resin having amino groups, or an amine compound (such as triethanolamine or monoethanolamine) on a porous carrier, have high carbon dioxide adsorption properties and easily adsorb low concentrations of carbon dioxide in living spaces and the atmosphere at room temperature. In addition, the adsorbed carbon dioxide can be easily desorbed by heating at a relatively low temperature of 40 to 70°C.

[0007] However, this heating causes the amino groups that make up the amine-based adsorbent to be oxidized or eliminated. That is, during the bond-desorption reaction between carbon dioxide and amine (R-NH), the amino groups are oxidized by heating (e.g., radical mechanism) or eliminated (e.g., Hoffman elimination), forming carbamic acid (R-NH-COOH), which gradually fixes carbon dioxide. For this reason, carbon dioxide adsorbents that use amine-based adsorbents are easily deteriorated by oxidation over time when used for a long period of time, and the carbon dioxide adsorption performance decreases.

[0008] When using amine-based adsorbents as carbon dioxide adsorbents, the adsorbents must be replaced at regular intervals, which not only causes problems such as the shutdown of the equipment, but also incurs frequent costs for replacing the adsorbents.For this reason, highly durable adsorbents, methods for maintaining performance for long periods without replacing the adsorbents, and methods for regenerating the adsorbents (restoring performance) are being developed and studied.

[0009] Patent Document 3 discloses a carbon dioxide separation device that separates carbon dioxide in the air by alternately repeating adsorption and desorption of carbon dioxide using an adsorbent-packed tank filled with a carbon dioxide adsorbent. An amine recovery device and an amine aqueous solution preparation device are connected to an adsorbent-packed tank filled with a carbon dioxide adsorbent having diethanolamine as an amine compound supported on activated carbon as a porous carrier, and the amine compound evaporated from the carbon dioxide adsorbent during operation is recovered, and the amine compound is resupported on the porous carrier by impregnating the carbon dioxide adsorbent with the amine aqueous solution in a resupport process, and the porous carrier is dried, thereby recovering the reduced carbon dioxide adsorption capacity and maintaining the carbon dioxide adsorption capacity without replacing the adsorbent.

[0010] Furthermore, Patent Document 4 discloses an amine-based adsorbent that uses an amine compound with an innovative chemical structure to suppress deterioration over time and exhibit high durability even when used repeatedly in carbon dioxide adsorption treatments.

[0011] Furthermore, Patent Document 5 discloses an air conditioning system and an adsorbent regeneration method that use an adsorbent having a carbon dioxide adsorbent, perform a drying step after a desorption step, and desorb all or a part of the moisture adhering to the adsorbent by bringing a drying fluid into contact with the adsorbent from which carbon dioxide has been desorbed, thereby suppressing a decrease in the adsorption capacity of the adsorbent due to repeated adsorption and desorption of carbon dioxide. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] Patent No. 6713301 [Patent Document 2] Japanese Patent Application Publication No. 5-049918 [Patent Document 3] Patent No. 5571085 [Patent Document 4] Patent No. 7290381 [Patent Document 5] JP 2023-059419 A Summary of the Invention [Problem to be solved by the invention]

[0013] Regarding carbonate-based adsorbents, the inventors supported potassium carbonate, potassium bicarbonate, sodium carbonate, and sodium bicarbonate on alumina, fabricated honeycombs supporting the adsorbents, and repeatedly performed adsorption and desorption tests of 1000 ppm carbon dioxide. As a result, it was confirmed that the carbon dioxide adsorption performance gradually decreased for all of these carbonates. This is thought to be because carbonates generate by-products of carbonate and alumina, such as KAl(CO3)(OH)2, which require decomposition at high temperatures of about 300°C due to repeated adsorption and desorption of carbon dioxide and moisture, and remain without being thermally decomposed. In addition, when the porous support is silica gel, the amount of carbon dioxide adsorption varies or decreases depending on the support conditions. When the porous support is zeolite, the pores are small, so when carbonate is supported, the pores are blocked, and the amount of carbon dioxide adsorption is small. When the porous carrier is an activated carbon carrier, especially when preparing a honeycomb rotor, the rotor is impregnated with a slurry of the activated carbon carrier and binder, dried, and then impregnated with an aqueous carbonate solution, dried, and supported. However, activated carbon is hydrophobic, so it disperses poorly in water, and there are few binders that are compatible with activated carbon, making it difficult to support it on a honeycomb. Regardless of the type of porous carrier, by-products such as K4H2(CO3)3·1.5H2O and Na5H3(CO3)4 are generated from the carbonate itself and carbon dioxide and water, and these remain without being thermally decomposed, leading to a decrease in performance.

[0014] The carbon dioxide adsorbent used in Patent Document 3 is usually in the form of pellets or granules, and a packed tank filled with these is used. In order to reload the amine compound, additional devices and equipment such as an amine recovery device, an amine aqueous solution preparation device, and two packed tanks are required, which is costly. The amine aqueous solution is supplied to the packed tank, and the adsorbent is immersed in it to reload it, which is difficult to apply to a continuous carbon dioxide adsorption device having a rotor, which is the subject of the present invention.

[0015] In Example 1 of Cited Document 4, an amine-based adsorbent was supported on a filter portion having a honeycomb structure, and a durability test was conducted, and it was confirmed that the durability was improved compared to the conventional product, as shown in Figure 11. However, even so, the carbon dioxide adsorption performance was reduced after the durability test, and deterioration of the carbon dioxide adsorbent over time due to long-term use is inevitable.

[0016] In Patent Document 5, the temperature of the desorption (regeneration) fluid and the temperature inside the desorption area are particularly preferably 120 to 160°C, and the temperature of the drying fluid and the temperature inside the drying area are particularly preferably 80 to 160°C, and it is said that the higher the temperature of the drying fluid, the more advantageous it is, and it is effective when zeolite or silica gel is used as the adsorbent. However, when an amine-based adsorbent is used, the desorption temperature is relatively low at 40 to 70°C, which leads to deterioration of the amine-based adsorbent and therefore cannot be applied. In addition, when the drying fluid is sprayed onto the adsorbent, it is said that the more moisture is desorbed from the adsorbent, but in the case of amine-based adsorbents and carbonate-based adsorbents, the adsorption reaction of carbon dioxide proceeds in the presence of moisture, so if the adsorbent is dried too much, the carbon dioxide adsorption performance will decrease. Heating the desorption fluid and drying fluid to a high temperature as in Patent Document 5 also wastes energy.

[0017] As described above, carbon dioxide adsorbents such as carbonate-based adsorbents and amine-based adsorbents inevitably lose their adsorption performance when used repeatedly for adsorption and desorption over a long period of time. A rotor carrying such a carbon dioxide adsorbent must be replaced with a new one when performance declines due to aging, which requires frequent replacement and is costly.

[0018] Therefore, in order to maintain performance for a long period of time without replacing the rotor with a new one, it is considered effective to reload the carbon dioxide adsorbent on the rotor, as in Patent Document 3. However, no regeneration method by reloading the carbon dioxide adsorbent has been disclosed that targets a continuous carbon dioxide adsorption device having a rotor loaded with a carbon dioxide adsorbent.

[0019] In view of this situation, the main object of the present invention is to provide a carbon dioxide adsorption device that is capable of maintaining its carbon dioxide adsorption performance over a long period of time by, in a continuous carbon dioxide adsorption device having a rotor carrying a carbon dioxide adsorbent, targeting carbon dioxide adsorbents such as carbonate-based adsorbents and amine-based adsorbents, whose adsorption performance deteriorates due to repeated adsorption and desorption of carbon dioxide, when performance deteriorates due to aging, by a method of simply regenerating the carbon dioxide adsorption performance of the adsorbent without replacing the rotor with a new one, or a method of simply regenerating the adsorbent while the device is operating. [Means for solving the problem]

[0020] In order to solve the above-mentioned problems, the present invention relates to a continuous carbon dioxide adsorption device having a rotor supported on a carbon dioxide adsorbent, and targets carbon dioxide adsorbents such as carbonate-based adsorbents and amine-based adsorbents whose adsorption performance deteriorates due to repeated adsorption and desorption of carbon dioxide.When performance deterioration occurs due to deterioration over time, the carbon dioxide adsorption device regenerates the adsorbent (restores the performance of the adsorbent) by using a method of simply re-supporting the carbon dioxide adsorbent, thereby enabling the carbon dioxide adsorption performance to be maintained over the long term.

[0021] Methods for regenerating the adsorbent by shutting down the apparatus and removing the rotor include impregnation reloading method, dropwise reloading method, flow reloading method, and fumigation reloading method.

[0022] Methods for regenerating the adsorbent after the device is stopped and the rotor is still mounted on the device include the drop reloading method, the flow reloading method, and the fumigation reloading method.

[0023] Further, methods for regenerating the adsorbent while the apparatus is in operation include a dropwise reloading method and a flow reloading method. Effect of the Invention

[0024] When the carbon dioxide adsorbent deteriorates due to repeated adsorption and desorption of carbon dioxide, and its carbon dioxide adsorption performance drops, the carbon dioxide adsorption performance of the adsorbent can be restored by reloading the carbon dioxide adsorbent in a simple manner, so there is no need to replace the rotor with a new one, which can significantly reduce costs. In addition, the amount of rotor waste is reduced, which is also environmentally friendly.

[0025] The adsorbent regeneration method performed while the apparatus is stopped and the rotor is mounted on the apparatus, and the adsorbent regeneration method performed while the apparatus is in operation, allow for a simple method of reloading the adsorbent when the rotor is heavy and difficult to remove. The adsorbent regeneration method performed while the apparatus is in operation saves the trouble of removing the rotor and reloading it, and does not cause problems such as stopping the operation of the apparatus. In addition, it is possible to maintain carbon dioxide adsorption performance over a long period of time while continuously operating the rotor to restore performance.

[0026] In addition to carbon dioxide, gases to be adsorbed, such as the air in living spaces and exhaust gases, contain volatile organic compounds (VOCs) and trace amounts of SOx, NOx, etc., and when these are attached to the surface of the adsorbent, the carbon dioxide adsorption performance of the adsorbent decreases. The method for regenerating a carbon dioxide adsorbent of the present invention makes it possible to easily recover the reduced carbon dioxide adsorption performance.

[0027] Because the present invention is a continuous carbon dioxide adsorption apparatus having a rotor, there is no need to provide large-scale equipment such as an amine recovery apparatus, an amine aqueous solution preparation apparatus, and two adsorbent filling tanks as in Patent Document 3, making the apparatus itself compact and leading to cost reduction. [Brief description of the drawings]

[0028] [Figure 1] FIG. 1 shows an example of a carbon dioxide adsorption device (disk rotor) of the present invention. [Diagram 2] FIG. 2 shows an example of the carbon dioxide adsorption device (cylindrical rotor) of the present invention. [Diagram 3]FIG. 3 is a diagram showing a method for producing the carbon dioxide adsorbing material used in the carbon dioxide adsorbing device of the present invention. [Figure 4] FIG. 4 is a diagram showing the impregnation reloading method according to the first embodiment of the present invention. [Diagram 5] FIG. 5 shows a comparison of the carbon dioxide adsorption / desorption performance after deterioration and after reloading, with the carbon dioxide adsorption / desorption performance of a new rotor set at 100, in the rotor reloaded by the impregnation reloading method according to Example 1 of the present invention. [Figure 6] FIG. 6 is a diagram showing a dropping reloading method according to a second embodiment of the present invention. [Figure 7] FIG. 7 is a diagram showing a flow reloading method according to a third embodiment of the present invention. [Figure 8] FIG. 8 is a diagram showing a fumigation reloading method according to Example 4 of the present invention. [Figure 9] FIG. 9 shows an example of the chamber of the carbon dioxide adsorption device of the present invention. [Figure 10] FIG. 10 is a diagram showing a case where a reloading zone is provided after the desorption zone in the carbon dioxide adsorption device of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] In the present invention, the term "rotor" refers to a honeycomb rotor in which a carbon dioxide adsorbent is embedded and / or supported on a substrate formed in a honeycomb shape, and a packed rotor in which a container is filled with pellet-shaped or granular adsorbent. The subject of the present invention is a carbon dioxide adsorption device (continuous carbon dioxide adsorption device) that continuously adsorbs and desorbs carbon dioxide by rotating the rotor and / or rotating a duct device connected to the rotor. The subject of the present invention is a carbon dioxide adsorbent such as a carbonate-based adsorbent or an amine-based adsorbent, whose adsorption performance decreases due to repeated adsorption and desorption of carbon dioxide, but whose carbon dioxide adsorption performance can be regenerated (recovered) by reloading. Note that the present invention is not limited to the following embodiments.

[0030] 1 and 2 are an example of the carbon dioxide adsorption device of the present invention. Hereinafter, the rotor will be described as a honeycomb rotor. As the form of the honeycomb rotor of the present invention, a honeycomb is wound into a cylindrical shape as shown in FIG. 1(A) to form a disk-shaped rotor 1, or as shown in FIG. 1(B) to form a disk-shaped rotor 1 by assembling the honeycomb into a sector-shaped block 8, and gas is ventilated in the axial direction. Alternatively, as shown in FIG. 2, the honeycomb may be made into a sector-shaped block 8, which is set in a cylindrical frame and assembled into a cylindrical rotor 1, and gas may be ventilated in the radial direction from the outer periphery to the inner periphery. In either case, the honeycomb rotor 1 is installed in an apparatus divided and sealed into at least an adsorption zone 2 and a desorption zone 3, and the rotor and / or duct device are continuously rotated. In the case of a packed rotor, a breathable material such as a mesh or net is used for the ventilation surface, and the end faces of the honeycomb rotors in FIG. 1 and FIG. 2 are the ventilation surfaces.

[0031] In FIG. 1(A), 1 is a honeycomb rotor, which is made by corrugating inorganic and / or non-combustible sheets such as ceramic fiber paper and glass fiber paper, metal sheets, plastic sheets, heat-resistant fiber nonwoven fabrics, etc., and laminating them into a block shape or winding them into a cylindrical (rotor) shape to form a filter section. The cross-sectional shape of the honeycomb in the filter section is not limited to a corrugated shape like the cross-section of cardboard, but may be any shape such as a triangle, trapezoid, or hexagon, as long as it does not cause a problem in allowing gas to pass through. Honeycombs have the advantage that they have a large contact area, low pressure loss, and are lightweight yet strong, making them easy to make large. In FIG. 1(B) or FIG. 2, the honeycomb is used as block 8 to assemble the rotor, so they are processed appropriately so that gas can pass through the honeycomb end faces.

[0032] The honeycomb rotor 1 supports carbon dioxide adsorbents such as carbonate-based adsorbents and amine-based adsorbents. As shown in FIG. 3(A), in the case of an adsorbent using a porous carrier 31, examples of the porous carrier 31 include alumina, zeolite, activated carbon, ion exchange resin, polymer adsorbent, silica gel, and mesoporous silica. The carbon dioxide adsorbent 32 is supported on the porous carrier 31 by spraying, immersion, coating, impregnation, evaporation to dryness, or other adhesion. The porous carrier 31 has many pores 31a on its surface. As shown in FIG. 3(B), the carbon dioxide adsorbent 32 such as carbonates and amine compounds penetrates not only the surface of the porous carrier 31 but also the pores 31a, so that a large amount of the carbon dioxide adsorbent 32 can be supported. Examples of the amine compounds include polyethyleneimine, monoethanolamine, diethanolamine, and triethanolamine. Among these, monoethanolamine and diethanolamine are preferable because they can desorb carbon dioxide by heating at a relatively low temperature and the desorbed amine can be easily recovered.

[0033] When a styrene-based gel resin carrying primary or secondary amines is used as an adsorbent as an ion exchange resin having amino groups, or when a carbonate-based adsorbent is used, the price is lower than other carbon dioxide adsorbents. Note that carbon dioxide adsorbents other than carbonate-based and amine-based adsorbents may also be used.

[0034] When the carbon dioxide adsorbent is supported on the honeycomb rotor, the carbon dioxide adsorbent is made into a solution, impregnated into the honeycomb rotor, and dried. A binder may be mixed into the solution. The number and time of impregnation and drying may be appropriately determined in consideration of the concentration of the solution, the amount of adsorbent supported, etc., and may be one time, or may be repeated multiple times until a predetermined amount is supported. In addition, the carbon dioxide adsorbent may be made into a solution and sprayed onto the honeycomb rotor by spraying, or may be supported by evaporating to dryness or coating. In this way, as shown in FIG. 3(C), a honeycomb rotor equipped with a filter portion 33 supporting the carbon dioxide adsorbent 32 is formed.

[0035] The honeycomb rotor 1 is divided into an adsorption zone 2 and a desorption zone 3. A gas to be adsorbed, such as indoor air or atmospheric air in a living space, is supplied to the adsorption zone 2 by a blower or the like (not shown as it is a general type).

[0036] The gas to be adsorbed is passed through a temperature regulator 4 and a humidity regulator 5 to adjust its temperature and humidity, and then ventilated into the adsorption zone 2, whereby the carbon dioxide contained in the gas to be adsorbed is adsorbed by the adsorbent in the rotor 1 and separated and removed from the gas to be adsorbed, thereby reducing the concentration of carbon dioxide.

[0037] In the desorption zone 3, the desorption gas heated by the temperature regulator 6 is passed through a humidity regulator 7 to adjust the temperature and humidity, and then ventilated into the desorption zone 3 to desorb the carbon dioxide adsorbed on the rotor 1 into the desorption gas, thereby regenerating the adsorbent of the rotor 1. The desorption temperature is, for example, 40 to 70°C for an amine-based adsorbent and 100 to 200°C for a carbonate-based adsorbent.

[0038] Although the temperature regulators 4, 6 and humidity regulators 5, 7 are provided in both the adsorption zone 2 and the desorption zone 3 to control the temperature and humidity, the present invention is not limited to this and may be provided in only one of the zones. The order of the temperature regulators 4, 6 and the humidity regulators 5, 7 may be reversed, and furthermore, only one of them may be provided to regulate the humidity or temperature alone. As the temperature regulators 4, 6, a cooling coil, a heating coil, a Peltier element, an electric heater, a steam heater, a condenser of a heat pump, an evaporator, or the like is used. As the humidity regulators 5, 7, a method is used in which moisture in the gas is condensed and removed by cooling with a cooling coil or an evaporator of a heat pump, and the gas is humidified to the desired humidity level as necessary with a humidifier. As the humidifier, various types such as a water heating type, an evaporation type, a water spray type, and an ultrasonic type are used, and condensed water generated in the evaporator of a heat pump may be used. When humidity control by the humidifier is not required, temperature and humidity control is performed only by condensing and removing moisture using a cooling coil or the like.

[0039] Saturated water vapor or a mixture of saturated water vapor and heated air may be introduced as the desorption gas. The water vapor introduced into the desorption zone 3 is cooled and condensed by heating the honeycomb and supplying the heat for desorption of carbon dioxide, and condenses on the honeycomb and the surface of the adsorbent. The heat of condensation raises the temperature of the adsorbent, and carbon dioxide is desorbed and released. The surface of the adsorbent is rotated and transferred to the adsorption zone 2 while still wet with water from the water vapor condensed in the desorption zone 3. When the gas to be adsorbed passes through the adsorption zone 2, the cooling of the honeycomb and the adsorbent is promoted by the vaporization cooling phenomenon of water, and the heat of adsorption of carbon dioxide is converted into the latent heat of vaporization of water and removed, thereby achieving the effect of adsorbing carbon dioxide with high efficiency. The enthalpy of water vapor is much larger than that of the atmosphere and carbon dioxide at the same temperature, so the large amount of heat possessed by the water vapor can be condensed and used for desorption of carbon dioxide. This reduces the flow rate of the desorption gas supplied to desorb carbon dioxide, and the area of ​​the desorption zone can be reduced. It also becomes possible to reduce the size of the rotor, blower, etc., which leads to reductions in power costs and initial costs. In the case of an amine-based adsorbent, the use of water vapor as the desorption gas suppresses the amine evaporation rate, which is proportional to the gas flow rate, and reduces the frequency of reloading, resulting in a more stable carbon dioxide adsorption device.

[0040] Since the heat of condensation of water vapor is almost constant regardless of temperature, in the case of an amine-based adsorbent in particular, desorption is possible even at low temperatures, for example, at 40 to 50° C. This has the effect of maintaining carbon dioxide adsorption performance even when desorbed at low temperatures, reducing thermal deterioration of the amine-based adsorbent, and enabling a longer life for the rotor.

[0041] In the carbon dioxide adsorption device described above, when carbon dioxide adsorbents such as carbonate-based adsorbents and amine-based adsorbents are used for a long period of time, the adsorbents easily deteriorate due to changes in quality and oxidation over time, and the carbon dioxide adsorption performance decreases. Therefore, the carbon dioxide adsorption performance can be restored by reloading the carbon dioxide adsorbent using the following method. There are two types of adsorbent regeneration methods: a regeneration method performed with the device stopped ((A) when the rotor is removed, and (B) when the rotor is installed in the device), and a regeneration method performed while the device is operating ((C) temporary regeneration method, and (D) continuous regeneration method).

[0042] (Method of regenerating adsorbent by shutting down the device) (A) When removing the rotor This section describes a regeneration method for recovering the carbon dioxide adsorption performance of the rotor by stopping the apparatus, removing the rotor, and reloading the carbon dioxide adsorbent. This method can be applied to cases where the rotor can be removed from the apparatus, such as a small and lightweight rotor. EXAMPLES

[0043] ((A)-1) Impregnation and reloading method For example, if the rotor is small and can be removed from the carbon dioxide adsorption device, remove the rotor from the device. If the carbon dioxide adsorbent supported on the rotor is a carbonate-based adsorbent or an amine-based adsorbent, the amine or carbonate (hereinafter referred to as "eluted components") is water-soluble, so the rotor is first immersed in water to dissolve and remove the eluted components that were supported (water washing process). In the case of a honeycomb rotor, the filter part does not fall apart even when immersed in water. The water washing process dissolves the eluted components into water. In the case of a honeycomb rotor using a porous carrier, the porous carrier is firmly supported on the honeycomb by the binder, so the porous carrier itself does not detach or dissolve, and only the eluted components are removed. The degree and amount of eluted components may be measured by measuring the pH of the immersed water or by drying and weighing. The number of water washes and the immersion time are appropriately determined depending on the degree and amount of eluted components. The water washing process is not limited to water, and other liquids may be used as long as they can remove target components such as eluted components. The water washing step is not essential, and the water washing step may be omitted and the process may start with the impregnation step described below. Also, the water washing step is preferably carried out first, but is not limited thereto.

[0044] Next, as shown in FIG. 4, the rotor is impregnated with the carbon dioxide adsorbent in a solution form (hereinafter referred to as the "reloading solution") (impregnation step). The reloading solution may be a mixture of the adsorbent and binder, or a carbonate aqueous solution or an amine aqueous solution. The reloading solution attached to the rotor is dried (drying step) to complete the reloading. The number and time of the impregnation step and the drying step may be appropriately determined in consideration of the concentration of the reloading solution, the amount of adsorbent supported, etc., and may be one time or may be performed multiple times by alternating the impregnation step and the drying step. The drying is performed, for example, by blowing heated air through the rotor, but natural drying may also be used, and is not limited to this. The reloading solution is not limited to one using water, and may be a liquid in which the adsorbent is diluted with a volatile liquid.

[0045] If there is a frame or container (hereinafter referred to as "outer frame") for storing the rotor, the rotor is immersed together with the outer frame in the reloading solution, so there is a risk that the outer frame will be corroded by the reloading solution. In this case, the outer frame is masked with anticorrosive / waterproof tape or sheet, etc. If the corroding effect of the reloading solution on the outer frame is small, it is also possible to remove the reloading solution adhering to the outer frame by washing or wiping the outer frame with water after impregnation without masking.

[0046] The impregnation reloading method is more effective than the dropwise reloading method and flow-through reloading method described below when it is desired to reload the adsorbent reliably and uniformly in the thickness direction of the rotor.

[0047] A honeycomb rotor 1 carrying an amine-based adsorbent was manufactured. This honeycomb rotor 1 was mounted on a carbon dioxide adsorption device shown in FIG. 1(A), and a durability test was performed by continuously operating the carbon dioxide adsorption device for 4500 hours at a desorption temperature of 45°C. The temperature, absolute humidity, and carbon dioxide concentration at the inlet of the adsorption zone, and the absolute humidity and carbon dioxide concentration at the inlet of the desorption zone were set to room conditions. After 4500 hours, the honeycomb rotor 1 was removed from the device, washed with water, impregnated with an amine-based reloading solution, dried, and reloaded by the impregnation reloading method. The amount of the amine compound loaded was the same as that of a new product (immediately after the honeycomb rotor was manufactured). Figure 5 shows a comparison of the carbon dioxide adsorption and desorption performance after deterioration (after a 4500-hour durability test) and after reloading by the impregnation loading method, with the carbon dioxide adsorption and desorption performance of a new product taken as 100. It can be seen that the carbon dioxide adsorption performance of the honeycomb rotor after reloading was restored to the same level as that of a new product.

[0048] When the rotor is removed and the carbon dioxide adsorbent is reloaded, methods for simply reloading the adsorbent by impregnation without contacting the outer frame of the rotor with a reloading solution include a dropwise reloading method and a flow-through reloading method. EXAMPLES

[0049] ((A)-2 Drop reloading method) As shown in Figure 6, droplets of the reloading solution are dripped onto the end faces of the removed rotor by showering or the like (dropping process). The droplets of the reloading solution attached to the rotor are then dried (drying process) to complete the reloading. In the drop reloading method, when both ends of the rotor are in an up-down position as shown in Figure 6, it is preferable to drip the solution from the upper end face, as the droplets will penetrate downwards under their own weight.

[0050] A honeycomb rotor 1 carrying a carbonate-based adsorbent (alumina as a porous carrier, NaHCO3 as a carbonate) was produced. This honeycomb rotor 1 was mounted on a carbon dioxide adsorption device shown in Figure 1 (A), and a dynamic performance test of carbon dioxide adsorption was carried out under the following conditions. The device was operated and stopped intermittently until 1400 hours had passed since the honeycomb rotor was produced. After 1400 hours had passed, the honeycomb rotor 1 was removed from the device, washed with water, and a NaHCO3 aqueous solution was dripped onto it with a dropper, and reloading was carried out by the drip reloading method. The initial NaHCO3 loading rate (the ratio of NaHCO3 loading weight to the total weight of the honeycomb rotor (excluding the outer frame)) was 20%, and after reloading it was 39%, which was about double. Table 1 shows the carbon dioxide adsorption amount [ppm] in the dynamic performance test of each honeycomb rotor immediately after the honeycomb rotor was produced (initial), 1400 hours after production, and after reloading. The rotor speed was set to 50 rph in all cases. Adsorption zone inlet: Temperature 25°C, absolute humidity 10g / kg (DA), carbon dioxide concentration 1000ppm Desorption zone entrance: Temperature 120°C, absolute humidity 10g / kg (DA), carbon dioxide concentration 1000ppm

[0051] [Table 1]

[0052] As shown in Table 1, after 1,400 hours, the carbon dioxide adsorption performance had fallen to about half of the initial level. This is partly due to the difference in NaHCO3 loading rate between the initial period and after reloading, and the shift in the optimal rotation speed of the honeycomb rotor, but it can be seen that the carbon dioxide adsorption performance was restored by reloading NaHCO3. EXAMPLES

[0053] ((A)-3 Distribution Repossession Act) The reloading mist and / or reloading gas is circulated over the rotor end surface by a spray (FIG. 7(A)) or a blower (FIG. 7(B)) (flow process). Thereafter, the reloading mist and / or reloading gas attached to the rotor is dried (drying process) to complete the reloading. In the flow reloading method, the rotor can be loaded with both end surfaces facing up and down or left and right, but the state in which both end surfaces of the rotor are facing up and down as shown in FIGS. 7(A) and (B) is preferable because the reloading mist and reloading gas that have penetrated into the rotor move downwards by their own weight.

[0054] When reloading is performed using a mist for reloading, for example, the reloading solution is sprayed into mist and circulated through the rotor. When reloading is performed using a gas for reloading, for example, the gas for reloading may be supplied from a cylinder, or the vapor of the reloading solution may be supplied on the gas stream by a blower or the like to circulate through the rotor. For example, when an amine aqueous solution is used, the amine aqueous solution is placed in a sealed container, and the vapor of the amine is mixed with air and circulated through the rotor. The gas for reloading is preferably in a state containing moisture, that is, it is preferably given a certain degree of humidity, for example, a relative humidity within the range of 30 to 70% RH. The reloading reaction hardly progresses with a dry gas, and conversely, if a gas with too high humidity is used, it takes time to dry. When water vapor is not used as the gas for reloading, that is, when the solvent of the reloading solution is a volatile liquid, it is preferable that the partial pressure of the solvent for the gas for reloading is within the range of 30 to 70%. When the carbon dioxide adsorbent is an ion exchange resin, the carbon dioxide adsorption performance can be restored by passing a basic gas such as ammonia as a reloading gas. In the case of an ion exchange resin, if the reloading gas has a certain degree of humidity, the resin is easily ionized, and the carbon dioxide adsorption performance is easily restored.

[0055] The dropwise reloading method and the flow-through reloading method are similar, but differ in that the dropwise reloading method uses droplets of the reloading solution, whereas the flow-through reloading method uses a mist or gas.

[0056] In order to reduce uneven loading in the thickness direction of the rotor, the pressure may be reduced by suction from the end face opposite to the end face through which the impregnation, dripping, or flow takes place, or the solution, droplets, mist, or gas may be pushed out in the thickness direction of the rotor by ventilation or pressurization from the end face through which the impregnation, dripping, or flow takes place. EXAMPLES

[0057] ((A)-4) Fumigation and reloading method As shown in Fig. 8, the removed rotor is sealed in a sealed mechanism such as a sealed container, and the sealed mechanism is filled with reloading mist and / or reloading gas by fumigation (fumigation process). Thereafter, the reloading mist and / or reloading gas attached to the rotor is dried (drying process), and reloading is completed. Both end faces of the rotor can be supported in either a top-bottom or left-right state, but when both end faces are top-bottom, it is preferable to float the lower end face side of the rotor so that it can easily come into contact with the reloading mist or reloading gas, or to use a breathable material such as a net or net to facilitate ventilation. The reloading mist or reloading gas may be vigorously vaporized in the sealed mechanism in a short time by a fumigation method, or may be supplied to the sealed mechanism in a manner similar to the above-mentioned flow reloading method, and then sealed to fill the mechanism.

[0058] The flow reloading method and the fumigation reloading method are similar in that they both use a reloading mist or a reloading gas. However, the flow reloading method differs in that the mist or gas is circulated around the rotor by using a spray or blower and brought into contact with the rotor, whereas the fumigation reloading method fumigates the inside of a sealed mechanism, filling it with the mist or gas, and brings it into contact with the rotor.

[0059] The number of times and the time of the dropping step, the flowing step, or the fumigation step, and the drying step may be appropriately determined in consideration of the concentration and the amount of the reloading solution, the reloading mist, or the reloading gas, and may be one time, or the dropping step, the flowing step, the fumigation step, and the drying step may be alternately repeated several times, or these may be combined. In the dropping step, the flowing step, or the fumigation step, the outer frame of the rotor may be corroded by the reloading solution, the reloading mist, or the reloading gas. In this case, the outer frame may be masked with anticorrosive / waterproof tape or sheet. In the dropping step or the flowing step, a guard may be provided around the rotor to protect the outer frame so that the reloading solution, the reloading mist, or the reloading gas contacts only the end face of the rotor.

[0060] In the above-mentioned drop reloading method (Example 2), flow reloading method (Example 3), and fumigation reloading method (Example 4), a water washing step may be performed first, or the water washing step may be omitted when reloading. The water washing step may be performed by dropping water onto the rotor as droplets, instead of immersing the rotor in water. Here, a method in which water is circulated or fumigated as a mist or water vapor for the water washing step has a small effect of dissolving eluted components and is not practical.

[0061] (Method of regenerating adsorbent by shutting down the equipment) (B) When the rotor is mounted on the device This section describes a regeneration method for recovering the carbon dioxide adsorption performance of the rotor by stopping the apparatus and reloading the carbon dioxide adsorbent while the rotor is still mounted in the apparatus without being removed. This method can be applied when the rotor is difficult to remove from the apparatus, for example, in the case of a large and heavy rotor. EXAMPLES

[0062] ((B)-1 Drop reloading method) As shown in FIG. 9, at both end faces of the rotor 1 (the inlet and outlet sides of the adsorption zone and the desorption zone), the rotor 1 is sandwiched by members (hereinafter referred to as "chambers") that divide and form the zones and connect to the duct device, and the portion where the rotor 1 comes into contact with the chamber 9 by rotating and sliding is sealed, forming an airtight structure. That is, two chambers 9 exist in a pair, sandwiching the rotor 1. Therefore, a mechanism for dripping droplets, such as showering, is provided in advance in the chamber or duct device at the inlet and / or outlet side of the adsorption zone and / or desorption zone, and droplets of the reloading solution are dripped (dropping step). Alternatively, a port may be provided appropriately at the inlet and / or outlet side of the adsorption zone and / or desorption zone, and a nozzle or the like may be inserted from this port as necessary to drip by showering or the like. Thereafter, the droplets of the reloading solution attached to the rotor are dried (drying step), and the reloading is completed. When both end faces of the rotor are in an up-down state, it is preferable to drip the liquid from the upper end face, since the liquid will penetrate downwards due to its own weight.

[0063] The re-supporting solution that has permeated the rotor seeps out from the end face of the rotor on the opposite side. The seeped re-supporting solution is discharged through a drain or collected and reused. If it is reused, a circulation device may be provided to circulate the solution and drip it again from the end face where it dripped. EXAMPLES

[0064] ((B)-2 Distribution Repossession Act) A mechanism for distributing mist or gas, such as a spray or blower, is provided in advance in the chamber or duct device on the inlet and / or outlet side of the adsorption zone and / or desorption zone, and the mist and / or gas for reloading are distributed (distribution step). Alternatively, a port may be provided appropriately on the inlet and / or outlet side of the adsorption zone and / or desorption zone, and a nozzle or the like may be inserted from this port as necessary to distribute the mist and / or gas for reloading that have adhered to the rotor is then dried (drying step), completing the reloading. This method allows reloading with both end faces of the rotor in either the up-down or left-right state. When both end faces are in the up-down state, the mist and gas for reloading that have permeated into the rotor move downwards by their own weight, which is preferable. A blower or the like of a device that supplies the gas to be adsorbed and / or the gas for desorption may be used to distribute the gas.

[0065] The reloading mist and reloading gas that have passed through the rotor are discharged from the chamber on the opposite side or are recovered and reused. When reused, they may be circulated again from the end face through which they flow. Since the reloading mist and reloading gas may turn into droplets when penetrating into the rotor, a drain may be provided.

[0066] In the drop reloading method (Example 5) and the flow reloading method (Example 6), the rotor cannot be removed, but in an apparatus in which the chamber can be removed, if both chambers can be removed, reloading may be performed in the same manner as in the drop reloading method (Example 2) or flow reloading method (Example 3) in which the rotor is removed (A). If only one chamber can be removed, the reloading solution is dropped from the end face from which the chamber is removed, or the reloading mist or reloading gas is circulated. At this time, the end face having the chamber is designed to receive the reloading solution that has seeped out, or the reloading mist or reloading gas that has passed through the rotor. In this case, in an apparatus in which both end faces of the rotor are mounted in a top-bottom state, it is preferable to make the upper chamber removable. EXAMPLES

[0067] ((B)-3) Fumigation and reloading method Taking advantage of the fact that the rotor and the chamber have a sealed structure, the reloading mist and / or the reloading gas is fumigated to fill the rotor, the chamber, and the duct device (sealing mechanism) (fumigation process). Thereafter, the reloading mist and / or the reloading gas attached to the rotor is dried (drying process), and the reloading is completed. An air volume control device such as a valve may be provided in the duct portion, and the air volume control device may be closed during the fumigation process to prevent the mist and gas from leaking. In this method, even if the chamber is a removable device, the chamber is not removed in order to maintain the airtightness. The fumigation process may be performed by first circulating the reloading mist and the reloading gas from one of the chambers or duct devices, and then closing the air volume control device to seal the device.

[0068] In the above-mentioned drop reloading method (Example 5), flow reloading method (Example 6), and fumigation reloading method (Example 7), the parts of the device such as the chamber and seal need to be waterproofed and anticorrosive, but when the rotor is heavy and difficult to remove, reloading can be performed by a simple method. In addition, although it depends on whether the chamber is removed, the outer frame does not directly come into contact with the reloading solution, reloading mist, or reloading gas compared to the method of removing the rotor and performing reloading. In the reloading methods of Examples 5 to 7, since the device is stopped, it is preferable to perform reloading in all zones such as the adsorption zone and the desorption zone. Note that, although it is described as the case where the device is stopped, if the rotor and / or the duct device can be rotated, for example, reloading can be performed without removing the chamber, reloading can also be performed while rotating. In this case, the reloading solution, reloading mist, or reloading gas may be dropped or circulated in one of the zones such as the adsorption zone and the desorption zone.

[0069] In the reloading methods of Examples 5 to 7, the drying step may be natural drying, or may be performed by operating a blower or the like of a device for supplying the gas to be adsorbed and / or the desorption gas after reloading, or the temperature adjustment devices 4, 6, or humidity adjustment devices 5, 7. In this case, the drying may be performed by passing the gas through the adsorption zone and / or desorption zone while rotating the rotor and / or duct device by operating the device, but is not limited thereto.

[0070] The number of times and the time of the dropping step, the flowing step, or the fumigation step, and the drying step may be set to an appropriate number of times in consideration of the concentration and the supported amount of the resupporting solution, the resupporting mist, or the resupporting gas, and may be performed once, or the dropping step, the flowing step, or the fumigation step, and the drying step may be performed multiple times by alternately repeating them.

[0071] (Method of regenerating adsorbent while the equipment is in operation) A regeneration method is described below in which the rotor is mounted on an apparatus and the carbon dioxide adsorbent is reloaded while the apparatus is in operation, thereby recovering the carbon dioxide adsorption performance of the rotor. This method can be applied when the rotor is difficult to remove from the apparatus, such as a large and heavy rotor, and the apparatus needs to be operated continuously. Depending on the application and purpose, a temporary regeneration method (C) in which the carbon dioxide adsorbent is temporarily reloaded when its performance deteriorates, and a constant regeneration method (D) in which the carbon dioxide adsorbent is constantly reloaded while the apparatus is in operation are used. However, the constant regeneration method (D) is not practical because the carbon dioxide adsorbent is constantly supplied, which increases the amount of carbon dioxide adsorbent used and is costly. Therefore, the temporary regeneration method (C) is basically used to reload the carbon dioxide adsorbent when its performance deteriorates.

[0072] (Reloading Zone) 10, a reloading zone 10 is provided after the desorption zone 3, and the performance of the carbon dioxide adsorbent is restored by dropping or circulating droplets of a reloading solution, a mist for reloading, or a gas for reloading in the reloading zone 10. The direction of the droplets, mist, or gas dropped or circulated in the reloading zone 10 may be the same as the gas to be adsorbed or the desorption gas, or may be the opposite direction, and is determined appropriately. EXAMPLES

[0073] ((C)-1 Drop reloading method) A mechanism capable of dripping droplets, such as showering, is provided in advance in the chamber or duct device of the reloading zone 10, and droplets of the reloading solution are dripped (dropping step). Alternatively, a suitable port may be provided on the inlet side of the reloading zone 10, and a nozzle or the like may be inserted from this port as necessary to drip the solution by showering or the like.

[0074] When the reloading zone 10 is not provided, a mechanism capable of dripping droplets, such as showering, is provided in advance in a chamber or duct device on the inlet and / or outlet side of the adsorption zone 2 and / or desorption zone 3, and droplets of the reloading solution are dripped (dropping step). Alternatively, an appropriate port may be provided on the inlet and / or outlet side of the adsorption zone 2 and / or desorption zone 3, and a nozzle or the like may be inserted from this port as necessary to drip the solution by showering or the like.

[0075] When both ends of the rotor are in an up-down state, when droplets are dropped from the upper end, the reloading solution falls from the lower end under its own weight and can be discharged as it is as a drain or recovered and reused. If it is reused, a circulation device may be provided to circulate the solution so that it is dropped again from the end where it was dropped.

[0076] The dropwise reloading method is preferably used as the (C) temporary regeneration method, in which reloading is performed temporarily when the performance of the carbon dioxide adsorbent deteriorates. In the (C) temporary regeneration method, when reloading is not performed, the reloading zone 10 can function as a cooling zone. In the (D) constant regeneration method, in which reloading is performed constantly, the carbon dioxide adsorbent must be constantly supplied, which increases the amount of adsorbent used and is costly. In addition, the rotor is constantly wet, which is not practical because there is a risk of the carbon dioxide adsorption performance deteriorating. EXAMPLES

[0077] ((C)-2 Distribution Repossession Act) A mechanism capable of distributing mist or gas, such as a spray or blower, is provided in advance in the chamber or duct device on the inlet and / or outlet side of the reloading zone 10, and the reloading mist and / or the reloading gas are circulated (distribution step). Alternatively, an appropriate port may be provided on the inlet side of the reloading zone 10, and a nozzle or the like may be inserted from this port as necessary to allow distribution. Reloading can be performed with both end faces of the rotor facing up or down or left or right. When both end faces of the rotor are mounted in the up or down position, this is preferable because the reloading mist and reloading gas that have penetrated into the rotor move downward by their own weight.

[0078] It is preferable to use a blower to pass the reloading gas, since the gas can be passed in the same manner as the gas to be adsorbed and the desorption gas. It is preferable that the reloading gas contains moisture, that is, that the gas is given a certain degree of humidity, for example, a relative humidity in the range of 30 to 70% RH. The reloading reaction hardly proceeds with dry gas, and conversely, if gas with too high a relative humidity is used, the rotor becomes wet and a separate drying process is required. In addition, the amount of water held by the honeycomb and adsorbent in the adsorption zone 2 increases, which reduces the carbon dioxide adsorption performance and requires special anti-corrosion and waterproof materials, which increases costs.

[0079] The surface velocity of the reloading gas is 0.05 to 5 m / s, preferably 0.1 to 3 m / s. If the surface velocity is too slow, the time required for the reloading reaction will be long, and if it is too fast, many gas components will escape without causing the reloading reaction. To adjust the reloading gas to a desired humidity, humidity regulators 5 and 7 may be used, or a humidity regulator may be provided separately. When water vapor is used in the desorption zone 3, the humidity of the reloading gas is adjusted taking into account the moisture retention of the rotor.

[0080] When the reloading zone 10 is not provided, a mechanism capable of distributing mist or gas is provided in advance in a chamber or duct device on the inlet side and / or outlet side of the adsorption zone 2 and / or desorption zone 3, and the mist for reloading or the gas for reloading is circulated (distribution step). Alternatively, a port may be provided appropriately on the inlet side and / or outlet side of the adsorption zone 2 and / or desorption zone 3, and a nozzle or the like may be inserted from this port to allow the mist to circulate as necessary.

[0081] The reloading mist and reloading gas that have passed through the rotor are discharged from the chamber on the opposite side or are recovered and reused. When reused, they may be circulated again from the end face through which they flow. Since the reloading mist and reloading gas may turn into droplets when penetrating into the rotor, a drain may be provided.

[0082] Basically, it is preferable to use the (C) temporary regeneration method in which reloading is performed temporarily when the carbon dioxide adsorbent performance deteriorates, but it is also possible to use the (D) constant regeneration method in which reloading is performed constantly depending on the application and purpose. In the (C) temporary regeneration method, when reloading is not performed, the reloading zone 10 can function as a cooling zone. In the (D) constant regeneration method in which reloading gas is always circulated through the reloading zone 10, the rotor is not sufficiently cooled after passing through the desorption zone 3, so that passing a gas containing moisture in the reloading zone 10 serves both to reload the adsorbent and to cool the rotor. Since the rotor is transferred to the adsorption zone 2 in a sufficiently cooled state, the carbon dioxide adsorption performance is improved.

[0083] When an amine-based adsorbent is used, heated gas is used in the desorption zone 3, so that part of the amine compound evaporates or desorbs with the desorption of carbon dioxide. For this reason, if part or all of the gas that has passed through the desorption zone 3 is used in the reloading zone 10, most of the amine compound that has evaporated or desorbed in the desorption zone 3 can be recovered and reloaded. The rotor after passing through the desorption zone 3 is not sufficiently cooled, and part of the amine compound evaporates or desorbs before its temperature drops, reducing waste of the amine compound and avoiding a decrease in the carbon dioxide adsorption performance of the adsorbent. In this case, the amine compound that evaporates or desorbs is recovered and reloaded, so that the consumption of the amine compound required for reloading can be reduced. If the reloading zone 10 is not provided, part or all of the gas that has passed through the desorption zone 3 can be circulated and introduced again into the desorption zone 3, or into the adsorption zone 2 to the extent that it does not affect performance, and the amine compound that has evaporated or desorbed in the desorption zone 3 can be recovered and reloaded.

[0084] By reloading, the amine compound lost by evaporation or desorption, or the amine compound fixed to the adsorbent as carbamic acid by oxidation and deactivated can be compensated for, thereby avoiding a decrease in the carbon dioxide adsorption performance of the carbon dioxide adsorbent, and the carbon dioxide adsorption performance can be maintained for a long period of time. In addition to carbon dioxide, VOCs and trace amounts of NOx, SOx, etc. are contained in the gas to be adsorbed, such as the air in the living space and exhaust gas, and when these are attached to the surface of the adsorbent, the carbon dioxide adsorption performance of the adsorbent decreases, but reloading makes it possible to recover the decreased carbon dioxide adsorption performance. In addition, the transpiration or desorption of the amine compound opens up pore spaces on the surface of the porous carrier, making reloading easier and avoiding a decrease in the specific surface area of ​​the adsorbent due to overloading, etc.

[0085] When reloading is performed by the (C) temporary regeneration method and the (D) continuous regeneration method, the device is operated to rotate the rotor and / or duct device, while droplets of the reloading solution, mist for reloading, or gas for reloading are dropped or circulated in at least one of the adsorption zone, desorption zone, or reloading zone, and gas such as the gas to be adsorbed or the desorption gas is circulated in the other zones. In this case, regardless of the presence or absence of the reloading zone, adsorption and desorption of carbon dioxide may be performed simultaneously with the reloading, but there is a risk that the adsorption performance of carbon dioxide may decrease during reloading. It is efficient to flow gas to a zone other than the zone where droplets of the reloading solution, mist for reloading, or gas for reloading are dropped or circulated, and it is preferable to flow heated desorption gas in the desorption zone for drying (drying step).

[0086] When the reloading zone 10 is provided, a drying zone may be provided after the reloading zone 10. Alternatively, since the heated desorption gas is passed through the desorption zone 3, the reloading zone may be provided before the desorption zone.

[0087] In the drop reloading method (Example 8) and the flow reloading method (Example 9), the chamber, seals, and other device parts require waterproofing and anticorrosion treatment, but there is no need to remove the rotor, and the carbon dioxide adsorption performance can be restored by a simple method of simply flowing the reloading gas (C) temporarily or (D) constantly while the device is in operation. Compared to the drop reloading method (Example 8), the flow reloading method (Example 9) does not require the flow of liquid through the rotor, so the device can be simplified and the drying process and time can be reduced.

[0088] The adsorbent regeneration method performed while the apparatus is in operation can eliminate the need to remove the rotor and reload it, as compared with the adsorbent regeneration method in which the apparatus is stopped and the rotor is removed or the rotor is mounted on the apparatus, and does not cause any trouble such as stopping the operation of the apparatus. Furthermore, it is possible to maintain the carbon dioxide adsorption performance over a long period of time while restoring the performance of the rotor with the rotor in operation.

[0089] In the various adsorbent regeneration methods, each method may be combined. A zone other than the adsorption zone, desorption zone, and reloading zone may be provided. A reloading solution, reloading mist, or reloading gas of a type different from that of the carbon dioxide adsorbent initially loaded may be used.

[0090] As described above, according to the method for regenerating the carbon dioxide adsorbent in the carbon dioxide adsorption device of the present invention, when the adsorption performance of a carbonate-based adsorbent or an amine-based adsorbent is reduced due to repeated adsorption and desorption of carbon dioxide, the carbon dioxide adsorption performance of the adsorbent can be restored by reloading the adsorbent in a simple manner without replacing the rotor with a new one. It is also possible to reload the adsorbent while the device is in operation, so that the carbon dioxide adsorption performance can be maintained for a long period of time. [Industrial Applicability]

[0091] Although the carbonate-based adsorbent and the amine-based adsorbent have been described as examples, the carbon dioxide adsorbent regeneration method in the carbon dioxide adsorption device of the present invention can be applied to carbon dioxide adsorbents whose performance deteriorates with long-term use. In addition, even for carbon dioxide adsorbents whose performance does not deteriorate easily, when it is desired to improve the carbon dioxide adsorption performance of the rotor, the adsorption performance can be improved by supporting the adsorbent using the carbon dioxide adsorbent reloading method of the present invention. Furthermore, the carbon dioxide adsorption device of the present invention has a wide range of applications, and can adsorb and remove carbon dioxide in the atmosphere and supply air with a low carbon dioxide concentration to living spaces. It can also be used to concentrate and separate relatively high concentrations of carbon dioxide contained in combustion exhaust gas from thermal power plants, etc. [Explanation of symbols]

[0092] 1 rotor 2 Adsorption Zone 3. Desorption Zone 4, 6 Temperature adjustment device 5, 7 Humidity adjustment device 8 Blocks 9. Chamber 10 Reloading Zone 31 Porous Carriers 31a Pore 32 Carbon dioxide absorbent 33 Filter section

Claims

1. A method for regenerating a carbon dioxide adsorbent, comprising: an impregnation step of impregnating a rotor carrying a carbon dioxide adsorbent with a reloading solution; and a drying step of drying the reloading solution attached to the rotor, the impregnation step and the drying step being repeated once or alternately multiple times.

2. A method for regenerating a carbon dioxide adsorbent, comprising: a dripping step of dripping droplets of a reloading solution onto a rotor carrying a carbon dioxide adsorbent; and a drying step of drying the droplets of the reloading solution attached to the rotor, the dripping step and the drying step being repeated once or alternately multiple times.

3. A method for regenerating a carbon dioxide adsorbent, comprising a circulation step of circulating a reloading mist and / or a reloading gas through a rotor carrying a carbon dioxide adsorbent, and a drying step of drying the reloading mist and / or the reloading gas adhered to the rotor, the circulation step and the drying step being repeated once or alternately multiple times.

4. A method for regenerating a carbon dioxide adsorbent, comprising: a fumigation process for sealing a rotor carrying a carbon dioxide adsorbent in a sealed mechanism and filling the sealed mechanism with a re-supporting mist and / or a re-supporting gas by fumigation; and a drying process for drying the re-supporting mist and / or the re-supporting gas that has adhered to the rotor, the fumigation process and the drying process being repeated once or alternately multiple times.

5. 5. The method for regenerating a carbon dioxide adsorbing material according to claim 1, further comprising a step of washing the rotor with water.

6. A carbon dioxide adsorption device in which a rotor carrying a carbon dioxide adsorbent is divided into at least an adsorption zone and a desorption zone, a gas to be adsorbed is ventilated through the adsorption zone to adsorb carbon dioxide contained in the gas to be adsorbed onto the carbon dioxide adsorbent, and a heated desorption gas is ventilated through the desorption zone to desorb the adsorbed carbon dioxide, characterized in that the carbon dioxide adsorbent is regenerated by dropping droplets of a reloading solution into the adsorption zone and / or the desorption zone, and / or by circulating a reloading mist and / or a reloading gas.

7. A carbon dioxide adsorption apparatus in which a rotor carrying a carbon dioxide adsorbent is divided into at least an adsorption zone, a desorption zone, and a re-support zone, a gas to be adsorbed is ventilated through the adsorption zone to adsorb carbon dioxide contained in the gas to be adsorbed onto the carbon dioxide adsorbent, and a heated desorption gas is ventilated through the desorption zone to desorb the adsorbed carbon dioxide, characterized in that the carbon dioxide adsorbent is regenerated by dropping droplets of a re-support solution into the re-support zone and / or by circulating a re-support mist and / or a re-support gas.

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