How to recycle direct air recovery equipment

Abstract

To provide a recycling method for a direct air recovery device which removes a used carbon dioxide absorbent from a porous carrier to be capable of reusing the porous carrier.SOLUTION: A recycling method for a direct air recovery device according to an embodiment is a recycling method for a direct recovery device with a porous carrier supporting a carbon dioxide absorbent. The porous carrier is composed of inorganic material including hydroxy groups, and the carbon dioxide absorbent is a hydrophilic polymer. The used carbon dioxide absorbent is removed from the porous carrier by heating the direct air recovery device up to a prescribed temperature, and then a new carbon dioxide absorbent is carried onto the porous carrier.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present disclosure relates to a method for recycling a direct air recovery device. [Background technology]

[0002] Direct air capture (DAC) devices are known to reduce carbon dioxide, a greenhouse gas, by directly capturing carbon dioxide from the air. In these devices, a carbon dioxide absorbent is supported on a porous carrier. As a carbon dioxide absorbent, for example, as disclosed in Patent Document 1, an amine-containing carbon dioxide absorbent is known. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-055886 Summary of the Invention [Problem to be solved by the invention]

[0004] In the direct air recovery device, the carbon dioxide absorbent deteriorates with use, so the direct air recovery device, that is, the porous carrier carrying the carbon dioxide absorbent, is periodically replaced. In response to this, the inventors are considering recycling of a direct air recovery device in which the used carbon dioxide absorbent is removed from the porous carrier and the porous carrier is reused.

[0005] The present disclosure has been made in consideration of the above circumstances, and provides a method for recycling a direct air recovery device in which a used carbon dioxide absorbent is removed from a porous carrier and the porous carrier can be reused. [Means for solving the problem]

[0006] A method for recycling a direct air recovery device according to one aspect of the present disclosure includes: A method for recycling a direct air recovery device comprising a porous carrier carrying a carbon dioxide absorbent, the method comprising: the porous carrier is made of an inorganic material having a hydroxyl group, the carbon dioxide absorbent is a hydrophilic polymer, The direct air recovery device is heated to a predetermined temperature, the used carbon dioxide absorbent is removed from the porous carrier, and then new carbon dioxide absorbent is supported on the porous carrier.

[0007] In one aspect of the present disclosure, the porous carrier is made of an inorganic material having a hydroxyl group, the carbon dioxide absorbent is a hydrophilic polymer, and the air recovery device is directly heated to a predetermined temperature to remove the used carbon dioxide absorbent from the porous carrier, and then new carbon dioxide absorbent is supported on the porous carrier. With this configuration, the used carbon dioxide absorbent can be removed from the porous carrier and the porous carrier can be reused.

[0008] The porous carrier may be a coating film formed on the substrate, and the amount of the porous carrier used may be reduced. The substrate may be made of ceramic.

[0009] The porous carrier may be a substrate having a honeycomb structure, which eliminates the need to separately form a coating film of the porous carrier on the substrate.

[0010] The porous carrier may be made of silica gel. The hydrophilic polymer may be an amine-based polymer. Furthermore, the predetermined temperature may be 500° C. or higher.

[0011] After removing the used carbon dioxide absorbent from the porous carrier, the porous carrier may be held in a water vapor atmosphere before new carbon dioxide absorbent is supported on the porous carrier. With this configuration, the hydroxyl groups lost from the porous carrier 12 can be restored. [Effects of the Invention]

[0012] The present disclosure provides a method for recycling a direct air recovery device that removes used carbon dioxide absorbent from a porous carrier and allows the porous carrier to be reused. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a perspective view of a direct air recovery device according to a first embodiment. [Figure 2] FIG. 2 is an enlarged cross-sectional view of the direct air recovery device according to the first embodiment. [Figure 3] FIG. 4 is an enlarged cross-sectional view of a direct air recovery device according to a modified example of the first embodiment. [Figure 4] 1 shows macrophotographs of silica gel beads before and after polyethyleneimine was supported thereon. [Figure 5] 1 is a macrophotograph of silica gel after heating to various temperatures to remove polyethyleneimine. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, specific embodiments of the present disclosure will be described in detail with reference to the drawings. However, the present disclosure is not limited to the following embodiments. In addition, the following description and drawings have been simplified appropriately for clarity of explanation.

[0015] (First embodiment) <Configuration of direct air recovery equipment> First, the configuration of the direct air recovery device according to the first embodiment will be described with reference to Figures 1 and 2. Figure 1 is a perspective view of the direct air recovery device according to the first embodiment. Figure 2 is an enlarged cross-sectional view of the direct air recovery device according to the first embodiment. It should be noted that the right-handed xyz coordinate system shown in the drawings is a matter of convenience for explaining the positional relationship of the components. The xyz coordinate system is common to all drawings, and the y-axis direction is the axial direction of the porous support 12.

[0016] As shown in Fig. 2, the direct air recovery device 10 includes a substrate 11 and a porous carrier 12. As shown in Fig. 1, the direct air recovery device 10 is a device that brings the porous carrier 12 carrying a carbon dioxide absorbent into contact with air and recovers carbon dioxide in the air by adsorbing it onto the carbon dioxide absorbent.

[0017] As shown in Fig. 1, the substrate 11 has, for example, a substantially cylindrical outer shape. As shown in Fig. 2, the substrate 11 has a honeycomb structure made up of a plurality of flow paths 13 extending in the y-axis direction. As shown in Fig. 2, the inner circumferential surface of each flow path 13 is coated with a porous carrier 12 carrying a carbon dioxide absorbent.

[0018] As shown by the white arrows in Figure 1, air passes through the inside of each flow path 13 coated with porous support 12 in the axial direction (y-axis direction), and carbon dioxide in the air is absorbed by the carbon dioxide absorbent supported on the porous support 12. 2, the cross-sectional shape of the flow channel 13 is square, but it may be hexagonal, etc. The outer shape of the substrate 11 is not limited, and may be, for example, a prismatic shape.

[0019] The substrate 11 is made of, for example, an inorganic material, specifically, for example, cordierite or ceramic such as SiC (silicon carbide) having electrical conductivity. The substrate 11 may be made of metal.

[0020] The porous support 12 supports a carbon dioxide absorbent in fine pores of, for example, about 2 to 100 nm. The porous support 12 is made of an inorganic material having a hydroxyl group, such as silica gel. Furthermore, because the porous support 12 is porous, the surface area of ​​the supported carbon dioxide absorbent that comes into contact with air is increased, allowing carbon dioxide to be adsorbed with high efficiency.

[0021] In this embodiment, the porous carrier 12 is a coating film formed on the substrate 11. For example, the porous carrier 12 can be formed by applying a mixture of powder of an inorganic material having a hydroxyl group (e.g., silica gel) and an inorganic binder such as water glass onto the substrate 11. In this embodiment, since the porous carrier 12 is a coating film, the amount of the porous carrier 12 used can be reduced compared to the modified examples described later.

[0022] The carbon dioxide absorbent is a hydrophilic polymer, specifically, an amine-based polymer such as polyethyleneimine, primary amine, secondary amine, or secondary alkanolamine.

[0023] In carbon dioxide recovery, a process of adsorbing carbon dioxide by passing air through the direct air recovery device 10 at room temperature (see FIG. 1) and a process of desorbing carbon dioxide by heating the direct air recovery device 10 to, for example, about 100°C (not shown) are repeated. Repeating this adsorption process and desorption process deteriorates the carbon dioxide absorbent.

[0024] For this reason, in conventional direct air recovery devices, the direct air recovery device, that is, the porous carrier carrying the carbon dioxide absorbent, has been periodically replaced. In contrast, in the direct air recovery device 10 according to this embodiment, the used carbon dioxide absorbent is removed from the porous carrier 12, and the substrate 11 and the porous carrier 12 are reused. A recycling method for the direct air recovery device 10 according to this embodiment will be described later. In the separation step, the substrate 11 may be heated by electrical current.

[0025] <Modification> Here, the configuration of a direct air recovery device according to a modified example of the first embodiment will be described with reference to Fig. 3. Fig. 3 is an enlarged cross-sectional view of a direct air recovery device according to a modified example of the first embodiment. Fig. 3 corresponds to Fig. 2.

[0026] 3, in the direct air recovery device 10 according to the modified example, the porous carrier 12 is a substrate having a honeycomb structure. That is, the porous carrier 12 may have a honeycomb structure composed of a plurality of flow paths 13 extending in the y-axis direction. In the direct air recovery device 10 shown in FIG. 3, the porous carrier 12 is the substrate, so unlike the direct air recovery device 10 shown in FIG. 2, there is no need to separately form a coating film of the porous carrier on the substrate.

[0027] A carbon dioxide absorbent is supported on the inner circumferential surface of each flow path 13 shown in Fig. 3. In the direct air recovery device 10 according to the modified example, the porous support 12 also supports the carbon dioxide absorbent in fine pores of, for example, about 2 to 100 nm. The porous support 12 is made of an inorganic material having a hydroxyl group, such as silica gel.

[0028] <How to recycle direct air recovery equipment> Next, a method for recycling the direct air recovery device according to this embodiment will be described. First, the direct air recovery device 10 shown in Figures 1 and 2 is heated to a predetermined temperature to remove the used carbon dioxide absorbent from the porous carrier 12. The heating temperature for removing the used carbon dioxide absorbent is higher than the heating temperature in the desorption step, and specifically, for example, is 500°C or higher. The heating may be performed by electrically heating the substrate 11, as in the separation step.

[0029] Heating to remove the carbon dioxide absorbent decomposes the carbon dioxide absorbent, which is made of a hydrophilic polymer. During this process, the hydroxyl groups in the porous carrier 12 are lost. Therefore, the direct air recovery device 10 from which the carbon dioxide absorbent has been removed may be held, for example, in a water vapor atmosphere to restore the hydroxyl groups lost from the porous carrier 12. Specifically, the direct air recovery device 10 is held, for example, in a saturated water vapor atmosphere at 80°C.

[0030] Next, a new carbon dioxide absorbent is supported on the porous carrier 12 from which the used carbon dioxide absorbent has been removed. In this way, only the porous carrier 12 is replaced, and the substrate 11 and the porous carrier 12 are reused, thereby reducing the cost of carbon dioxide recovery.

[0031] As described above, in the recycling method for the direct air recovery device 10 according to this embodiment, the direct air recovery device 10 is heated to a predetermined temperature, the used carbon dioxide absorbent is removed from the porous carrier 12, and then a new carbon dioxide absorbent is supported on the porous carrier 12. In other words, only the porous carrier 12 is replaced, and the substrate 11 and the porous carrier 12 are reused, thereby reducing the cost of carbon dioxide recovery. [Example]

[0032] The recycling method for the direct air recovery device 10 according to the first embodiment will be described in detail below with reference to examples. However, the recycling method for the direct air recovery device 10 according to the first embodiment is not limited to the following examples.

[0033] <Test conditions> Branched polyethyleneimine (manufactured by Fujifilm WAKO) with an average molecular weight of 600 was used as a carbon dioxide absorbent. 24 g of ethanol was added to 6 g of this polyethyleneimine to prepare a 20% by mass polyethyleneimine solution. Beaded silica gel (CARiACT Q-10, manufactured by Fuji Silysia Chemical) was added as a porous carrier to this polyethyleneimine solution, and the mixture was stirred in a sealed container. The ethanol was then removed under reduced pressure, and the mixture was dried at 80°C. Here, silica gel is an inorganic material having hydroxyl groups, and polyethyleneimine is a hydrophilic polymer.

[0034] Through the above steps, polyethyleneimine, a carbon dioxide absorbent, was supported on the surface of the silica gel, which was a porous carrier. This porous carrier corresponds to porous carrier 12 in Figure 2. This silica gel had mesopores with a pore distribution of 1.1 mL / g, and polyethyleneimine was supported in the mesopores.

[0035] Here, Figure 4 shows macrophotographs of bead-shaped silica gel before and after polyethyleneimine was supported. As shown in Figure 4, before polyethyleneimine was supported, the silica gel was transparent, but after polyethyleneimine was supported in the mesopores, the silica gel became cloudy.

[0036] Next, in order to remove the polyethyleneimine carried on the silica gel, the silica gel carrying the polyethyleneimine was heated to a predetermined temperature and maintained at this temperature for 6 hours while air was flowing through at a rate of 2 L / min. The heating temperature was changed to 400℃, 450℃, and 500℃ to observe the removal status of polyethyleneimine, a carbon dioxide absorbent, and measure the pore size distribution.

[0037] <Test Results> Figure 5 shows macroscopic photographs of silica gel after heating to various temperatures to remove polyethyleneimine. When polyethyleneimine is heated above a certain temperature, it oxidizes, generating carbon dioxide and nitrogen dioxide, and the polyethyleneimine disappears.

[0038] As shown in Figure 5, at heating temperatures of 400°C and 450°C, some polyethyleneimine was not completely removed and remained, causing the silica gel to turn black. The pore size distributions at heating temperatures of 400°C and 450°C were 0.91 mL / g and 0.97 mL / g, respectively. As shown in Figure 5, at a heating temperature of 500°C, polyethyleneimine was sufficiently removed and the silica gel became transparent again. The pore size distribution at a heating temperature of 500°C was 1.2 mL / g, which was higher than the 1.1 mL / g before use.

[0039] From the results of the above examples, it was found that when a direct air recovery device in which a carbon dioxide absorbent, which is a hydrophilic polymer, is supported on a porous carrier made of an inorganic material having hydroxyl groups is heated to 500°C or higher, the carbon dioxide absorbent is sufficiently removed and the porous carrier can be reused.

[0040] The present disclosure is not limited to the above-described embodiments, and can be modified as appropriate within the scope of the present disclosure. This disclosure also contributes to carbon neutrality, decarbonization, and the Sustainable Development Goals (SDGs). [Explanation of symbols]

[0041] 10 Direct Air Recovery Device 11 Base material 12 Porous carrier 13 Flow path

Claims

1. A method for recycling a direct air recovery device that includes a porous carrier carrying a carbon dioxide absorbent on a substrate having a honeycomb structure, the method comprising: the porous carrier is a coating film formed by coating a mixture of silica gel powder and an inorganic binder on the substrate, the carbon dioxide absorbent is an amine-based polymer, The direct air recovery device is heated to a predetermined temperature, and the used carbon dioxide absorbent is absorbed into the porous After removing the carbon dioxide absorbent from the porous carrier, a new carbon dioxide absorbent is supported on the porous carrier. How to recycle direct air recovery equipment.

2. The substrate is made of ceramic.

10. The method for recycling a direct air recovery unit according to claim 1.

3. The predetermined temperature is 500°C or higher.

3. A method for recycling a direct air recovery device according to claim 1 or 2.

4. After removing the used carbon dioxide absorbent from the porous carrier, a new carbon dioxide absorbent is placed on the porous carrier. Before loading the new carbon dioxide absorbent, The porous carrier is maintained in a water vapor atmosphere.

3. A method for recycling a direct air recovery device according to claim 1 or 2.

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