JP2010184229A - Carbon dioxide adsorbent and carbon dioxide recovery apparatus using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adsorbent having higher adsorbing performance on carbon dioxide than conventional carbon dioxide adsorbents, and to improve the efficiency of a carbon dioxide recovery apparatus by using the adsorbent having high adsorbing performance. <P>SOLUTION: The carbon dioxide adsorbent for adsorbing and separating carbon dioxide from a gas containing the carbon dioxide has its carrier made of mesoporous silica and has at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Y and La supported by the carrier. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a carbon dioxide adsorbent and a carbon dioxide recovery device using the same.

The problem of global warming due to greenhouse gas emissions has been widely recognized. The greenhouse gas carbon dioxide _(CO 2), methane _(CH 4), but fluorocarbons (CFCs), and the like, emissions is large, having a large substantial impact is carbon dioxide, the discharge Reduction of volume is an urgent issue.

  Currently, carbon dioxide recovery technology using a carbon dioxide absorbing liquid (Patent Document 1) has begun to be used, but the cost for maintenance of the carbon dioxide absorbing liquid is high.

  Accordingly, development of a solid carbon dioxide adsorbent (Patent Document 2) that is relatively low in maintenance costs has been underway.

Patent Document 1, an absorption tower by contacting the exhaust gas and the CO ₂ absorbing solution containing CO ₂ removing CO _2, and regeneration tower for reproducing rich solution that has absorbed CO _2, CO in the regenerator ₂ is a CO ₂ recovery system to recycle the lean solution which is removed in the absorption tower, the absorbing tower, and the CO ₂ recovery unit that absorbs CO ₂ in the exhaust gas in the CO ₂ absorbing solution, the CO ₂ recovery provided on the upper side of the section, to cool the gas to remove CO _2, and water washing unit for collecting the entrained CO ₂ absorbing solution, the condensed water containing CO ₂ absorbing liquid that has been condensed in the water-washing section, the Surplus condensate supplying an excess of condensed water containing the CO ₂ absorbent to a circulation line that circulates directly from the top of the water washing section and a lean solution supply pipe that supplies the lean solution from the regeneration tower to the absorption tower CO ₂ having a supply line Osamu apparatus is disclosed.

Patent Document 2 discloses a CO ₂ adsorption method in which CO ₂ or a CO ₂ -containing gas is brought into contact with a transition metal-supported zeolite at about 20 to 100 ° C.

Patent Document 3 discloses a method for treating exhaust gas in which exhaust gas containing CO ₂ and moisture is brought into contact with a support chemically bonded with a silane coupling agent, selectively adsorbed and desorbed with CO _2. Has been.

However, solid carbon dioxide adsorbing material of Patent Document 3, CO ₂ and chemically react to produce a structure of CO ₂ increases varied compound, there is a barrier activation energy, energy required for desorption even growing.

Patent Document 4 discloses a carbon dioxide absorption process comprising a carbon dioxide absorption process in which a metal oxide and CO ₂ are contacted to form a metal carbonate, and a process in which the metal carbonate is thermally decomposed to separate carbon dioxide. And an apparatus are disclosed. However, in this Patent Document 4, CO ₂ requires a high temperature of about 600 ° C. in order to react with the metal oxide, and in order to desorb CO ₂ from the metal carbonate, the higher temperature is 900. A temperature of about ℃ is required, and the energy required for absorption and regeneration becomes very high.

JP 2007-284272 A JP-A-5-131116 JP 2004-261670 A JP-A-8-24571

  An object of the present invention is to provide an adsorbent having a higher carbon dioxide adsorption capacity than a conventional carbon dioxide adsorbent, and to improve the efficiency of a carbon dioxide recovery device using an adsorbent having a high adsorption capacity. .

  The carbon dioxide adsorbing material of the present invention is a carbon dioxide adsorbing material for adsorbing / separating carbon dioxide from a gas containing carbon dioxide, wherein the carbon dioxide adsorbing material carrier is formed of mesoporous silica, and Mg, It is characterized in that at least one element selected from the group consisting of Ca, Sr, Ba, Y and La is supported.

  ADVANTAGE OF THE INVENTION According to this invention, while providing the carbon dioxide adsorbent which has higher adsorption capacity than the conventional carbon dioxide adsorbent, the efficiency of a carbon dioxide recovery apparatus can be improved using an adsorbent with high adsorption capacity. .

It is a schematic block diagram of the carbon dioxide recovery apparatus using the heating and cooling operation which shows the Example by this invention. It is a schematic block diagram of the carbon dioxide recovery apparatus using the pressurization and pressure reduction operation which shows the Example by this invention. It is a schematic block diagram of the carbon dioxide recovery apparatus using the heating and cooling operation which shows the Example by this invention. It is a schematic block diagram of the carbon dioxide recovery apparatus using the pressurization and pressure reduction operation which shows the Example by this invention. It is a schematic block diagram of the carbon dioxide recovery apparatus using the heating and pressurization operation which shows the Example by this invention. It is a schematic block diagram of the carbon dioxide recovery apparatus using the heating and pressurization operation which shows the Example by this invention. It is a schematic block diagram of the carbon dioxide recovery apparatus using the heating and pressurization operation which shows the Example by this invention. It is a schematic diagram which shows the molecular structure of the silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to the silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the silica of the water vapor | steam calculated | required by the first principle calculation. It is a schematic diagram which shows the molecular structure of the amine modification silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the amine modification silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to the amine modification silica of the water vapor | steam calculated | required by the first principle calculation. It is a schematic diagram which shows the molecular structure of the Na carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to the Na carrying | support silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to Na carrying | support silica of the water vapor | steam calculated | required by the first principle calculation. It is a schematic diagram which shows the molecular structure of the K carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to the K carrying | support silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the K carrying | support silica obtained by the first principle calculation. It is a schematic diagram which shows the molecular structure of Rb carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the Rb carrying | support silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to the Rb carrying | support silica of the water vapor | steam calculated | required by the first principle calculation. It is a schematic diagram which shows the molecular structure of Cs carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the Cs carrying | support silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to the Cs carrying | support silica of the water vapor | steam calculated | required by the first principle calculation. It is a schematic diagram which shows the molecular structure of Mg carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to the Mg carrying | support silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to the Mg carrying | support silica of the water vapor | steam calculated | required by the first principle calculation. It is a schematic diagram which shows the molecular structure of the Ca carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the Ca carrying | support silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to Ca carrying | support silica obtained by the first principle calculation. It is a schematic diagram which shows the molecular structure of the Sr carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the Sr carrying | support silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to the Sr carrying | support silica of the water vapor | steam calculated | required by the first principle calculation. It is a schematic diagram which shows the molecular structure of Ba carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the Ba carrying | support silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to Ba carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the molecular structure of the Y carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption state to the Y carrying | support silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the Y carrying | support silica obtained by the first principle calculation. It is a schematic diagram which shows the molecular structure of La carrying | support silica calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the La carrying | support silica of the carbon dioxide calculated | required by the first principle calculation. It is a schematic diagram which shows the adsorption | suction state to the La carrying | support silica of the water vapor | steam calculated | required by the first principle calculation. It is the graph showing the carbon dioxide adsorption energy and water vapor | steam adsorption energy in Comparative Examples 1 and 2 and Examples 1-10. It is a schematic block diagram which shows the thermal analyzer for measuring the desorption temperature of a carbon dioxide.

  Hereinafter, the present invention will be described in detail.

The carbon dioxide adsorbent of the present invention comprises a carrier formed of silica (SiO ₂ ) having a large specific surface area, Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), Y (yttrium) and And an active ingredient which is at least one element selected from the group of La (lanthanum).

  The carbon dioxide recovery apparatus of the present invention includes an adsorption part provided with a carbon dioxide adsorbent for adsorbing and separating carbon dioxide from a gas containing carbon dioxide, and a carbon dioxide adsorbed on the carbon dioxide adsorbent by the adsorption part. A desorption part for desorbing and recovering carbon by heating; and a gas heating part for heating a gas that passes through the adsorption part and flows into the desorption part, wherein the adsorption part and the desorption part The carbon dioxide adsorbent can be exchanged between them, and the carbon dioxide adsorbent carrier is formed of mesoporous silica. The carrier is at least one selected from the group consisting of Mg, Ca, Sr, Ba, Y and La. An element is supported.

  The carbon dioxide recovery apparatus of the present invention includes an adsorption part provided with a carbon dioxide adsorbent for adsorbing and separating carbon dioxide from a gas containing carbon dioxide, and a carbon dioxide adsorbed on the carbon dioxide adsorbent by the adsorption part. Desorbing part for desorbing and collecting carbon by reducing the pressure, a gas pressurizing part for increasing the pressure of the gas sent to the adsorbing part, and reducing the pressure of the gas that has passed through the adsorbing part A gas decompression section for exchanging the carbon dioxide adsorbent between the adsorption section and the desorption section, and a carrier for the carbon dioxide adsorbent is formed of mesoporous silica. , Sr, Ba, Y, and La, at least one element selected from the group is supported.

  The carbon dioxide recovery device of the present invention comprises an adsorption part provided with a carbon dioxide adsorbent for adsorbing and separating carbon dioxide from a gas containing carbon dioxide, and a carbon dioxide adsorbed on the carbon dioxide adsorbent by the adsorption part. A desorption unit for desorbing and collecting carbon by heating, a gas pressurization unit for increasing the pressure of the gas sent to the adsorption unit, and heating the gas that has passed through the adsorption unit A gas heating part, and the carbon dioxide adsorbing material can be exchanged between the adsorbing part and the desorbing part, and a carrier of the carbon dioxide adsorbing material is formed of mesoporous silica, and Mg, Ca, Sr is formed on the carrier. At least one element selected from the group consisting of Ba, Y and La is supported.

  The carbon dioxide recovery apparatus of the present invention includes an adsorption part provided with a carbon dioxide adsorbent for adsorbing and separating carbon dioxide from a gas containing carbon dioxide, and a carbon dioxide adsorbed on the carbon dioxide adsorbent by the adsorption part. A desorption part for desorbing and collecting carbon by heating, and an adsorbent heating part for heating the carbon dioxide adsorbent of the desorption part, between the adsorption part and the desorption part The carbon dioxide adsorbent can be exchanged, and the carrier of the carbon dioxide adsorbent is formed of mesoporous silica. At least one element selected from the group consisting of Mg, Ca, Sr, Ba, Y and La is formed on the carrier. It is supported.

  The carbon dioxide recovery device of the present invention further includes a gas pressurization unit for increasing the pressure of the gas sent to the adsorption unit.

  The carbon dioxide recovery device of the present invention further includes a first weight detection unit for detecting the weight of the carbon dioxide adsorbent in the adsorption unit and a weight of the carbon dioxide adsorbent in the desorption unit. The carbon dioxide adsorption amount of the carbon dioxide adsorbent is calculated from the values detected by the second weight detector, the first weight detector and the second weight detector, and the carbon dioxide adsorbent replacement time is calculated. And a control unit for carrying out the control.

  The carbon dioxide recovery device of the present invention further includes a gas circulation unit for returning a part of the gas flowing out from the desorption unit to the desorption unit.

  In the carbon dioxide recovery device of the present invention, each of the adsorption unit and the desorption unit is composed of a plurality of stages of carbon dioxide adsorbents, and a weight detection unit for detecting the weight of each of the plurality of stages of carbon dioxide adsorbents. Each of the weight detectors detects a weight of the carbon dioxide adsorbent, and the controller calculates a carbon dioxide adsorption amount of the carbon dioxide adsorbent from a value detected by the weight detector, and It is characterized by controlling the replacement time of the carbon adsorbent.

  Carbon dioxide generally combines with an alkali metal or alkaline earth metal to form a salt. Examples of the alkali metal include Na (sodium), K (potassium), Rb (rubidium), and Cs (cesium). Examples of the alkaline earth metal include Mg (magnesium), Ca (calcium), Sr (strontium), and Ba. (Barium). Similarly, if Y (yttrium) and La (lanthanum), which are Group 3 elements having a large ion radius, are supported on silica having a large specific surface area, an adsorbent having a large carbon dioxide adsorption capacity may be obtained. is there.

  In order to compare the carbon dioxide adsorption capacity of the conventional carbon dioxide adsorbent (Patent Document 3) and the carbon dioxide adsorbent of the present invention, the carbon dioxide adsorption energy was calculated by the first principle calculation. The first-principles calculation method is as shown in Table 1.

  However, the calculation method of carbon dioxide adsorption energy shall be based on following formula (1), and it represents that it becomes so stable at the time of carbon dioxide adsorption that the value of adsorption energy is large.

(Carbon dioxide adsorption energy)
=-[(Energy after carbon dioxide adsorption)-{(energy before carbon dioxide adsorption) + (energy of carbon dioxide)}] (1)

以下、比較例１、２及び実施例１〜１０の分子構造について説明する。

Hereinafter, the molecular structures of Comparative Examples 1 and 2 and Examples 1 to 10 will be described.

(Comparative Example 1)
The structure of silica in which O (oxygen) is four-coordinated to Si (silicon) was obtained from AMCSD (American Mineralist Crystal Structure Database) and used as a support. Furthermore, a hydroxyl group (OH group) was introduced on the surface of the silica, and the structure optimization calculation was performed by the first principle calculation to obtain the adsorbent of Comparative Example 1 (FIG. 8a).

(Comparative Example 2)
In the adsorbent of Comparative Example 1, a structure in which ethylamine was chemically bonded instead of hydrogen of two hydroxyl groups was prepared, and structure optimization calculation was performed. This was used as the adsorbent of Comparative Example 2 (FIG. 9a).

  The structure optimization calculation was performed by replacing H atoms of two hydroxyl groups in the adsorbent of Comparative Example 1 with Na atoms. This was used as the adsorbent of Example 1 (FIG. 10a).

  The structure optimization calculation was performed by replacing H atoms of two hydroxyl groups in the adsorbent of Comparative Example 1 with K atoms. This was used as the adsorbent of Example 2 (FIG. 11a).

  The structure optimization calculation was performed by substituting R atoms for H atoms of two hydroxyl groups in the adsorbent of Comparative Example 1. This was used as the adsorbent of Example 3 (FIG. 12a).

  The structure optimization calculation was performed by substituting H atoms of two hydroxyl groups in the adsorbent of Comparative Example 1 with Cs atoms. This was used as the adsorbent of Example 4 (FIG. 13a).

  The structure optimization calculation was performed by replacing H atoms of two hydroxyl groups in the adsorbent of Comparative Example 1 with Mg atoms. This was used as the adsorbent of Example 5 (FIG. 14a).

  The structure optimization calculation was performed by replacing H atoms of two hydroxyl groups in the adsorbent of Comparative Example 1 with Ca atoms. This was used as the adsorbent of Example 6 (FIG. 15a).

  The structure optimization calculation was performed by replacing H atoms of two hydroxyl groups in the adsorbent of Comparative Example 1 with Sr atoms. This was used as the adsorbent of Example 7 (FIG. 16a).

  The structure optimization calculation was performed by replacing H atoms of two hydroxyl groups in the adsorbent of Comparative Example 1 with Ba atoms. This was used as the adsorbent of Example 8 (FIG. 17a).

  The structure optimization calculation was performed by substituting H atoms of two hydroxyl groups in the adsorbent of Comparative Example 1 with Y atoms. This was used as the adsorbent of Example 9 (FIG. 18a).

  The structure optimization calculation was performed by replacing H atoms of two hydroxyl groups in the adsorbent of Comparative Example 1 with La atoms. This was used as the adsorbent of Example 10 (FIG. 19a).

  For the adsorbents of Comparative Examples 1 and 2 and Examples 1 to 10, the structure optimization by the first principle calculation was performed under the conditions shown in Table 1 in order to obtain the structure and energy in which carbon dioxide was adsorbed.

  FIGS. 8b, 9b, 10b, 11b, 12b, 13b, 14b, 15b, 16b, 17b, 18b and 19b are schematic views showing the adsorption state of carbon dioxide on the adsorbents of each comparative example and each example. Further, Table 2 shows carbon dioxide adsorption energy.

  In FIG. 8b, carbon dioxide does not form a chemical bond with silica and is physically adsorbed by electrostatic force. This shows that the adsorption energy of carbon dioxide on silica is small.

In FIG. 9b, carbon dioxide is adsorbed so as to be sandwiched between two amines. This shows a stable state due to the reaction of —NH ₂ + —NH ₂ + CO ₂ → —NHCO ₂ ⁽⁻⁾ + ^— NH ₃ ⁽⁺⁾ .

As shown in FIGS. 10b, 11b, 12b, 13b, 14b, 15b, 16b, 17b, 18b and 19b, the metal-supported silica which is an example according to the present invention has metal atoms (Na, K, Rb, Two of Cs, Mg, Ca, Sr, Ba, Y, and La) are stable in an adsorption state in which they are bonded to two oxygen atoms (O) of carbon dioxide (CO ₂ ).

  As shown in Table 2, compared with the carbon dioxide adsorption energy by the silica modified with amine, in Examples 5 to 10, the carbon dioxide adsorption energy is large, and the carbon dioxide adsorption ability is improved. It is clear that the higher the carbon dioxide adsorption capacity of each adsorption site, the higher the probability that carbon dioxide will be adsorbed to the carbon dioxide adsorption site, and the amount of carbon dioxide adsorption will increase. Examples of the component supported on the silica of the carbon dioxide adsorbent include Mg, Ca, Sr, Ba, Y, and La.

二酸化炭素吸着の阻害要因となる水蒸気が二酸化炭素吸着材に吸着する能力を調べるために、比較例１、２及び実施例１〜１０における水蒸気吸着エネルギー算出した。表１に示す条件で第一原理計算によって構造最適化を行った。水蒸気吸着エネルギーは、下記式（２）で与えられる。

In order to examine the ability of water vapor, which is an inhibition factor for carbon dioxide adsorption, to be adsorbed on the carbon dioxide adsorbent, the water vapor adsorption energy in Comparative Examples 1 and 2 and Examples 1 to 10 was calculated. The structure was optimized by the first principle calculation under the conditions shown in Table 1. The water vapor adsorption energy is given by the following formula (2).

(Water vapor adsorption energy)
=-[(Energy after water vapor adsorption)-{(Energy before water vapor adsorption) + (Water vapor energy)}] (2)
8c, 9c, 10c, 11c, 12c, 13c, 14c, 15c, 16c, 17c, 18c and 19c show the water vapor adsorption structure on the adsorbents of the comparative examples and examples, and Table 3 shows the water vapor adsorption energy. .

  FIG. 20 is a graph showing the carbon dioxide adsorption energy and water vapor adsorption energy of each comparative example and each example.

  This figure shows that in Examples 5-10, the carbon dioxide adsorption energy is relatively high.

  Moreover, from this figure, in Examples 5, 6, 7, 8 and 10, it can be seen that the water vapor adsorption energy is smaller than the carbon dioxide adsorption energy, and carbon dioxide is preferentially adsorbed. In Example 9, the water vapor adsorption energy is higher than the carbon dioxide adsorption energy.

  From this, in order to promote recovery by adsorption separation of carbon dioxide from a gas containing carbon dioxide and water vapor, after removing the water vapor contained in the gas, the gas is brought into contact with an adsorbent to remove carbon dioxide. Adsorption is desirable. This is remarkable in Example 9.

  Further, it has been experimentally found that the carbon dioxide adsorbing material of the above-described embodiment has a larger carbon dioxide adsorption amount as the carbon dioxide adsorption energy increases.

  Therefore, the carbon dioxide adsorbent having water vapor resistance and suitable for the present invention is one in which Mg, Ca, Sr, Ba, and La are supported on a carrier. Furthermore, mesoporous silica is desirable as the carrier.

  Here, physical properties of mesoporous silica suitable as a carrier will be described with examples.

This mesoporous silica is SILFAM-A (manufactured by Nippon Chemical Industry Co., Ltd.), has a specific surface area of 977 m ² / g, a pore volume of 1.02 cm ³ / g, an average pore diameter of 4.2 nm, and an average particle diameter. (D50) is 49 μm. It is a special porous body having a pore diameter peak in the vicinity of the average pore diameter.

  By applying this mesoporous silica, it is possible to provide an adsorbent that facilitates gas diffusion into the adsorbent, selectively adsorbs carbon dioxide, and has a large amount of adsorbed carbon dioxide. .

（比較例３）
実施例６と同様にＣａを用いた材料である特許文献４の酸化カルシウム（ＣａＯ）を吸着材に用いた場合、二酸化炭素を吸収して生成する炭酸カルシウム（Ｃａ（ＣＯ_３）_２）の二酸化炭素の脱離温度は９００℃以上である。

(Comparative Example 3)
Similarly to Example 6, when calcium oxide (CaO) of Patent Document 4 which is a material using Ca is used as an adsorbent, carbon dioxide (Ca (CO ₃ ) ₂ ) dioxide produced by absorbing carbon dioxide. The desorption temperature of carbon is 900 ° C. or higher.

  The carbon dioxide adsorbents produced in Examples 6, 7 and 8 were once saturated with carbon dioxide at 50 ° C. and then heated to measure the temperature at which carbon dioxide was released.

  FIG. 21 is a schematic configuration diagram showing a thermal analyzer for heating a carbon dioxide adsorbent and measuring a change with time of the amount of released carbon dioxide.

  The thermal analysis apparatus includes an electric furnace 201, a heater 203, a reaction tube 204, a thermocouple 205, a pipe 206, a He mass flow meter 207, and a gas chromatography 208. A reaction tube 204 is installed inside the electric furnace 201, and the surroundings can be heated by a heater 203. The adsorbent 202 is installed at the center of the reaction tube 204, and a thermocouple 205 is inserted in the vicinity of the adsorbent 202 so that the temperature of the adsorbent 202 can be measured.

  In this figure, helium (He) gas is supplied to the upper part of the reaction tube 204 through the pipe 206, and carbon dioxide released from the adsorbent 202 can be detected together with the helium (He) gas by the gas chromatography 208. It is like that.

  The heating rate was 4 ° C./min.

  Table 4 shows carbon dioxide desorption temperatures when the materials of Examples 6 to 8 and Comparative Example 3 were used. The desorption temperature was defined as the temperature near the adsorbent when the carbon dioxide release rate reached its maximum.

From this table, it can be seen that the desorption temperature of carbon dioxide is very low in Examples 6 to 8 as compared with Comparative Example 3. From this result, it is clear that the desorption temperature of CO ₂ can be significantly reduced by supporting the metal on mesoporous silica without using the metal as an oxide.

  FIG. 1 is a schematic configuration diagram illustrating a carbon dioxide recovery device using the carbon dioxide adsorbents of Examples 5 to 10.

  In this figure, the carbon dioxide recovery device includes a flow channel 1 for introducing a gas containing carbon dioxide, an adsorption unit 2, a flow channel 4, a heating device 5, and a desorption unit 6 in order from the upstream side. The carbon dioxide adsorbing material 3 is enclosed in the adsorbing portion 2 and the carbon dioxide adsorbing material 7 is enclosed in the desorbing portion 6. The carbon dioxide adsorbing material 3 of the adsorbing unit 2 and the carbon dioxide adsorbing material 7 of the desorbing unit 6 are arranged so that their installation positions can be exchanged.

  The adsorbing part 2 and the desorbing part 6 each have a semi-cylindrical shape, the carbon dioxide adsorbing material 3 and the carbon dioxide adsorbing material 7 have a single cylindrical shape having a gap, and a rotor that is rotatable about the central axis of the circular cylinder as a rotation axis; By doing so, the carbon dioxide adsorbing material 3 and the carbon dioxide adsorbing material 7 may be rotated at a predetermined speed so that the carbon dioxide adsorbing material 3 and the carbon dioxide adsorbing material 7 stay in the adsorption unit 2 and the desorption unit 6 respectively. In this case, the rotational speed of the rotor may be varied or stopped by detecting the temperature change speed of the carbon dioxide adsorbent 3 and the carbon dioxide adsorbent 7.

  A gas whose temperature is sufficiently lowered is caused to flow through the flow path 1 to adsorb carbon dioxide to the carbon dioxide adsorbing material 3 of the adsorption unit 2. The gas adsorbed / separated with carbon dioxide is heated through the flow path 4 and the heating device 5 and introduced into the desorption part 6. In the desorption unit 6, the carbon dioxide adsorbing material 7 that has adsorbed carbon dioxide in the adsorption unit 2 is heated by the heated gas to desorb and recover the carbon dioxide. And the gas which collect | recovered the carbon dioxide is sent to the carbon dioxide processing apparatus or the carbon dioxide storage apparatus through the flow path 8. Further, the flow path 4 may be provided with a bypass flow path 21 so that a part of the gas whose carbon dioxide concentration is lowered by adsorption / separation of carbon dioxide in the adsorption section 2 may be released to the atmosphere. Here, the heating device 5 may be called a gas heating unit.

  In the carbon dioxide recovery device of the present embodiment, carbon dioxide is rapidly desorbed by rapidly heating the carbon dioxide adsorbent 7 that has adsorbed carbon dioxide, and the carbon dioxide concentration of the gas introduced from the flow path 1 is The carbon dioxide concentration in the flow path 8 can be increased. Further, by providing the bypass channel 21, the flow rate of the gas having a low carbon dioxide concentration can be reduced, and the carbon dioxide concentration in the channel 8 can be further increased.

  In addition, when the gas flowing into the flow path 1 contains not only carbon dioxide but also water vapor, the water vapor contained in this gas selectively adsorbs (absorbs) water vapor as compared with carbon dioxide (drying). It is desirable that the material is placed in the flow path 1 to remove water vapor, and then the carbon dioxide is adsorbed on the carbon dioxide adsorbent 3 of the adsorption section 2. Thereby, the collection | recovery by adsorption separation of a carbon dioxide can be accelerated | stimulated.

  FIG. 2 is a schematic configuration diagram illustrating a carbon dioxide recovery device using the carbon dioxide adsorbing materials of Examples 5 to 10.

  In this figure, the carbon dioxide recovery device includes a flow channel 1 for introducing a gas containing carbon dioxide, a pressurizing device 11, an adsorption unit 2, a flow channel 4, and a decompression device 12 in order from the upstream side. The pressure reducing valve, the desorption part 6 and the flow path 8 are connected to each other, and the carbon dioxide adsorbing material 3 is enclosed in the adsorption part 2 and the carbon dioxide adsorbing material 7 is enclosed in the desorption part 6. . The carbon dioxide adsorbing material 3 of the adsorbing unit 2 and the carbon dioxide adsorbing material 7 of the desorbing unit 6 are arranged so that their installation positions can be exchanged. Here, the pressurizing device 11 may be called a gas pressurizing unit.

  The adsorbing part 2 and the desorbing part 6 each have a semi-cylindrical shape, the carbon dioxide adsorbing material 3 and the carbon dioxide adsorbing material 7 have a single cylindrical shape having a gap, and a rotor that is rotatable about the central axis of the circular cylinder as a rotation axis; By doing so, the carbon dioxide adsorbing material 3 and the carbon dioxide adsorbing material 7 may be rotated at a predetermined speed so that the carbon dioxide adsorbing material 3 and the carbon dioxide adsorbing material 7 stay in the adsorption unit 2 and the desorption unit 6 respectively. In this case, since the internal pressures of the adsorption unit 2 and the desorption unit 6 are different, it is desirable to ensure the sealing performance of the rotor. A partition plate for maintaining a predetermined pressure may be provided radially inside the rotor.

  A gas whose temperature has been sufficiently lowered is supplied to the flow path 1 on the upstream side, and the gas is pressurized by the pressurizing device 11 and supplied to the adsorption unit 2. Then, carbon dioxide is adsorbed on the carbon dioxide adsorbent 3 of the adsorption unit 2. The gas adsorbed / separated with carbon dioxide is decompressed through the flow path 4 and the decompression device 12 and introduced into the desorption part 6. In the desorption unit 6, the carbon dioxide adsorbing material 7 that has adsorbed carbon dioxide in the adsorption unit 2 is desorbed with a low-pressure gas, and carbon dioxide is recovered. And the gas which collect | recovered the carbon dioxide is sent to the carbon dioxide processing apparatus or the carbon dioxide storage apparatus through the flow path 8. Further, the flow path 4 may be provided with a bypass flow path 21 so that a part of the gas whose carbon dioxide concentration is lowered by adsorption / separation of carbon dioxide in the adsorption section 2 may be released to the atmosphere. Here, the decompression device 12 may be called a gas decompression unit.

  In the carbon dioxide recovery device of the present embodiment, the carbon dioxide adsorbent 7 that has adsorbed carbon dioxide has its adsorption equilibrium rapidly changed in the desorption section 6, so that carbon dioxide is desorbed rapidly and introduced from the flow path 1. The carbon dioxide concentration in the flow path 8 can be made higher than the carbon dioxide concentration in the gas. Further, by providing the bypass channel 21, the flow rate of the gas having a low carbon dioxide concentration can be reduced, and the carbon dioxide concentration in the channel 8 can be further increased.

  In addition, about the means in case the gas which flows in into the flow path 1 contains not only a carbon dioxide but water vapor | steam, it is the same as that of Example 11. FIG.

  FIG. 3 is a schematic configuration diagram illustrating a carbon dioxide recovery device using the carbon dioxide adsorbents of Examples 5 to 10.

  In this figure, the carbon dioxide recovery device includes, in order from the upstream side, a flow path 101 for introducing a gas containing carbon dioxide, an adsorption part in which a carbon dioxide adsorbent 102 before carbon dioxide adsorption is installed, and a carbon dioxide. The flow path 103 through which the gas from which carbon has been removed flows, the heating devices 105 and 106, and the carbon dioxide adsorbent 104 after carbon dioxide adsorption are connected to each other, and the flow path 107 and the carbon dioxide recovery section 116 are connected. This is the configuration. The carbon dioxide adsorbent 102 before adsorbing carbon dioxide in the adsorption section and the carbon dioxide adsorbent 104 in the desorption section are arranged so that their installation positions can be exchanged.

  The adsorbing part and the desorbing part are each semi-cylindrical, and the carbon dioxide adsorbing material 102 and the carbon dioxide adsorbing material 104 are one cylindrical shape having a gap, and the rotor is rotatable about the central axis of the circular cylinder. Accordingly, the carbon dioxide adsorbing material 102 and the carbon dioxide adsorbing material 104 may be rotated at a predetermined speed so as to stay in the adsorption portion and the desorption portion for a predetermined time. In this case, the speed of temperature change of the carbon dioxide adsorbent 102 and the carbon dioxide adsorbent 104 may be detected to vary or stop the rotational speed of the rotor.

  A gas whose temperature is sufficiently lowered is caused to flow through the flow path 101 to adsorb carbon dioxide to the carbon dioxide adsorbent 102 of the adsorption portion. The gas having adsorbed and separated carbon dioxide is discharged from the flow path 103. In the desorption unit, carbon dioxide is discharged from the carbon dioxide adsorbent 104 heated by the heating devices 105 and 106, and the carbon dioxide is collected by the carbon dioxide collection unit 116 through the flow path 107. And the gas which collect | recovered carbon dioxide is sent to a carbon dioxide processing apparatus or a carbon dioxide storage apparatus. Further, a part of carbon dioxide may be circulated through the flow path 117 to the desorption part. Here, the heating devices 105 and 106 may be referred to as an adsorbent heating unit.

  Further, the gas flow rate may be adjusted by installing valves 108, 110, and 109 in the flow paths 101, 107, and 117, respectively.

  In the carbon dioxide recovery device of the present embodiment, carbon dioxide is rapidly desorbed by rapidly heating the carbon dioxide adsorbent 104 that has adsorbed carbon dioxide, and the carbon dioxide concentration of the gas introduced from the flow path 101 is The carbon dioxide concentration in the channel 107 can be increased. Further, by providing the flow path 103, the gas having a low carbon dioxide concentration can be discharged.

  In addition, when the gas flowing into the channel 101 contains not only carbon dioxide but also water vapor, the water vapor contained in this gas selectively adsorbs (absorbs) water vapor as compared with carbon dioxide (drying). It is desirable that the material is placed in the flow path 101 to remove water vapor, and then the carbon dioxide is adsorbed to the carbon dioxide adsorbent 102 of the adsorption portion. Thereby, the collection | recovery by adsorption separation of a carbon dioxide can be accelerated | stimulated.

  FIG. 4 is a schematic configuration diagram illustrating a carbon dioxide recovery device using the carbon dioxide adsorbents of Examples 5 to 10.

  In this figure, the carbon dioxide recovery device is composed of a flow channel 101 for introducing a gas containing carbon dioxide, a pressurizing device 111 and a carbon dioxide adsorbent 102 before carbon dioxide adsorption in order from the upstream side. A configuration in which the adsorbing section configured, the flow path 103 through which the gas from which carbon dioxide has been removed flows, the desorption section in which the carbon dioxide adsorbing material 104 after carbon dioxide adsorption is installed, and the flow path 107 and the carbon dioxide recovery section 116 are connected. It is. The carbon dioxide adsorbent 102 before adsorbing carbon dioxide in the adsorber and the carbon dioxide adsorbent 104 in the desorber are arranged so that their installation positions can be exchanged.

  The adsorbing part and the desorbing part are each semi-cylindrical, and the carbon dioxide adsorbing material 102 and the carbon dioxide adsorbing material 104 are one cylindrical shape having a gap, and the rotor is rotatable about the central axis of the circular cylinder. Thus, the carbon dioxide adsorbing material 102 and the carbon dioxide adsorbing material 104 may be rotated at a predetermined speed so as to stay in the adsorption portion and the desorption portion for a predetermined time. In this case, since the internal pressure is different between the adsorption portion and the desorption portion, it is desirable to ensure the sealing performance of the rotor. A partition plate for maintaining a predetermined pressure may be provided radially inside the rotor.

  A gas whose temperature is sufficiently lowered is caused to flow through the flow path 101, and the gas is pressurized by the pressurizing device 111 and supplied to the carbon dioxide adsorbent 102. Then, carbon dioxide is adsorbed on the carbon dioxide adsorbent 102 of the adsorption unit. The gas having adsorbed and separated carbon dioxide is discharged from the flow path 103. In the desorption part, a small amount of gas is circulated and the pressure is lower than that of the adsorption part. In the desorption unit, the carbon dioxide adsorbing material 104 that has adsorbed carbon dioxide is desorbed by a low-pressure gas, and the carbon dioxide recovery unit 116 recovers carbon dioxide through the flow path 107. And the gas which collect | recovered carbon dioxide is sent to a carbon dioxide processing apparatus or a carbon dioxide storage apparatus. Further, a part of carbon dioxide may be circulated through the flow path 117 to the desorption part.

  In the carbon dioxide recovery apparatus of the present embodiment, the carbon dioxide adsorbent 104 that has adsorbed carbon dioxide has its adsorption equilibrium rapidly changed at the desorption part, so that the carbon dioxide is rapidly desorbed and the gas introduced from the flow path 101. The carbon dioxide concentration of the flow path 107 can be made higher than the carbon dioxide concentration of. Further, by providing the flow path 103, the gas having a low carbon dioxide concentration can be discharged.

  In addition, about the means in case the gas which flows in into the flow path 101 contains not only a carbon dioxide but water vapor | steam, it is the same as that of Example 13. FIG.

  FIG. 5 is a schematic configuration diagram illustrating a carbon dioxide recovery device using the carbon dioxide adsorbents of Examples 5 to 10.

  In this figure, the carbon dioxide recovery device is composed of a flow channel 101 for introducing a gas containing carbon dioxide, a pressurizing device 111 and a carbon dioxide adsorbent 102 before carbon dioxide adsorption in order from the upstream side. A configured adsorbing section, a flow path 103 in which a gas from which carbon dioxide has been removed flows, a desorption section configured by two parts, a carbon dioxide adsorbing material 104 after heating carbon dioxide and heating devices 105 and 106, and a flow path 107. And the carbon dioxide recovery unit 116 are connected. The carbon dioxide adsorbent 102 before adsorbing carbon dioxide in the adsorber and the carbon dioxide adsorbent 104 in the desorber are arranged so that their installation positions can be exchanged.

  The adsorbing part and the desorbing part are each semi-cylindrical, the carbon dioxide adsorbing material 102 and the carbon dioxide adsorbing material 104 are one cylindrical shape having a gap, and a rotor that is rotatable about the central axis of the circular cylinder as a rotation axis. Accordingly, the carbon dioxide adsorbing material 102 and the carbon dioxide adsorbing material 104 may be rotated at a predetermined speed so as to stay in the adsorption portion and the desorption portion for a predetermined time.

  A gas whose temperature is sufficiently lowered is caused to flow through the flow path 101, and the gas is pressurized by the pressurizing device 111 and supplied to the carbon dioxide adsorbent 102. Then, carbon dioxide is adsorbed on the carbon dioxide adsorbent 102 of the adsorption unit. The gas having adsorbed and separated carbon dioxide is discharged from the flow path 103. In the desorption part, a small amount of gas is circulated and the pressure is lower than that of the adsorption part. In the desorption unit, the carbon dioxide adsorbing material 104 that has adsorbed carbon dioxide is desorbed by low-pressure gas, and carbon dioxide is collected by the carbon dioxide collecting unit 116 through the flow path 107. And the gas which collect | recovered carbon dioxide is sent to a carbon dioxide processing apparatus or a carbon dioxide storage apparatus. Further, a part of carbon dioxide may be circulated through the flow path 117 to the desorption part. In this embodiment, a pump 122 is installed in the flow path 117 to promote the circulation of carbon dioxide. That is, a gas containing high-concentration carbon dioxide flowing out from the desorption part is recirculated to the desorption part. You may call these flow paths 117 and the pump 122 a gas circulation part.

  In addition, a compressor 121 may be installed to send carbon dioxide from the flow path 107 to the carbon dioxide recovery unit 116.

  In the carbon dioxide recovery device of the present embodiment, by pressurizing in front of the carbon dioxide adsorbent 102 of the adsorbing portion, carbon dioxide is adsorbed rapidly, and the carbon dioxide adsorbent 104 adsorbing carbon dioxide is rapidly heated. Thus, carbon dioxide can be desorbed rapidly, and the carbon dioxide concentration in the channel 107 can be made higher than the carbon dioxide concentration of the gas introduced from the channel 101. Further, by providing the flow path 103, the gas having a low carbon dioxide concentration can be discharged.

  In addition, about the means in case the gas which flows in into the flow path 101 contains not only a carbon dioxide but water vapor | steam, it is the same as that of Example 13. FIG.

  FIG. 6 is a schematic configuration diagram illustrating a carbon dioxide recovery device using the carbon dioxide adsorbing materials of Examples 5 to 10.

  In this figure, the carbon dioxide recovery device includes, in order from the upstream side, a flow path 101 for introducing a gas containing carbon dioxide, a pressurizing device 111, a carbon dioxide adsorbent 102 before carbon dioxide adsorption, and carbon dioxide adsorption. An adsorbing section composed of three weight detecting sections 112 (referred to as first weight detecting sections) for measuring the weight of the material 102, a flow path 103 through which a gas from which carbon dioxide has been removed flows, and after carbon dioxide adsorption The carbon dioxide adsorbing material 104, the heating devices 105 and 106, and the carbon dioxide adsorbing material 104 and the carbon dioxide adsorbing material 104 after the carbon dioxide adsorbing are measured by a weight detecting unit 113 (referred to as a second weight detecting unit). This is a configuration in which a desorption part constituted by three, a flow path 107 and a carbon dioxide recovery part 116 are connected. The carbon dioxide adsorbent 102 before adsorbing carbon dioxide in the adsorption section and the carbon dioxide adsorbent 104 in the desorption section are arranged so that their installation positions can be exchanged. Further, the data of the weight detection unit 112 and the weight detection unit 113 is sent to the control device 114, and commands the exchange of the carbon dioxide adsorbent 102 and the carbon dioxide adsorbent 104. Here, the control device 114 may be referred to as a control unit.

  The adsorbing part and the desorbing part are each semi-cylindrical, and the carbon dioxide adsorbing material 102 and the carbon dioxide adsorbing material 104 are one cylindrical shape having a gap, and the rotor is rotatable about the central axis of the circular cylinder. Accordingly, the carbon dioxide adsorbing material 102 and the carbon dioxide adsorbing material 104 may be rotated at a predetermined speed so as to stay in the adsorption portion and the desorption portion for a predetermined time.

  A gas whose temperature is sufficiently lowered is caused to flow through the flow path 101, and the gas is pressurized by the pressurizing device 111 and supplied to the carbon dioxide adsorbent 102. Then, carbon dioxide is adsorbed on the carbon dioxide adsorbent 102 of the adsorption unit. The gas having adsorbed and separated carbon dioxide is discharged from the flow path 103. In the desorption part, a small amount of gas is circulated and the pressure is lower than that of the adsorption part. In the desorption unit, the carbon dioxide adsorbing material 104 that has adsorbed carbon dioxide is desorbed by a low-pressure gas, and the carbon dioxide recovery unit 116 recovers carbon dioxide through the flow path 107. And the gas which collect | recovered carbon dioxide is sent to a carbon dioxide processing apparatus or a carbon dioxide storage apparatus. Further, a part of carbon dioxide may be circulated through the flow path 117 to the desorption part. When the carbon dioxide adsorbent 102 and the carbon dioxide adsorbent 104 are exchanged, the carbon dioxide adsorption amount is calculated from the data transmitted from the weight detection unit 112 to the control device 114, and the carbon dioxide adsorption amount of the carbon dioxide adsorbent 102 is saturated. When approaching, the controller 114 issues a replacement instruction for the carbon dioxide adsorbent 102 and the carbon dioxide adsorbent 104.

  In the carbon dioxide recovery device of the present embodiment, by pressurizing in front of the carbon dioxide adsorbent 102 of the adsorbing portion, carbon dioxide is adsorbed rapidly, and the carbon dioxide adsorbent 104 adsorbing carbon dioxide is rapidly heated. Thus, carbon dioxide can be desorbed rapidly, and the carbon dioxide concentration in the channel 107 can be made higher than the carbon dioxide concentration of the gas introduced from the channel 101. Further, by providing the flow path 103, the gas having a low carbon dioxide concentration can be discharged.

  In addition, about the means in case the gas which flows in into the flow path 101 contains not only a carbon dioxide but water vapor | steam, it is the same as that of Example 13. FIG.

  FIG. 7 shows a configuration (multistage type) in which the number of stages of each of the carbon dioxide adsorbents 102a to 102c and the carbon dioxide adsorbents 104a to 104c is made plural in the carbon dioxide recovery apparatus of the sixteenth embodiment. From the weight detectors 112a to 112c for measuring the weight of each carbon dioxide adsorbent 102a to 102c and the weight detectors 113a to 113c for measuring the weight of the carbon dioxide adsorbents 104a to 104c to the control device 114 (also referred to as a controller). Data is transmitted, and if the carbon dioxide adsorbents 102a to 102c are close to carbon dioxide adsorption saturation, the weight of the carbon dioxide adsorbents 104a to 104c is reduced and the carbon dioxide is desorbed as in the sixteenth embodiment. Give orders to exchange for the most advanced.

  In the carbon dioxide recovery apparatus of the present embodiment, the same effects as those of the embodiment 16 can be obtained, and the carbon dioxide adsorbents 102a to 102c and the carbon dioxide adsorbents 104a to 104a to 104a to 102e can be efficiently performed without stopping the flow of gas containing carbon dioxide. An exchange of 104c can be performed.

  ADVANTAGE OF THE INVENTION According to this invention, while providing the carbon dioxide adsorbent which has higher adsorption capability than the conventional carbon dioxide adsorbent, the efficiency of a carbon dioxide recovery apparatus can be improved using an adsorbent with high adsorption capability. In addition, an adsorbent having a carbon dioxide desorption temperature lower than that of a conventional carbon dioxide adsorbent can be provided, and the operating cost of the carbon dioxide recovery device can be reduced by using an adsorbent having a low desorption temperature.

  INDUSTRIAL APPLICABILITY The present invention can be used for the purpose of adsorbing and recovering carbon dioxide from exhaust gas containing carbon dioxide.

  1: flow path, 2: adsorption section, 3: carbon dioxide adsorbent, 4: flow path, 5: heating device, 6: desorption section, 7: carbon dioxide adsorbent, 8: flow path, 11: pressurization apparatus, 12: decompression device, 105, 106: heating device, 111: pressurization device, 112, 113: weight detection unit, 114: control device, 116: carbon dioxide recovery unit, 121: compressor, 122: pump.

Claims (9)

  In a carbon dioxide adsorbent for adsorbing and separating carbon dioxide from a gas containing carbon dioxide, a carrier of the carbon dioxide adsorbent is formed of mesoporous silica, and Mg, Ca, Sr, Ba, Y and La are formed on the carrier. A carbon dioxide adsorbent characterized in that at least one element selected from the group of the above is supported.   An adsorption part in which a carbon dioxide adsorbent for adsorbing and separating carbon dioxide from a gas containing carbon dioxide is installed, and the carbon dioxide adsorbed to the carbon dioxide adsorbent in this adsorption part is desorbed and recovered by heating. And a gas heating unit for heating the gas that passes through the adsorption unit and flows into the desorption unit, and exchanges the carbon dioxide adsorbent between the adsorption unit and the desorption unit. The carbon dioxide adsorbent support is formed of mesoporous silica, and the support carries at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Y, and La. Carbon dioxide recovery device.   An adsorbing part provided with a carbon dioxide adsorbing material for adsorbing and separating carbon dioxide from a gas containing carbon dioxide, and the carbon dioxide adsorbed on the carbon dioxide adsorbing material in this adsorbing part are desorbed by depressurization. A desorption unit for recovery, a gas pressurization unit for increasing the pressure of the gas sent to the adsorption unit, and a gas decompression unit for reducing the pressure of the gas that has passed through the adsorption unit, The carbon dioxide adsorbing material can be exchanged between the adsorbing portion and the desorbing portion, and the carrier of the carbon dioxide adsorbing material is formed of mesoporous silica, and Mg, Ca, Sr, Ba, Y, and La are formed on the carrier. A carbon dioxide recovery device on which at least one element selected from the group is supported.   An adsorbing part in which a carbon dioxide adsorbing material for adsorbing and separating carbon dioxide from a gas containing carbon dioxide is installed, and the carbon dioxide adsorbed on the carbon dioxide adsorbing material in this adsorbing part is desorbed by heating. A desorption part for recovery, a gas pressurization part for increasing the pressure of the gas sent to the adsorption part, and a gas heating part for heating the gas that has passed through the adsorption part, The carbon dioxide adsorbent can be exchanged between a part and the desorption part, and the carrier of the carbon dioxide adsorbent is formed of mesoporous silica, and the carrier is made of Mg, Ca, Sr, Ba, Y and La. A carbon dioxide recovery device, wherein at least one selected element is supported.   An adsorbing part in which a carbon dioxide adsorbing material for adsorbing and separating carbon dioxide from a gas containing carbon dioxide is installed, and the carbon dioxide adsorbed on the carbon dioxide adsorbing material in this adsorbing part is desorbed by heating. A desorption unit for collecting and an adsorbent heating unit for heating the carbon dioxide adsorbent of the desorption unit, wherein the carbon dioxide adsorbent can be exchanged between the adsorption unit and the desorption unit. The carbon dioxide adsorbent carrier is formed of mesoporous silica, and the carrier carries at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Y and La. Carbon dioxide recovery device.   The carbon dioxide recovery apparatus according to claim 5, further comprising a gas pressurizing unit for increasing the pressure of the gas sent to the adsorption unit.   Furthermore, a first weight detection unit for detecting the weight of the carbon dioxide adsorbent of the adsorption unit, a second weight detection unit for detecting the weight of the carbon dioxide adsorbent of the desorption unit, A control unit for calculating the carbon dioxide adsorption amount of the carbon dioxide adsorbent from values detected by the first weight detection unit and the second weight detection unit, and for controlling the replacement timing of the carbon dioxide adsorbent; The carbon dioxide recovery device according to any one of claims 2 to 6, wherein   The carbon dioxide recovery device according to claim 7, further comprising a gas circulation unit configured to recirculate a part of the gas flowing out from the desorption unit to the desorption unit.   Each of the adsorption unit and the desorption unit includes a plurality of stages of carbon dioxide adsorbents, and includes a weight detection unit for detecting the weight of each of the plurality of stages of carbon dioxide adsorbents. The weight of the carbon dioxide adsorbent is detected, and the controller calculates the carbon dioxide adsorption amount of the carbon dioxide adsorbent from the value detected by the weight detector, and controls the replacement timing of the carbon dioxide adsorbent. It implements, The carbon dioxide recovery device of Claim 7 or 8 characterized by the above-mentioned.

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