JP2967166B2 - Carbon dioxide gas separation and recovery method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for separating and recovering carbon dioxide contained in a mixed gas.

[0002]

2. Description of the Related Art In order to solve global environmental problems, the need to recover carbon dioxide has been increased. As a method of separating and recovering carbon dioxide from mixed gas such as combustion exhaust gas, there is a method of supplying carbon dioxide in a solution containing sodium ions and recovering it as sodium carbonate. Are required, and a membrane separation method, an adsorption separation method, and a cryogenic separation method are being studied. However, in order to perform treatment using these methods alone, the concentration of carbon dioxide in the mixed gas is often insufficient, and good separation results cannot be obtained. For example, the cryogenic separation method is inefficient in the treatment of a mixed gas in which the concentration of carbon dioxide in the gas to be treated is not high, and good results cannot be obtained. In general, it is said that it is difficult to efficiently collect carbon dioxide in a mixed gas when any of the adsorption separation method, the membrane separation method, and the cryogenic separation method is used alone. Therefore, a method of treating a mixed gas using a combination of a membrane separation method and a cryogenic separation method has been proposed. In the method by this combination, when performing the separation treatment by the membrane separation method, the mixed gas having a carbon dioxide concentration of about 10% can be concentrated to 30 to 90%, so that the subsequent cryogenic separation method is efficiently performed. It becomes possible. Generally, in the membrane separation method, in consideration of the efficiency, a non-permeate gas is used as a recycle gas and added to an inlet gas of a membrane separation device. For this reason, also in the method using the above-mentioned combination, a method is employed in which the entire amount of off-gas from the cryogenic separation process in the subsequent stage is recycled to the inlet gas of the membrane separation device in the preceding stage. As a result, there is a problem that the amount of processing gas in the membrane separation apparatus increases, and as a result, the energy required for separating carbon dioxide increases. In addition, the raw material supplied to the cryogenic separation step needs to remove moisture contained therein, and dehumidification is performed by an adsorbent. In the case of the conventional method, the moisture adsorbed by the adsorbent is desorbed. Since a regeneration gas from the outside is introduced into the system and used as the regeneration gas for regeneration, there is a problem that a large amount of energy is required.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a method for separating and recovering carbon dioxide contained in a mixed gas from a mixed gas by a method including a membrane separation step and a cryogenic separation step. The task is to provide.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, in the method of separating and recovering carbon dioxide contained in the mixed gas as liquefied carbon dioxide from the mixed gas, (i) a first method of separating the mixed gas into a gas containing concentrated carbon dioxide and a residual gas A membrane separation step, (ii) a pressurizing step of increasing the pressure of the gas containing the concentrated carbon dioxide gas, (iii) a dehumidifying step of dehumidifying the increased pressure gas, and (iv) cooling the dehumidified gas to form a gas therein. A cooling step of liquefying the carbon dioxide gas contained therein, (v) a cryogenic separation step of separating the gas containing the liquefied carbon dioxide gas into an off gas containing the carbon dioxide gas and liquefied carbon dioxide gas, and (vi) the cryogenic separation step. The second off-gas is separated into a gas containing concentrated carbon dioxide gas and a residual gas.
A membrane separation step, and (vii) a circulation step of circulating the gas containing the concentrated carbon dioxide gas obtained in the second membrane separation step to an optional step selected from the above-mentioned pressure increasing step, dehumidifying step and cooling step. The present invention provides a method for separating and recovering carbon dioxide from a mixed gas. Further, according to the present invention, in the method for separating and recovering carbon dioxide contained in the mixed gas as liquefied carbon dioxide from the mixed gas, (i) first separating the mixed gas into a gas containing concentrated carbon dioxide and a residual gas A membrane separation step, (ii) a pressurizing step of increasing the pressure of the gas containing the concentrated carbon dioxide gas, (iii) a dehumidifying step of dehumidifying the pressurized gas using an adsorbent, and (iv) an adsorbent that has adsorbed the moisture. Adsorbent regeneration process for regeneration by contact with regeneration gas,
(V) a cooling step of cooling the dehumidified gas to liquefy carbon dioxide contained in the gas, and (vi) separating the gas containing liquefied carbon dioxide into an off gas containing carbon dioxide and liquefied carbon dioxide. A cryogenic separation step, (vii) a second membrane separation step of separating off gas obtained in the cryogenic separation step into a gas containing concentrated carbon dioxide gas and a residual gas, and (viii) the second membrane separation step. A circulating step of circulating at least a part of the obtained gas containing concentrated carbon dioxide gas as an adsorbent regenerating gas to the adsorbent regenerating step, (ix) a gas after contacting the adsorbent in the adsorbent regenerating step The pressurizing step, a circulating step of circulating to any step selected from the dehumidifying step and the cooling step, the separation and separation of carbon dioxide from the mixed gas, characterized by including
A recovery method is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The mixed gas to be treated in the present invention is a mixed gas containing carbon dioxide, and such a mixed gas is supplied to a boiler such as a thermal power plant or various factories.
And exhaust gas generated from various facilities such as blast furnaces at steelworks,
Natural gas produced including carbon dioxide gas is included. These mixed gases generally contain about 5 to 95% by volume of carbon dioxide.

FIG. 1 shows a flow sheet of a conventional method in which a mixed gas containing carbon dioxide is treated in two steps of a membrane separation step and a cryogenic separation step. In this conventional method, a mixed gas containing carbon dioxide is supplied to a membrane separation step 1 through a line 11, where the carbon dioxide is concentrated. The gas containing the concentrated carbon dioxide gas is introduced into the pressurizing step 2, and after being pressurized, is introduced into the dehumidifying step 3 with the adsorbent through the line 13, where the moisture in the gas is removed. The gas from which water has been removed enters a cooling step 4 through a line 14, where it is cooled to a temperature at which carbon dioxide gas liquefies, and then supplied to a cryogenic separation step 5 through a line 15, where it is cooled. It is cryogenically separated by a cold separation tower. Liquefied carbon dioxide gas is extracted from the bottom of the cryogenic separation tower through the line 17, while off-gas containing high-pressure carbon dioxide is separated from the top of the cryogenic separation tower. This offgas is on line 1
6 and is introduced into a power recovery step 6, where the energy held by the high-pressure gas is recovered as power. The gas discharged from the power recovery step 6 is circulated through the line 18 to the membrane separation step 1.

Next, FIG. 2 shows a flow sheet of a method for treating a mixed gas containing carbon dioxide gas according to the present invention. In the method of the present invention, the mixed gas containing carbon dioxide is supplied to the line 11.
To the first membrane separation step 1 where the carbon dioxide gas is concentrated. The gas containing the concentrated carbon dioxide gas is introduced into the pressurizing step 2, and after being pressurized, is introduced into the dehumidifying step 3 with the adsorbent through the line 13, where the moisture in the gas is removed. The degassed gas enters a cooling step 4 through a line 14, where it is cooled to a temperature at which carbon dioxide gas is liquefied, and then passed through a line 15 to a cryogenic separation step 5.
Where it is cryogenically separated by a cryogenic separation tower.
Liquefied carbon dioxide gas is extracted from the bottom of the cryogenic separation tower through the line 17, while off-gas containing high-pressure carbon dioxide is separated from the top of the cryogenic separation tower. This off-gas is introduced into the second membrane separation step 7 through the line 16, where the off-gas is subjected to membrane separation under high pressure conditions, and the carbon dioxide in the off-gas is concentrated. The concentrated off-gas of the carbon dioxide gas is circulated through the line 19 to the adsorbent regenerating step 8, where it is used as a regenerating gas for the adsorbent that has absorbed moisture and is brought into contact with the adsorbent. The off-gas containing water and carbon dioxide gas after regenerating the adsorbent in the adsorbent regeneration step 8 is supplied to the line 20.
And is circulated to the cryogenic separation step 5 via the pressure step 2, the dehumidification step 3 and the cooling step 4. The residual gas (high-pressure off-gas that has not passed through the membrane) obtained in the second membrane separation step 7 passes through the power recovery step 6 through the line 18, and is then discharged to the atmosphere through the line 21. When the mixed gas is treated as described above, the gas containing the concentrated carbon dioxide gas obtained in the second membrane separation step 7 does not necessarily need to be circulated to the adsorbent regeneration step 8, and the entire amount thereof is transferred to the line 12.
And a part thereof can be circulated to the adsorbent regeneration step 8, and the remainder can be added to the line 12.

[0008] The first membrane separation step 1 used in the present invention is carried out using a membrane separation apparatus. Various types of conventionally known membrane separation devices are used. In addition, as the membrane (gas separation membrane) used in this case, various conventionally known membranes such as polyimide, polysulfone, cellulose triacetate, and silicone can be used. In this membrane separation device, a mixed gas containing carbon dioxide gas is introduced from a gas inlet on the supply side of the membrane, flows in the direction of the outlet, and the residual gas (membrane non-permeated gas) is discharged from an outlet on the gas supply side. You. On the other hand, on the gas permeable side of the membrane, a gas having an increased carbon dioxide concentration is obtained as a membrane permeable component. The operation pressure on the gas supply side in this membrane separation step is 0 to 150 kg /
cm ² G, and the pressure ratio on the gas permeation side to the pressure on the gas supply side is 0.001 to 0.5, and preferably 0.01 to 0.5.
０．２0.2. The operating temperature is about 10 to 80C.

In the first separation step 1, 5-95
The raw material gas containing carbon dioxide gas of 30% to 98% by volume
Is separated into a gas containing concentrated carbon dioxide gas (membrane-permeable gas) and a residual gas (membrane-impermeable gas). The gas containing the concentrated carbon dioxide gas obtained in this membrane separation step is sent to the next pressurization step 2. On the other hand, the residual gas is released into the atmosphere after further performing a carbon dioxide gas removal treatment as necessary.

The pressurizing step 2 used in the present invention is carried out by using a combination of a compressor and a KO (knockout) drum. In this pressurization step, the gas containing the concentrated carbon dioxide gas obtained from the membrane separation step 1 is 10 to 50 kg /
The pressure is raised to cm ² G, preferably 10 to 30 kg / cm ² G.

[0011] The dehumidification step 3 used in the present invention is carried out using a dehumidification tower containing an adsorbent. As the adsorbent, conventionally known ones, for example, silica gel, alumina, zeolite, activated carbon and the like are used. In this dehumidification process,
At least two dehumidification towers are used. A part of the dehumidifying tower is used for a dehumidifying operation, and the dehumidifying tower which has absorbed the remaining moisture is subjected to regeneration of the adsorbent.

The adsorbent regenerating step 8 used in the present invention is carried out by bringing a regenerating gas into contact with the adsorbent having adsorbed moisture and desorbing the adsorbed moisture. As the regeneration gas, various conventionally known gases can be used, but in the case of the present invention, it is preferable to use a gas containing concentrated carbon dioxide gas (off gas) obtained in the second membrane separation step 7.
Thus, the regeneration of the adsorbent can be performed efficiently and with a reduced energy consumption in a closed system without introducing a special regeneration gas from the outside.
In such a method, for example, it is not necessary to purge the raw material gas into the atmosphere, and it is possible to prevent a decrease in the carbon dioxide concentration when the adsorption tower is switched. Heating from outside,
No cooling is required.

The cooling step 4 used in the present invention is performed using a cooler using a refrigerant. In this cooling step, the gas from the dehumidifying step is at a temperature at which the carbon dioxide gas is liquefied,
Usually, -10 to -50C, preferably -20 to -50C
Cooled to a temperature of

The cryogenic separation step 5 used in the present invention is carried out using a cryogenic separation column (rectification column). A conventionally known cryogenic separation tower is used. In this cooling separation column, gaseous off-gas is extracted from the top of the column, and liquefied carbon dioxide gas is extracted from the bottom of the column. In this case, the tower top temperature is about −20 to −50 ° C., and the tower bottom temperature is 0
~ -30 ° C. As described above, in this cryogenic separation step, the gas containing liquefied carbon dioxide is separated into gaseous offgas and liquefied carbon dioxide, and the offgas is usually 20 to 98% by volume of carbon dioxide. including. In the present invention, this off-gas is sent to the second membrane separation step. On the other hand, the liquefied carbon dioxide gas is sent to the storage tank and stored in the tank.

The second membrane separation step 7 used in the present invention comprises the first
This is carried out using the same membrane separation device as used in the membrane separation step. The operating pressure (pressure on the gas supply side) in this membrane separation step is 5 to 100 kg / cm ² G, and the ratio of the pressure on the gas permeation side to the pressure on the gas supply side is 0.001 to
0.5, preferably 0.01 to 0.2. The operating temperature is between 0 and 60C, preferably between 10 and 50C. At least a part of the gas containing the concentrated carbon dioxide gas obtained in the membrane separation step is supplied to the pressure increasing step 2, the dehumidifying step 3, and the cooling step 4.
Is circulated to any process selected from
It is circulated to the cryogenic separation step 5. When circulating the gas containing the concentrated carbon dioxide gas to the dehumidifying step 3 or the cooling step 4, the gas is circulated by adjusting the pressure so as to be the same as the pressure in those steps. Further, in the present invention, all or a part of the gas containing the concentrated carbon dioxide gas can be sent to the adsorbent regeneration step 8. The residual gas obtained in the second membrane separation step 7 is sent to the next power recovery step 6.

The power recovery step 6 used in the present invention can be carried out by using a conventional apparatus for recovering the energy held from high-pressure gas, for example, an expander. The exhaust gas from the power recovery step is released to the atmosphere after further performing a carbon dioxide gas removal treatment as necessary.

FIG. 3 shows a detailed flow chart of a method including a second membrane separation step and a cryogenic separation step according to the present invention. In FIG. 3, 31 is a compressor, 32 is a water-cooled cooler, 33 is a KO drum, 34 and 35 are dehumidification towers, 36 is a cryogenic separation tower, 37 is a flash drum, 38 is a liquefied carbon dioxide gas storage tank, and 41 is a refrigerant. , 42 is a pump, 43 is a heat exchanger, 44 is an expander, and M is a second
1 shows a membrane separation device.

According to the flow sheet shown in FIG. 3, in order to carry out the method including the second membrane separation step and the cryogenic separation step according to the present invention, the concentrated carbon dioxide obtained in the first membrane separation step (not shown) is used. Gas, including gas, passes through line 51 to the first
After being sent to the compressor 31 where the pressure is increased, it is introduced into the first KO drum 33 through the line 52 and the cooler 32. The gas component obtained in the first KO drum 33 is sent to the second compressor 31 through a line 53,
After the pressure is increased here, the pressure is introduced into the second KO drum 33 through the line 54 and the cooler 32. Second KO drum 3
The gas component obtained in 3 is sent to the third compressor 31 through a line 55, where it is pressurized, and then introduced into a third KO drum 33 through a line 56 and a cooler 32. The gas component obtained in the third KO drum 33 is sent to the fourth compressor 31 through a line 57, where it is pressurized, and then introduced into the fourth KO drum 33 through a line 58 and a cooler 32. The gas component obtained in the fourth KO drum 33 is sent to the dehumidification tower 34 through the line 59, where the water contained in the gas is removed.

The dehumidified gas passes through a cooling process consisting of a line 60, a heat exchanger 43, a line 61, a cooler 41, a line 62, a heat exchanger 43, a line 63, and a cooler 41, and becomes liquefied carbon dioxide gas. Cryogenic separation column 3 in the form of a mixture with gas
6 is introduced.

In the cryogenic separation column 36, the mixture of the introduced liquefied carbon dioxide and gas is distilled, and liquefied carbon dioxide is extracted from the bottom of the column through a line 66 and introduced into the flash drum 37. Is done. Flash drum 37
The liquefied carbon dioxide gas forming the liquid component obtained in is introduced into the liquefied carbon dioxide gas storage tank 38 through the line 69,
Is stored. The liquefied carbon dioxide stored in this tank is
It is withdrawn through line 70 and pump 42 as needed. On the other hand, the gas component obtained by the flash drum 37 is sent to the compressor 31 through a line 68, and after being pressurized there, is circulated through a line 45 to a line 62 in a cooling process.

The off-gas containing carbon dioxide gas obtained from the top of the cryogenic separation tower 36 is introduced into the flash drum 37 through the line 64 and the cooler 41. The liquid component obtained by the flash drum is returned to the top of the cryogenic separation tower 36 through the line 65. On the other hand, the gas component obtained by the flash drum 37 is supplied to the line 71, the heat exchanger 43,
After passing through the line 72 and the heat exchanger 43, the second membrane separator M
Where the membrane is separated.

The gas containing the concentrated carbon dioxide gas obtained as a membrane permeable component in the second membrane separation device M is used as an adsorbent regeneration gas, and is introduced into the dehumidification tower 35 through the line 75 after the dehumidification process. Here, the adsorbent is brought into contact with the adsorbent to remove water adsorbed on the adsorbent, thereby regenerating the adsorbent. The gas containing carbon dioxide and moisture that has passed through the dehumidification tower 35 is circulated through the line 61 to the compressor 31 which forms a pressure increasing step. The high-pressure residual gas obtained as a non-membrane component from the second membrane separator M is introduced into the expander 44 through the line 74, and a part of the energy of the high-pressure gas is recovered. The gas from the expander 44 enters the expander 44 through the cold heat recovery unit 41, where the energy of the gas is further recovered. The exhaust gas from the expander 44 is discharged to the atmosphere through a line 77 and a cold / heat recovery unit 41 and a line 78.

[0023]

Next, the present invention will be described in more detail with reference to examples.

Example 1 A mixed gas composed of 13.2 vol% of carbon dioxide gas, 12.0 vol% of moisture, 71.3 vol% of nitrogen, and 3.5 vol% of oxygen was subjected to a first membrane separation treatment, and then a second gas shown in FIG. The treatment was performed according to a flow chart of a method including a membrane separation step and a cryogenic separation step. The main operation conditions in the process in this case are shown below. (1) First membrane separation step (i) Separation membrane: polyimide-based separation membrane (ii) Operating temperature: 50 ° C. (iii) Gas supply side pressure: 0.05 kg / cm ² G (iv) Gas permeation side pressure: 0 .925 kg / cm ² G (v) Component composition of membrane-permeable gas Carbon dioxide gas: 37.5 vol% Water content: 44.7 vol% Nitrogen: 14.7 vol% Oxygen: 3.1 vol% (vi) Component composition of non-membrane gas Carbon dioxide: 6.7 vol% Water: 2.0 vol% Nitrogen: 87.5 vol% Oxygen: 3.8 vol%

(2) Cryogenic separation step (i) Feed temperature: -30 ° C (ii) Bottom temperature: -20 ° C (iii) Top temperature: -40 ° C (iv) Operating pressure: 19 kg / cm ² G (v) Component composition of off gas Carbon dioxide: 30.0 vol% Water: 0 vol% Nitrogen: 57.8 vol% Oxygen: 12.2 vol% (vi) Liquefied carbon dioxide purity: 99.9 wt% (3) Second membrane separation Step (i) Separation membrane: polyimide-based separation membrane (ii) Operating temperature: 40 ° C. (iii) Gas supply side pressure: 18 kg / cm ² G (iv) Gas permeation side pressure: 0.5 kg / cm ² G (v) Component composition of membrane-permeable gas Carbon dioxide: 67.5 vol% Water: 0 vol% Nitrogen: 18.5 vol% Oxygen: 14.0 vol% (vi) Component composition of non-membrane-permeating gas Carbon dioxide: 3.5 vol% Water: 0 vol% Nitrogen: 85.6 vol% Oxygen: 10 9 vol% (4) dehumidifying step (i) adsorbents: activated carbon (ii) adsorption ^{pressure: 20kg / cm 2 A (iii} ) regeneration pressure: atmospheric pressure (iv) Operation Temperature: room temperature (v) drying gas dew point temperature: -40 ° C

When processing the raw material mixed gas under the above conditions,
Carbon dioxide in the raw material mixed gas was obtained at a recovery rate of 60%. When the method of the present invention is compared with the conventional method as shown in FIG. 1, the amount of energy required to separate and recover carbon dioxide in the mixed gas as liquefied carbon dioxide is smaller than that of the method of the present invention. In the case of the present embodiment, only about 94% of the energy required for the conventional method is required.

[0027]

According to the present invention, in the second membrane separation step, the off-gas containing carbon dioxide gas from the cryogenic separation step is subjected to membrane separation, and at least a part of the obtained gas containing concentrated carbon dioxide gas is subjected to a pressure increasing step. By circulating to the cryogenic separation step via the dehumidification step and the cooling step, the rate of separation and recovery of carbon dioxide from the mixed gas is improved, and the amount of energy required per kg of liquefied carbon dioxide can be reduced. Further, in the present invention, by using at least a part of the concentrated off-gas of the carbon dioxide gas obtained in the second membrane separation step as a regeneration gas of an adsorbent that has adsorbed moisture after the dehumidification treatment, it can be externally provided. The regeneration of the adsorbent can be performed efficiently and economically as a closed system without introducing a special regeneration gas.

[Brief description of the drawings]

FIG. 1 shows a flow sheet according to a conventional method.

FIG. 2 shows an example of a flow sheet according to the method of the present invention.

FIG. 3 shows a detailed flow chart of a method including a second membrane separation step and a cryogenic separation step according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 1st membrane separation process 2 Pressurization process 3 Dehumidification process 4 Cooling process 5 Cryogenic separation process 6 Power recovery process 7 2nd membrane separation process 8 Adsorbent regeneration process 31 Compressor 33 KO drum 37 Flash drum 34, 35 Dehumidification tower 38 Liquefaction Carbon dioxide storage tank 44 Expander M Membrane separation device

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI F25J 1/00 F25J 1/00 D (73) Patentee 000176763 Mitsubishi Chemical Engineering Corporation 5-34-6 Shiba, Minato-ku, Tokyo, Japan (74) Attorney Toshiaki Ikeura, Attorney Attorney No. 4 (72) Inventor Norifumi Matsumiya 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8th Floor CO2 Fixation for Global Environmental Technology Institute (72) Inventor Norio Inoue 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8F The Institute for Global Environmental Innovation Technology Project Room for CO2 fixation etc. (72) Inventor Kenji Takagi 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8F CO2 Fixation Project for Global Environmental Industry Institute of Technology Project Room (72) Inventor Hiroshi Mano 8th Floor, 7th Oriental Maritime Building 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo Project Center for Global Environmental Innovation, Japan (72) Inventor Haraya Kenji Kenji, Tsukuba City, Ibaraki 1-1-1 Higashi Industrial Technology Institute, Institute of Materials Science and Technology, Examiner Misako Anzai (56) References JP-A-59-73418 (JP, A) 59-69415 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C01B 31/20 B01D 53/22 F25J 1/00

Claims (2)

(57) [Claims] 1. A method for separating and recovering carbon dioxide contained in mixed gas as liquefied carbon dioxide from a mixed gas, wherein: (i) a first membrane separation step of separating the mixed gas into a gas containing concentrated carbon dioxide and a residual gas (Ii) a pressurizing step of pressurizing the gas containing the concentrated carbon dioxide gas, (iii) a dehumidifying step of dehumidifying the pressurized gas, and (iv) a carbon dioxide contained in the gas by cooling the dehumidified gas. A cooling step of liquefying the gas, (v) a cryogenic separation step of separating the gas containing the liquefied carbon dioxide gas into an offgas containing carbon dioxide gas and liquefied carbon dioxide gas, and (vi) an offgas obtained in the cryogenic separation step. A second membrane separation step of separating a gas containing concentrated carbon dioxide and a residual gas, (vii) the step of depressurizing the gas containing concentrated carbon dioxide obtained in the second membrane separation, For any process selected from the cooling process A method for separating and recovering carbon dioxide from a mixed gas, comprising a circulation step of circulating. 2. A method for separating and recovering carbon dioxide contained in mixed gas as liquefied carbon dioxide from a mixed gas, comprising: (i) a first membrane separation step of separating the mixed gas into a gas containing concentrated carbon dioxide and a residual gas; (Ii) a depressurizing step of pressurizing the gas containing the concentrated carbon dioxide gas, (iii) a dehumidifying step of dehumidifying the pressurized gas using an adsorbent, and (iv) a regeneration gas that adsorbs the adsorbent having adsorbed the water. (V) a cooling step of cooling the dehumidified gas to liquefy carbon dioxide contained in the gas, and (vi) a carbon dioxide gas containing the liquefied carbon dioxide gas. (Vii) a second membrane separation step of separating the offgas obtained in the cryogenic separation step into a gas containing concentrated carbon dioxide gas and a residual gas (Viii) obtained in the second membrane separation step A circulation step of circulating at least a part of the gas containing the compressed carbon dioxide gas as an adsorbent regeneration gas to the adsorbent regeneration step; (ix) increasing the pressure of the gas after contacting with the adsorbent in the adsorbent regeneration step A method of separating and recovering carbon dioxide from a mixed gas, comprising: a circulation step of circulating to an arbitrary step selected from a step, a dehumidification step, and a cooling step.