JP6336934B2 - Gas separation membrane element, gas separation membrane module, and carbon dioxide production method - Google Patents

Description

  The present invention relates to a gas separation membrane element that selectively separates a specific gas from a mixed gas containing a plurality of component gases.

At present, in order to prevent global warming, which is a global problem, it is required to reduce the amount of warming effect gas, mainly carbon dioxide generated from human activities, to the outside air. However, in terms of energy security, it is not realistic to change the policy of energy production methods centering on fossil fuels. Therefore, the development of technology with high energy efficiency and low carbon dioxide emissions and its application are being sought. One of them is a method in which an efficient carbon dioxide separation and recovery technique is combined with an integrated coal gasification combined cycle (IGCC) technique (hereinafter referred to as IGCC (Integrated Coal Gasification Combined Cycle)). Among the carbon dioxide separation and recovery technologies, as a promising technology, technology development of a facilitated transport membrane, which is one of gas separation membranes, has been carried out. The gas separation membrane is used to efficiently and selectively separate carbon dioxide from the gas mixture obtained by gasifying coal with IGCC, and power generation is efficiently performed using the gas from which carbon dioxide has been separated. Is.
In order to improve the power generation efficiency, it is necessary to improve the selectivity (carbon dioxide selectivity) and carbon dioxide permeability with respect to carbon dioxide separation in the separation membrane, and to recover carbon dioxide with high concentration and high recovery rate. It becomes a problem.

  Here, Patent Document 1 includes, as an example of a facilitated transport film, a polymer having a primary amino group and a vinyl alcohol polymer containing a carboxyl group and a polymer having a primary amino group. , A gas separation composite membrane comprising a certain amount of a polyamidoamine dendrimer and a certain amount of an amine-based polymer is disclosed. By using such a gas separation composite membrane, the separation performance of carbon dioxide is improved.

  By the way, when separating and recovering carbon dioxide using the above facilitated transport membrane, a method of ionizing carbon dioxide using a substance that becomes a carrier gas, for example, water vapor, and dissolving and moving the ionized carbon dioxide is generally used. Are known.

JP 2012-192316 A

However, in the current technology, a technology for supplying a sufficient amount of water vapor to the facilitated transport membrane with respect to the mixed gas has not been established. For example, a method of introducing water vapor together with a mixed gas is conceivable, but even if such a method is used, the amount of water vapor supply is not sufficient and it is difficult to efficiently separate carbon dioxide.
Here, if the water vapor pressure is increased by increasing the water vapor pressure by supplying the water vapor at a temperature higher than 100 ° C., it becomes possible to sufficiently supply the water vapor to the facilitated transport film, Separation efficiency can be improved. However, in order to supply high-temperature water vapor, it is necessary to make the apparatus for installing the facilitated transport membrane and the separation membrane material compatible with high temperatures, and large energy for heating the water vapor is required. For this reason, there exists a problem that it leads to the complexity of an apparatus and the fall of electric power generation efficiency.

  The present invention has been made in view of the above-described circumstances, and has a simple structure and can efficiently separate carbon dioxide from a mixed gas, a gas separation membrane element, a gas separation membrane module, and production of carbon dioxide Provide a method.

The present invention employs the following means in order to solve the above problems.
That is, the gas separation membrane element in the invention of claim 1 is provided around the collection tube for recovering the carbon dioxide flows into through the suction holes formed on an outer peripheral surface, by the supply of water, the carbon dioxide A gas separation membrane that ionizes and selectively permeates the carbon dioxide in the mixed gas containing gas and flows into the collection pipe through the suction hole , and is disposed in the vicinity of the gas separation membrane, And a liquid absorbing member that evaporates the water from the surface and supplies the water as vapor to the gas separation membrane.

  According to such a gas separation membrane element, water can be constantly supplied to the gas separation membrane by sucking up water from the storage portion by the liquid absorbing member and evaporating them. For this reason, there is no shortage of water in the gas separation membrane. Therefore, the gas separation membrane efficiently separates and permeates carbon dioxide from the mixed gas, and allows more carbon dioxide to flow into the collection tube through the suction hole and be collected.

  In the gas separation membrane element according to the invention of claim 2, the liquid absorbing member according to claim 1 stores a high-temperature liquid in which the water is 100 ° C. or lower (more preferably 40 ° C. or higher and 100 ° C. or lower). From the above, the water may be sucked up.

  As described above, the water sucked up by the liquid absorbing member is a high-temperature liquid, so that it is possible to compensate for the latent heat when the water evaporates from the liquid absorbing member. That is, the temperature decrease of the liquid absorbing member when water evaporates can be suppressed, and the decrease in water evaporation can be suppressed. As a result, a sufficient amount of water can be supplied to the gas separation membrane.

  In the gas separation membrane element according to the invention of claim 3, the liquid absorbing member according to claim 1 or 2 has a membrane shape and is laminated on the gas separation membrane to form a laminated member together with the gas separation membrane. Also good.

  As described above, the gas separation membrane and the membrane-like liquid absorbing member form a laminated member, so that the gas separation membrane can be reduced while keeping the volume in the apparatus in which the liquid absorbing member and the gas separation membrane are installed small. A sufficient amount of steam can be supplied.

  In the gas separation membrane element according to the invention of claim 4, the gas separation membrane and the liquid absorbing member according to claim 3 cover the outer peripheral surface of the collection tube and are laminated in the radial direction of the collection tube. A member may be formed.

  Thus, a larger number of liquid-absorbing members can be installed by providing the laminated members in the radial direction so as to cover the collection tube.

  In the gas separation membrane element according to the invention of claim 5, the liquid-absorbing member according to claim 3 or 4 may be formed of filter paper.

  Thus, easily available filter paper can be used for the liquid absorbing member, and water absorption and evaporation can be promoted.

  In the gas separation membrane element according to the invention of claim 6, the liquid absorbing member according to claim 3 or 4 may be formed of a hollow fiber.

  Thus, by using a hollow fiber for the liquid absorbing member, it is possible to further promote liquid absorption and evaporation while reducing the weight of the liquid absorbing member.

Further, in the gas separation membrane element according to the invention of claim 7, the liquid absorbing member forming the laminated member according to any one of claims 3 to 6 protrudes downward from the gas separation membrane. A portion is arranged in the storage portion for storing the water, and the liquid absorbing member is formed with a communicating portion penetrating in the stacking direction between the protruding portion and the gas separation membrane. Also good.

  By forming the communication part in the liquid absorbing member in this way, the remaining component gas (non-permeate gas that does not permeate the gas separation membrane) in the mixed gas excluding carbon dioxide separated by the gas separation membrane is communicated. It is possible to pass through the hole. For this reason, the liquid absorbing member does not hinder the flow of the non-permeable gas, and the non-permeable gas can be discharged to the outside without passing through the water in the storage section, and the discharge efficiency can be improved.

  According to an eighth aspect of the present invention, a gas separation membrane module includes the gas separation membrane element according to any one of the first to seventh aspects.

  According to such a gas separation membrane module, the gas separation membrane element is provided, so that water from the storage portion is sucked up by the liquid absorption member and evaporated to constantly supply water to the gas separation membrane. it can. For this reason, there is no shortage of water in the gas separation membrane. Therefore, the gas separation membrane efficiently separates and permeates carbon dioxide from the mixed gas, and allows more carbon dioxide to flow into the collection tube through the suction hole and be collected.

  Moreover, the manufacturing method of the carbon dioxide in invention of Claim 9 manufactures a carbon dioxide using the gas separation membrane element as described in any one of Claim 1 to 7.

  According to such a carbon dioxide production method, water can be constantly supplied to the gas separation membrane by sucking up water from the storage portion by the liquid absorbing member in the gas separation membrane element and evaporating them. For this reason, there is no shortage of water in the gas separation membrane. Therefore, the gas separation membrane efficiently separates and permeates carbon dioxide from the mixed gas, allows more carbon dioxide to flow into the collection pipe through the suction hole, and collects it to produce carbon dioxide. it can.

  According to the gas separation membrane element of the first aspect, by providing the liquid absorbing member arranged close to the gas separation membrane, carbon dioxide from the mixed gas can be efficiently separated with a simple structure. .

  According to the gas separation membrane element of the second aspect, it is possible to secure the amount of heat necessary for water evaporation in the liquid absorbing member, and to further improve the carbon dioxide separation efficiency.

  According to the gas separation membrane element of the third aspect, carbon dioxide can be efficiently separated while saving space.

  According to the gas separation membrane element of the fourth aspect, carbon dioxide can be efficiently separated while further saving space.

  According to the gas separation membrane element of the fifth aspect, carbon dioxide can be efficiently separated while suppressing cost by using easily available filter paper for the liquid absorbing member.

  According to the gas separation membrane element of claim 6, carbon dioxide can be efficiently separated by using a liquid absorbing member as a membrane using a hollow fiber.

  According to the gas separation membrane element of the seventh aspect, by forming the communication hole in the liquid absorbing member, it is possible to suppress the non-permeating gas from staying in the apparatus that accommodates the gas separation membrane element, and to make the carbon dioxide efficient. Can be separated.

  According to the gas separation membrane module of claim 8, by providing the liquid absorbing member disposed in the vicinity of the gas separation membrane, carbon dioxide from the mixed gas can be efficiently separated with a simple structure. .

  According to the method for producing carbon dioxide of claim 9, by providing the liquid absorbing member disposed in the vicinity of the gas separation membrane, carbon dioxide from the mixed gas is efficiently separated with a simple structure, and Carbon can be produced.

1 is a schematic overall view of a gas separation membrane module provided with a gas separation membrane element according to an embodiment of the present invention. It is a perspective view showing a gas separation membrane element concerning an embodiment of the present invention partially fractured. It is sectional drawing which shows the mode of lamination | stacking of the gas separation membrane element which concerns on embodiment of this invention. It is a schematic whole figure of the gas separation membrane module provided with the gas separation membrane element which concerns on the modification of embodiment of this invention. It is the schematic of the experimental apparatus which confirmed the water absorption effect of the liquid absorption member (filter paper) in a gas separation membrane element, (a) is a front view, (b) shows a side view. It is a graph which shows the result of the experiment which confirmed the water absorption effect of the liquid absorption member (filter paper) in a gas separation membrane element. It is the schematic of the experimental apparatus which confirmed the water absorption effect of the liquid absorption member (filter paper) in a gas separation membrane element, and the carbon dioxide separation effect from the mixed gas in a facilitated-transport film | membrane, (a) is a front view, ( b) shows a side view.

Hereinafter, the gas separation membrane element 1 of the embodiment of the present invention will be described.
The gas separation membrane element 1 is incorporated in the gas separation membrane module 100.
The gas separation membrane module 100 is, for example, an apparatus used for coal gasification combined power generation, and is an apparatus that selectively separates carbon dioxide C from coal that has been gasified to become a mixed gas G (IGCC gas).

  As shown in FIG. 1, the gas separation membrane module 100 includes a collection tube 3 formed around an axis O, a vessel 5 covering the collection tube 3 from the outer periphery, and a collection tube between the collection tube 3 and the vessel 5. 3 is provided with a gas separation membrane element 1 provided around 3.

  The collection tube 3 is a tubular member extending in the direction of the axis O, and a plurality of suction hole portions 3a that are spaced apart from each other in the direction of the axis O and communicate with each other are formed on the outer peripheral surface.

The vessel 5 has a cylindrical body portion 11 centering on the axis O, an upper lid 12 that closes the upper opening 11a of the body portion 11, and a lower lid 13 that closes the lower opening 11b of the body portion 11. doing. A vessel 5 is provided so that the inner peripheral surface of the trunk portion 11 is separated from the outer peripheral surface of the collection tube 3 in the radial direction of the collection tube 3.
The upper lid 12 passes through the upper portion of the collecting tube 3 (one end in the axial direction), and the collecting tube 3 protrudes upward from the vessel 5.

  A gas supply port 5 a that protrudes radially outward from the outer peripheral surface and communicates with the inside and outside of the vessel 5 is formed at a position on the upper end side of the body portion 11 in the vessel 5. A pipe or the like (not shown) is connected to the gas supply port 5a so that the mixed gas G can flow into the vessel 5 through the gas supply port 5a.

Further, a gas discharge port 5 b that protrudes radially outward from the outer peripheral surface and communicates the inside and outside of the vessel 5 is formed at a position on the lower end side (the other side in the axial direction) of the body portion 11 in the vessel 5. . From the gas discharge port 5b, the remaining component gas (non-permeate gas G1) in the mixed gas G after the carbon dioxide C is separated can be discharged to the outside of the vessel 5.
In this embodiment, the gas discharge port 5b is formed at a position spaced apart from the gas supply port 5a by 180 degrees around the axis O in the circumferential direction.
Note that the flow of the mixed gas can be reversed. In this case, 5a serves as a gas discharge port and 5b serves as a gas supply port.

Further, the vessel 5 has a water supply port 5c that protrudes downward through the lower lid 13, and a water discharge port 5d that protrudes radially outward from the outer peripheral surface of the trunk portion 11 at a position further below the gas discharge port 5b. And are formed. The water supply port 5 c is provided in the lower lid 13 at a position on the radially outer side of the collection tube 3.
The water W discharged from the drain port 5d is supplied to the inside of the vessel 5 again from the water supply port 5c while being heated to a predetermined temperature by a circulation device (not shown). Here, the predetermined temperature indicates a temperature of 100 ° C. or lower (more preferably 40 ° C. or higher and 100 ° C. or lower), that is, the water W is warm water (high-temperature liquid).

Further, since the water surface is maintained at the position of the drain outlet 5d at the lower part of the vessel 5, the lower part of the vessel 5 serves as a storage part 14 for storing water W.
In addition, the storage part 14 does not necessarily need to be provided in the lower part of the vessel 5 like this embodiment, and may be provided in the upper part or the intermediate part.

Further, the vessel 5 is formed with a carrier gas supply port 5e that penetrates the lower lid 13 and protrudes downward. The carrier gas supply port 5e is formed on the axis O, and is connected to and communicates with the collection pipe 3.
From this carrier gas supply port 5e, a carrier gas (sweep gas) G2 such as water vapor is introduced as necessary. The carrier gas G2 pushes the carbon dioxide C sucked into the collection pipe 3 from the suction hole 3a upward.
Here, the collection tube 3 is provided with a closing member 4 such as a plug for closing the collection tube 3 so as to be detachable below the suction hole portion 3a located at the bottom. When the carrier gas G2 is unnecessary, the collection tube 3 is closed by the closing member 4.

Next, the gas separation membrane element 1 will be described in detail.
The gas separation membrane element 1 is inserted between the outer peripheral surface of the collection tube 3 and the inner peripheral surface of the vessel 5 so as to be inserted into the vessel 5. The gas separation membrane element 1 is provided so as to be positioned below the gas supply port 5a.

  As shown in FIG. 2, the gas separation membrane element 1 includes a membrane-like facilitated transport membrane 18 (gas separation membrane) and a liquid absorbing member 17, and these are laminated.

The facilitated transport film 18 is a film that selectively permeates carbon dioxide C in the mixed gas G by supplying water W. Specifically, for example, a film formed from a polymer having a primary amino group and a vinyl alcohol polymer containing a carboxyl group.
Here, although this embodiment demonstrates the case where the facilitated-transport film | membrane 18 is used as an example of a gas separation membrane, a gas-separation film is not limited to the facilitated-transport film | membrane 18, An amine compound, a polyvinyl alcohol-type polymer, and polyethyleneglycol Any gas separation membrane that requires water containing a polymer may be used. Moreover, the film | membrane containing an inorganic compound may be sufficient.

  The liquid absorbing member 17 is made of, for example, filter paper.

The facilitated transport film 18 and the liquid absorbing member 17 are laminated in the radial direction of the collection tube 3 to form a laminated member. That is, the facilitated transport film 18 and the liquid absorbing member 17 are provided in multiple cylinders so as to be wound around the outer peripheral surface of the collecting tube 3 to form a laminated member.
More specifically, as shown in FIG. 3, in one layer of the laminated member, a film-like supply spacer 20 (a thermoplastic resin such as a polyolefin resin) is provided so as to sandwich the liquid absorbing member 17 formed from filter paper from both sides. Further, the supply spacer 20 is provided with a membrane-like permeable spacer 21 (a thermoplastic resin such as a polyolefin resin) sandwiched between the facilitated transport films 18.
That is, in the laminated member, the facilitated transport film 18, the permeable spacer 21, the facilitated transport film 18, the supply spacer 20, the liquid absorbing member 17 (filter paper), and the supply spacer 20 are repeatedly laminated in this order.

  Further, the liquid absorbing member 17 forming this laminated member protrudes downward from the facilitated transport film 18, and the protruding tip end portion 17 a is arranged in the storage portion 14 and immersed in the water W in the storage portion 14. ing. On the other hand, the film forming the laminated member other than the liquid absorbing member 17 (facilitated transport film 18, supply spacer 20, transmission spacer 21) is above the gas discharge port 5 b, that is, above the water surface of the reservoir 14. It extends to the position.

  According to such a gas separation membrane element 1, the water W can be constantly supplied to the facilitated transport membrane 18 by sucking and evaporating the water W from the reservoir 14 by the liquid absorbing member 17 formed from filter paper. For this reason, there is no shortage of moisture in the facilitated transport film 18. Therefore, the facilitated transport film 18 ionizes the carbon dioxide C in the mixed gas G and efficiently separates and permeates the carbon dioxide C, and more carbon dioxide C enters the collection pipe 3 through the suction hole 3a. Can be introduced.

  Further, since the water W sucked up from the storage part 14 by the liquid absorbing member 17 is warm water, it is possible to compensate for the latent heat taken away from the liquid absorbing member 17 when the water W evaporates from the liquid absorbing member 17. That is, the temperature decrease of the liquid absorbing member 17 when the water W evaporates can be suppressed, and the decrease in the evaporation amount of the water W from the liquid absorbing member 17 can be suppressed. As a result, a sufficient amount of moisture can be supplied to the facilitated transport membrane 18, and the carbon dioxide C separation efficiency can be further improved.

  Further, since the facilitated transport film 18 and the liquid absorbing member 17 form a laminated member, the volume of the vessel 5 in which the liquid absorbent member 17 and the facilitated transport film 18 are installed is kept small, thereby saving space. A sufficient amount of steam can be supplied to the facilitated transport membrane 18, and the separation efficiency of carbon dioxide C can be further improved.

  In addition, the liquid absorbing member 17 can be easily separated by using a filter paper that can be easily obtained, while reducing the cost and promoting water absorption and evaporation. .

Here, in this embodiment, filter paper is used for the liquid absorbing member 17, but a membrane made of hollow fibers may be used instead of the filter paper. Since the hollow fiber is a cylindrical fiber, it is lightweight and can further promote the effects of water absorption and evaporation.
Instead of filter paper, a gel-like polymer material formed into a film may be sandwiched between thin films of Teflon (registered trademark). That is, the liquid absorbing member 17 is not limited to that of the present embodiment, and various members can be used as long as they promote the effects of water absorption and evaporation.

  Further, as shown in FIG. 4, the liquid absorbing member 17 </ b> B is a position that protrudes from the facilitated transport film 18 toward the storage part 14, at a position between the water surface of the storage part 14 and the facilitated transport film 18. The communicating portion H (hole, slit, etc.) may be formed so as to penetrate in the stacking direction of the liquid absorbing member 17B and the facilitated transport film 18.

  By forming such a communication portion H, the remaining component gas in the mixed gas G excluding the carbon dioxide C separated by the facilitated transport film 18, that is, the non-permeate gas G1 that does not permeate the facilitated transport film 18, It can pass through the communication hole H. For this reason, the liquid absorbing member 17B does not hinder the flow of the non-permeable gas G1, and the non-permeable gas G1 can be discharged to the outside without passing through the storage unit 14. Therefore, the discharge efficiency of the non-permeating gas G1 can be improved.

  Therefore, by forming the communication hole H in the liquid absorbing member 17B, it is possible to suppress the non-permeating gas G1 from staying in the vessel 5, and the carbon dioxide C can be efficiently separated from the mixed gas G.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the structure shown by the above-mentioned embodiment, It can change in the range which does not deviate from the meaning of this invention.

  Unlike the case shown in FIG. 2, the facilitated transport film and the liquid absorbing member may be simply arranged in a flat film shape around the collection tube 3.

  In addition, the liquid absorbing member 17 (17 </ b> B) is not limited to the case where the laminated member is formed together with the facilitated transport film 18, and may only be disposed in proximity to the facilitated transport film 18.

[Example 1]
Here, an experiment was conducted to confirm the water absorption effect of the filter paper (liquid absorbing member) in the present embodiment. As shown in FIGS. 5A and 5B, the apparatus 201 used in the experiment simulates the gas separation membrane module 100 in the above-described embodiment.
Specifically, in this apparatus 201, filter paper 203 (ADVANTEC 51B) sandwiched from both sides by spacers 204 is accommodated in a rectangular transparent case 202, and colored water W is stored in the lower part of the transparent case 202. Thus, the filter paper 203 is immersed.

  The transparent case 202 has a gas inlet hole 202a formed on the surface on one side of the upper portion and communicating with the inside and outside of the transparent case 202, and a gas outlet hole 202b formed on the surfaces on both sides of the lower portion and communicating with the inside and outside of the transparent case 202. And are formed. The liquid level of the stored water W is located below the gas outlet hole 202b.

In the experiment using such an apparatus 201, as shown in FIG. 6, in all the results from the first time to the third time, the water absorption height [cm] is drastically until about 50 minutes have passed since the start of water absorption. After that, the water absorption height gradually increased and reached 30 [cm] at about 250 minutes from the start of water absorption.
The water absorption height indicates a height dimension of the filter paper 203 from the liquid level of the water W.

[Example 2]
Next, an experiment was conducted to confirm the water absorption effect of the filter paper 303 and the carbon dioxide C separation effect of the facilitated transport membrane 304.

  As shown in FIGS. 7A and 7B, the apparatus 301 used in the experiment simulates the gas separation membrane module 100 in the above-described embodiment.

In this apparatus 301, a supply spacer 308, a filter paper 303, a supply spacer 308, a facilitated transport film 304, and a transmission spacer 309 are stacked in this order and sandwiched between flat membrane test cells 302 (C10-T manufactured by Nitto Denko Corporation). .
The flat membrane test cell 302 has a gas inlet hole 302a that communicates the inside and outside of the flat membrane test cell 302 with one surface at the bottom, and a gas outlet hole 302b that communicates the inside and outside of the flat membrane test cell 302 with one surface at the top. And are formed. Similarly, a gas inlet hole 302c that communicates the inside and outside of the flat membrane test cell 302 with a surface opposite to the gas inlet hole 302a in the lower portion of the flat membrane test cell 302, and a surface opposite to the gas outlet hole 302b in the upper portion. In addition, a gas outlet hole 302 d that communicates the inside and outside of the flat membrane test cell 302 is formed.

A nozzle 305 is connected to the gas inlet hole 302 a so that the mixed gas G and water W are supplied into the flat membrane test cell 302.
Here, the mixed gas G was a mixture of carbon dioxide C and helium at a ratio of CO ₂ / He = 80/20 [volume percent], and the flow rate was 100 [ml / min].
Water W was supplied into the flat membrane test cell 302 at a flow rate of 0.01 [ml / min] by a pump (not shown).

A nozzle 310 is connected to the gas inlet hole 302c so that the carrier gas G2 is supplied.
A nozzle 306 is connected to the gas outlet hole 302b, and a hygrometer 307 is attached. The water W and the non-permeate gas G1 are discharged from the gas outlet hole 302b.
In addition, a nozzle 311 is connected to the gas outlet hole 302d, and the carrier gas G2 and the carbon dioxide C are discharged.

  And said apparatus was installed in the thermostat kept at 40 degreeC.

  As a result of experiments using such an apparatus 301, the relative humidity measured at the gas outlet hole 302b increased from 8.2 [% RH] at the start of the experiment to 90.8 [% RH] at the maximum. In addition, even after 2 hours after the supply of water W was stopped, the relative humidity could be maintained at a value of 90 [% RH] or more.

Furthermore, Table 1 shows the results of measuring the separation performance of carbon dioxide C using the above-described apparatus.

Q _co2 in Table 1 indicates the permeation amount of carbon dioxide C in unit time, unit area, and unit pressure difference, and is called “permeance (permeation amount)”.
As shown in Table 1, when water is not supplied under the conditions that the total pressure in the flat membrane test cell 302 is 0.1 [MPa] and the temperature is 40 [° C.] (case 1), the permeation amount of carbon dioxide C Was 1.8 × 10 ⁻¹⁰ [m ³ / (m ² spa)], and the separation performance of carbon dioxide C (separation coefficient α: CO ₂ / He) was 144.7.
On the other hand, after supplying water W at 0.01 [ml / min] for 82 minutes under the same conditions as in case 1 (case 2), the permeation amount of carbon dioxide C was 2.0 × 10 ⁻¹⁰ [ m ³ / (m ² spa)], and the carbon dioxide C separation performance was 212.3.

Further, when water is not supplied under the conditions that the total pressure in the flat membrane test cell 302 is 0.7 [MPa] and the temperature is 40 [° C.] (case 3), the separation performance of carbon dioxide C is 8.7. It became.
On the other hand, after supplying water W at 0.01 [ml / min] for 82 minutes under the same conditions as in case 3 (case 4), the separation performance of carbon dioxide C was 21.7.

Further, when water supply is not performed under the conditions that the total pressure in the flat membrane test cell 302 is 0.7 [MPa] and the temperature is 50 [° C.] (case 5), the separation performance of carbon dioxide C is 27.1. It became.
On the other hand, after supplying water W at 0.01 [ml / min] for 82 minutes under the same conditions as in case 5 (case 6), the separation performance of carbon dioxide C was 94.3.

Thus, it has been confirmed that the separation effect of carbon dioxide C by water supply can be improved under any experimental conditions.
The gas flow rate on the gas supply side (gas inlet hole 302a side) is 100 [ml / min], and the gas flow rate on the gas permeation side (gas outlet hole 302b side) is 35 [ml / min]. is there.

1 ... Gas separation membrane element
3 ... Collection tube
3a ... Suction hole
4 ... Occlusion member
5 ... Vessel
5a ... Gas supply port
5b ... Gas outlet
5c ... Water inlet
5d ... Drain outlet
5e ... Carrier gas supply port
11 ... trunk
11a ... upper opening
11b ... lower opening
12 ... Upper lid
13 ... Lower lid
14 ... Reservoir
17, 17B ... Liquid absorbing member
17a ... tip
18 ... facilitated transport membrane (gas separation membrane)
20 ... Supply spacer
21 ... Transparent spacer
G ... mixed gas
G1 ... Non-permeating gas
G2 ... Carrier gas (sweep gas)
C ... carbon dioxide
H ... Communication part
W ... water
O ... axis
100: Gas separation membrane module
201 ... Device
202 ... Transparent case
202a ... Gas inlet hole
202b ... Gas outlet hole
203 ... filter paper
204 ... Spacer
301 ... Device
302 ... flat membrane test cell
302a, 302c ... Gas inlet holes
302b, 302d ... Gas outlet holes
303 ... filter paper
304 ... facilitated transport membrane
305 ... Nozzle
306 ... Nozzle
307 ... Hygrometer
308 ... Supply spacer
309: Transmission spacer
310 ... Nozzle
311 ... Nozzle

Claims (9)

Provided around the collection tube for recovering the carbon dioxide flows into through the suction holes formed on an outer peripheral surface, by the supply of water, the carbon dioxide in the mixed gas containing the carbon dioxide ionized A gas separation membrane that selectively permeates and flows into the collection pipe through the suction hole ,
A liquid-absorbing member that is disposed in the vicinity of the gas separation membrane, sucks up the water from the outside, evaporates the water from the surface, and supplies the water as vapor to the gas separation membrane;
A gas separation membrane element comprising:   2. The gas separation membrane element according to claim 1, wherein the liquid absorption member sucks up the water from a storage portion that stores a high-temperature liquid in which the water is 100 ° C. or less.   3. The gas separation membrane element according to claim 1, wherein the liquid absorbing member has a membrane shape and is laminated on the gas separation membrane to form a laminated member together with the gas separation membrane.   The gas separation membrane element according to claim 3, wherein the gas separation membrane and the liquid absorbing member cover the outer peripheral surface of the collection tube and are laminated in the radial direction of the collection tube to form the laminated member.   The gas separation membrane element according to claim 3 or 4, wherein the liquid absorbing member is formed of filter paper.   The gas separation membrane element according to claim 3 or 4, wherein the liquid absorbing member is formed of a hollow fiber. The liquid-absorbing member forming the laminated member protrudes downward from the gas separation membrane, and the protruding portion is disposed in a storage portion that stores the water, and the liquid-absorbing member protrudes from the liquid-absorbing member. The gas separation membrane element according to any one of claims 3 to 6, wherein a communication portion penetrating in the stacking direction is formed between the portion and the gas separation membrane. A gas separation membrane module for separating carbon dioxide in a mixed gas,
A gas separation membrane module comprising the gas separation membrane element according to any one of claims 1 to 7. A method for producing carbon dioxide by producing carbon dioxide by separating carbon dioxide in a mixed gas,
The manufacturing method of a carbon dioxide which manufactures a carbon dioxide using the gas separation membrane element as described in any one of Claim 1 to 7.

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