JP2017087101A - Gas separator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an efficient gas separator housing a gate-type porous polymer complex inside.SOLUTION: A gas separator provided with an adsorption tower filled with a gate-type porous polymer complex exhibiting a gate phenomenon includes at least: a gas supply means for supplying a mixed gas containing a plurality of kinds of gas to the adsorption tower and causing the gate phenomenon in the adsorption tower; and a means for controlling parameters associated with expression of the gate phenomenon so as to control distribution for expressing the gate phenomenon homogeneously in the adsorption tower.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a gas separation apparatus using a porous polymer complex exhibiting a gate phenomenon (hereinafter also simply referred to as “gate type porous polymer complex”).

  A pressure swing adsorption (PSA) system using a solid adsorbent is widely used as a method for producing an important gas in industries such as oxygen and nitrogen. This is because, for example, when separating a gas from a mixture of two types of gas, if the adsorption tower is filled with a solid adsorbent that has a difference in adsorption power to the two types of gas and one of the gases is selectively introduced. As a result of the adsorption, a large amount of gas that has not been adsorbed remains in the gas layer. For this purpose, solid adsorbents called so-called porous bodies, such as zeolite and activated carbon, are widely used, and oxygen-producing PSA, nitrogen-producing PSA, etc. are widely used (Patent Document 1, etc.).

  In general, existing porous bodies such as zeolite and activated carbon can be classified into six categories of so-called IUPAC adsorption isotherms. That is, the existing porous body has a characteristic that the gas adsorption force increases with an increase in pressure, and the existing PSA system is optimized to such a characteristic. On the other hand, materials exhibiting special adsorption isotherms that cannot be classified by the 6 classifications of IUPAC have been announced. These are a kind of porous polymer complex (PCP: Porous Coordination Polymer) formed from metal ions and ligands. These are called gate-type porous polymer complexes and flexible porous polymer complexes. The special gas adsorption behavior shown by is called the gate phenomenon, gate adsorption.

  The gate phenomenon is a phenomenon in which the gas adsorption amount changes abruptly due to a change in the structure of the porous polymer complex. When the gas pressure is low, the gate-type porous polymer complex hardly adsorbs the gas, but when the gas pressure reaches a certain value (this pressure is called the gate pressure), the structure of the PCP changes (for example, The stacking is shifted, the layers are spread, etc.), and gas molecules are taken in. For this reason, the amount of gas adsorption increases rapidly with the gate pressure as a boundary. Below the gate pressure, it is more energetically stable if the gate-type porous polymer complex and gas molecules exist separately, but above the gate pressure, the gate-type porous polymer complex and gas molecules are more stable. It is considered that gas molecules taken into the inside of PCP form a more stable inclusion and become energetically advantageous rather than being separately present.

  The opposite phenomenon occurs in gas release. In other words, when the gas pressure falls below the gate pressure, the gas molecules incorporated in the gate-type porous polymer complex are released, and the gas is released because it tries to return to the original structure of the gate-type porous polymer complex. Suddenly occurs. That is, such a gate phenomenon is based on the flexibility of the gate-type porous polymer complex structure, and the gate phenomenon does not occur in zeolite and activated carbon that are existing porous bodies that do not have such a flexibility. This is a phenomenon peculiar to the gate type porous high molecular complex.

When this gate phenomenon is applied to gas separation, there are mainly two major advantages. The first is high-efficiency gas separation due to rapid gas adsorption and release. The existing porous body shows an adsorption isotherm in which the gas pressure and the adsorption amount are approximately proportional. In order to collect the entire amount of gas adsorbed on such a material, a large pressure fluctuation is required. On the other hand, in the case of a gate-type porous polymer complex that exhibits a gate phenomenon, gas can be recovered with very little pressure fluctuation (FIG. 1).
Pressure fluctuations during gas recovery are directly linked to power costs. That is, the gate-type porous polymer complex that can recover the gas with a small pressure fluctuation is a material that can separate the gas at a low cost.

  The second merit is high gas separation efficiency. As described above, the gas adsorption of the gate-type porous polymer complex is not a simple mechanism in which the gas molecules are taken into the pores as in the conventional case. Above a certain gas pressure (gate pressure), it is based on a mechanism of forming a stable inclusion body with a gate-type porous polymer complex. In the case of an existing porous body, even if it has an affinity different from that of the two kinds of gases, a co-adsorption phenomenon in which a gas having a low affinity is also taken into the pores tends to occur as long as there are pores. On the other hand, the gate-type porous polymer complex, due to the co-adsorption phenomenon, lowers the stability of the inclusion body when gas molecules with low affinity are also incorporated, so that the gas with high affinity is selectively incorporated, making it more stable. It has the characteristic of trying to form a complete inclusion body. For this reason, the gate-type porous polymer complex has high gas selectivity, and when applied to a PSA system, it is possible to produce a gas with high efficiency and high purity.

  However, when this gate type porous polymer complex is actually applied to a PSA system, various problems arise. In the case of an existing porous material, gas adsorption gradually occurs as the pressure rises. Therefore, when gas flows in the adsorption tower, adsorption gradually occurs from the gas entrance side. On the other hand, when a gate-type porous polymer complex is used, gas adsorption suddenly occurs as a gate phenomenon, so that the temperature and gas partial pressure may fluctuate rapidly at specific locations in the adsorption tower. However, since the gate pressure generally varies greatly depending on the temperature and gas partial pressure (Non-patent Document 1), when the temperature and gas partial pressure in the adsorption tower change rapidly, the gas once adsorbed in the adsorption tower rapidly An unusual phenomenon such as being re-released in the existing porous material may occur. When such a rapid gas re-release phenomenon occurs, the temperature in the tower is lowered, which may lead to a vibration phenomenon in which gas adsorption occurs again as a gate phenomenon. As a result, problems such as abnormal distribution unevenness of the temperature and gas partial pressure in the adsorption tower occur and gas separation becomes difficult, and the purity of the separated gas decreases. A PSA system using this gate type porous polymer complex has not yet been put into practical use, and this problem has not been solved.

JP 2000-061244 A

Kano et al., Journal of Colloid and Interface Science (2009) 334, 1

  An object of the present invention is to provide a gas separation device in which a gate type porous polymer complex is accommodated.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention homogenize the gas concentration distribution change, temperature change, pressure change, etc. accompanying the gate phenomenon in advance in the PSA adsorption tower. As described above, it is found that stable and highly efficient gas separation can be achieved by actively causing the distribution of parameters (for example, temperature and pressure) and suppressing the rapid development of the gate phenomenon. It came to. The present invention provides a highly efficient gas separation device in which a gate type porous polymer complex is housed.

  That is, the present invention is as follows.

(1) A gas separation device including an adsorption tower packed with a gate-type porous polymer complex exhibiting a gate phenomenon,
A gas supply means for supplying a mixed gas containing a plurality of gases to the adsorption tower to cause a gate phenomenon in the adsorption tower;
A gas separation apparatus comprising at least means for controlling a parameter distribution for controlling the parameter related to the onset of the gate phenomenon so that the gate phenomenon is uniformly expressed in the adsorption tower.
(2) The gas separation device according to (1), wherein the parameter is a temperature and / or a gas pressure in the adsorption tower.
(3) The means for controlling the parameter related to the onset of the gate phenomenon includes a temperature sensor, a temperature controller, a heating means, and a cooling means attached to the entire area in the adsorption tower (1) or (2) Gas separation device.
(4) The means for controlling the parameter related to the onset of the gate phenomenon includes a pressure sensor, a pressure controller, a pressurizing means, and a depressurizing means attached to the entire area of the adsorption tower. The gas separator described.
(5) The means for controlling the parameter related to the occurrence of the gate phenomenon is a pressure sensor, a temperature sensor, a pressure controller, a temperature controller, a heating means, a cooling means, a pressurizing means, and the like attached to the entire area of the adsorption tower The gas separation device according to (1) or (2), comprising a decompression means.
(6) The gas separation device according to any one of (1) to (5), wherein the gate-type porous polymer complex exhibits a gate-type isotherm with respect to at least one of the mixed gases.
(7) The gas separation device according to (6), wherein the gate-type porous polymer complex is selected from ELMs, kagome, MILs, and CIDs.
(8) The gas separator according to (7), wherein the gate-type porous polymer complex has an adsorption gate coefficient of 0.7 to 75 and a desorption gate coefficient of 0.4 to 80.
(9) The gas separation device according to (7), wherein the pressure difference between the adsorption completion gate pressure and the desorption completion gate pressure of the gate type porous polymer complex is 2 kPa to 8000 kPa.
(10) The gas species according to any one of (1) to (9), wherein the gas species is any one of oxygen, nitrogen, argon, carbon dioxide, carbon monoxide, hydrogen, alkanes, alkenes, and alkynes. Gas separation device.

  An apparatus filled with the gate type porous polymer complex of the present invention can perform highly efficient gas separation. Examples of the gas separation device of the present invention include a pressure swing adsorption method (hereinafter abbreviated as “PSA method”) gas separation device. As a method, either vacuum swing adsorption (VSA) or pressure swing adsorption (PSA) can be suitably used.

The graph which shows the relationship between the gas pressure of the existing solid adsorbent and the adsorbent which consists of a porous polymer complex used for this invention, and the amount of gas adsorption. The figure showing each gate pressure of the adsorbent which consists of a porous polymer complex used for this invention. The figure explaining a gate coefficient for ELM-11 as an example. The schematic diagram which shows an example of the gas separation apparatus of this invention.

  The gate type porous polymer complex of the present invention is a material showing a gate type isotherm. The gate type means an adsorption and / or desorption isotherm showing an inflection point as shown in FIG. 2 mainly due to structural change. As shown in FIG. 2, the isotherm of the gate type porous polymer complex is defined by the adsorption start gate pressure, the adsorption completion gate pressure, the gate adsorption amount, the desorption start gate pressure, the desorption completion gate pressure, and the gate desorption amount. .

  The adsorption start gate pressure is a pressure at which in the adsorption process, the proportional relationship between the adsorption amount and the pressure at the initial stage of adsorption suddenly increases (the adsorption amount increment suddenly increases with respect to the gas pressure increment). The adsorption completion gate pressure is a pressure in which the proportional relationship between the adsorption amount and the pressure after the adsorption start gate pressure in the adsorption step is abruptly reduced (the desorption amount increment is abruptly smaller than the gas pressure increment). The gate adsorption amount is an adsorption amount between the adsorption start gate pressure and the adsorption completion gate pressure. In addition, the desorption start gate pressure is a pressure at which the proportional relationship between the adsorption amount and the pressure at the initial stage of desorption in the desorption step increases abruptly (the desorption amount increment suddenly increases with respect to the gas pressure increment). The desorption completion gate pressure is a pressure in which the proportional relationship between the adsorption amount and the pressure after the desorption start gate pressure in the desorption step is abruptly reduced (the desorption amount increment is abruptly smaller than the gas pressure increment). It is. The gate desorption amount is a desorption amount from the desorption start gate pressure to the desorption completion gate pressure.

  The gate-type porous polymer complex adsorption property and desorption property of the gate can be defined by the following two formulas.

Formula 1: Adsorption gate coefficient = (Adsorption amount at adsorption completion gate pressure−Adsorption amount at adsorption start gate pressure) / (Adsorption completion gate pressure−Adsorption start gate pressure)
Formula 2: Desorption gate coefficient = (Adsorption amount at desorption start gate pressure−Adsorption amount at desorption completion gate pressure) / (Desorption start gate pressure−Desorption completion gate pressure)
Note) The adsorption amount is the adsorption amount at the measurement temperature of the measurement gas, and the unit is mL / g (STP).
Note) Pressure is kPa.

  Currently known gate-type porous polymer complexes include ELM (Elastic Layer-structured metal organic frameworks), Kagome, MILs, CIDs, and others. The literature of these gate type porous polymer complexes is as follows. ELM is described in the literature of Int. J. Mol. Sci. 2010, 11,3803. Kagome species are described in Sato et al., SCIENCE (2014) 343, 167, and Zaworotko et al., Chem. Commun., 2004, 2534. MILs are shown in the literature of Ferey et al., Chem. Soc. Rev., 2009, 38, 1380. CIDs are shown in the literature of Inubushi et al., Chem. Commun., 2010, 46, 9229, and Nakagawa et al., Chem. Commun., 2010, 46, 4258. Other examples are given in the literature of Kitaura et al., Angew. Chem. Int. Ed. 2003, 42, 428. Among these, ELMs, Kagome, MILs, and CIDs are preferable in that the gate phenomenon is clear and the effect of the present invention is high.

  Taking the ELM-11 as an example, the gate coefficient will be described with reference to FIG. The adsorption / desorption isotherm of carbon dioxide at 273 K of ELM-11 is as shown in FIG. The x-axis is the pressure (kPa), and the y-axis is the adsorption amount (mL / g (STP)). In this case, since each isotherm passes the following points, those isotherms can be approximated by the following equation.

Adsorption isotherm before adsorption gate:
Typical passing point 1: x = 5.23, y = 0.188; passing point 2: x = 27.4, y = 0.665, and approximate expression y = 0.0002x + 0.0753.
Adsorption isotherm after adsorption gate:
Typical passing point 1: x = 34.2, y = 23.3; passing point 2: x = 35.2, y = 50.7, and approximate expression y = 27.4x−913.

Solving the above simultaneous equations, x (“adsorption start gate pressure”) = 33.4 kPa (adsorption amount before gate is 1.1 mL / g (STP)).
Similarly, the “adsorption completion gate pressure” calculated from the isotherm is 36.0 kPa, and the adsorption amount at that time is 74.4 mL.
From the above, the adsorption gate coefficient = (77.4-1.1) / (36.0-33.4) = 29.3.
Similarly, the desorption start gate pressure is 28.41 kPa (adsorption amount is 75.2 mL / g (STP)). Desorption completion gate pressure = 26.20 kPa (adsorption amount is 2.71 mL / g (STP)).
From the above, the desorption gate coefficient = (75.2-2.71) / (28.41-26.20) = 32.8 is calculated.

The gate-type porous polymer complex that can be used in the gas separation device of the present invention preferably has an adsorption gate coefficient of 0.7 to 75 and a desorption gate coefficient of 0.4 to 80.
When the adsorption gate coefficient is less than 0.7, the fluctuation amount of the adsorption amount with respect to the pressure fluctuation is too small, and a clear difference from a general adsorbent cannot be obtained. When the adsorption gate coefficient exceeds 75, the amount of fluctuation of the adsorption amount with respect to the pressure fluctuation is too steep and there is a sudden change in the concentration ratio of the mixed gas due to sudden heat generation or sudden adsorption of the specific gas. It is practically difficult to use as a separation material (hard to control). When the desorption gate coefficient is less than 0.4, the amount of fluctuation of the adsorption amount with respect to the pressure fluctuation is too small, and a clear difference from a general adsorbent cannot be obtained, so it is difficult to say a gate type behavior. When the desorption gate coefficient exceeds 80, the desorption amount fluctuation amount with respect to pressure fluctuation is too steep, and there is a drastic change in the concentration ratio of the mixed gas due to rapid desorption heat and a sudden release of a specific gas. As a gas separation material, it is difficult to use practically (hard to control).

  In the gate type porous polymer complex that can be used in the gas separation apparatus of the present invention, the pressure difference between the adsorption completion gate pressure and the desorption completion gate pressure is preferably 2 kPa to 8000 kPa. When the pressure difference between the adsorption completion gate pressure and the desorption completion gate pressure is less than 2 kPa, the adsorption pressure and the desorption pressure are too close to each other and cannot be controlled by the PSA device. On the other hand, if it exceeds 8000 kPa, the adsorption pressure and the desorption pressure are too far apart, and in order to recover the adsorbed gas from such a material, it is necessary to perform a very large pressure fluctuation. Time is large and there is no merit of using the gate phenomenon for gas separation.

  The apparatus filled with the gate type porous polymer complex of the present invention can be applied to separation of various gases. Examples of the gas species include oxygen, nitrogen, argon, carbon dioxide, carbon monoxide, hydrogen, alkanes, alkenes, alkynes, and the like. When the apparatus filled with the gate type porous polymer complex of the present invention is applied to gas separation, a high-purity gas can be easily separated with high efficiency using the gate phenomenon.

  In the gas separation apparatus filled with the gate type porous polymer complex of the present invention, the container shape, the container material, the type of the gas valve, etc. need not be particularly used, and are used in the gas separation apparatus. Can be used. In addition, the means for forming a temperature gradient or pressure gradient in these devices to homogenize the pressure change and temperature change accompanying the gas concentration distribution change of the gas separation device accompanying the gate phenomenon is the temperature gradient, pressure Any existing technique may be used as long as the gradient is properly controlled. However, improvement of various apparatuses is not excluded, and any apparatus is included in the technical scope of the present invention as long as the gas polymer metal complex of the present invention is used.

  The gas separation apparatus filled with the gate type porous polymer complex of the present invention is an apparatus that actively causes parameter distribution. Here, “actively causing parameter distribution” means, for example, by setting a high temperature on the entrance side of the adsorption tower, a low temperature on the exit side (or vice versa) with a heating device, or by using a partition wall or the like. It means that the high pressure on the entrance side of the tower and the low pressure on the exit side (or vice versa). Typical parameters for controlling the gate phenomenon that occurs in the gas separation apparatus using the gate type porous polymer complex of the present invention include temperature and pressure.

  How these parameter values are distributed in the tower depends on where the gate phenomenon occurs in the tower, but where the gate phenomenon occurs in the tower depends on the characteristics of the gated porous polymer complex. (The gate pressure such as adsorption gate pressure and desorption gate pressure, the amount of heat generated and absorbed by gas adsorption and desorption, heat transfer characteristics, etc.) and the mixture ratio, gas flow rate, and gas temperature of the mixed gas are largely different. Cannot be decided. However, by actually measuring the parameters in the adsorption tower and actively applying a parameter gradient corresponding to the measured parameters, the concentration of the separation gas can be improved and the recovery rate can be improved.

  As one of the methods for actively providing the parameter gradient, when the parameter is temperature, the mixed gas is passed through the adsorption tower packed with the gate-type porous polymer complex without temperature control, and the adsorption tower A method of measuring the temperature with a temperature sensor and cooling a portion having a high temperature or heating a portion having a low temperature in relation to the occurrence of a gate phenomenon according to the value of the temperature can be mentioned. This is because the gate phenomenon is less likely to occur at high temperatures, so it is possible to prevent the gate phenomenon from becoming difficult by cooling, and the vibration phenomenon by homogenizing the temperature distribution in the tower after completion of adsorption. It is a method of stopping. Moreover, the method of heating a part with high temperature or cooling from a part with low temperature as a reverse means is also mentioned. Contrary to the method described above, by further heating the high-temperature part where the gate is unlikely to occur, the part where the gate is prone to actively occur and the part where the gate is unlikely to occur are created separately in the tower, and the temperature distribution is fixed. This is a method for suppressing the vibration phenomenon. Which method is more effective can be determined by the material characteristics of the gate-type porous polymer complex to be used and the actual operating conditions such as the partial pressure, gas flow rate, and temperature of the gas species to be adsorbed.

  The method for heating or cooling the adsorption tower may be any method that can substantially increase or decrease the material temperature of the gate-type porous polymer complex, and the method is not limited. Preferred methods include a method of installing a heating or cooling device outside, a method of installing a heating or cooling device inside, a method of dispersing a heat storage material or the like in the material, and the like. As another method, in order to suppress heat generation, a method of mixing and using a low gas adsorbing material in a gate-type porous polymer complex is used in a place where the temperature is to be lowered. A method using a mixture of gate type porous polymer complexes and a method using a mixture of non-gate type adsorbents are also included. When heating is desired, a method of mixing and using an adsorbent with a large calorific value is also included.

  As a result of performing the temperature control as described above, the gate of the gate-type porous polymer complex may suddenly open, and the position of heat generation may move in the tower. In this case, the active temperature control based on the temperature measurement is performed again, and this is repeated to maximize the gas separation efficiency and the like. For example, by using a temperature controller that attaches a temperature sensor to the entire area of the adsorption tower packed with the gate type porous polymer complex and compares the signal from the temperature sensor with a predetermined signal of the gate phenomenon expression temperature to obtain a difference signal The temperature of a specific position of the adsorption tower can be controlled by controlling the heating device or the cooling device.

  When there are a plurality of high temperature portions before or after performing active temperature control, optimization can be performed by performing temperature control on each location.

  One method of actively applying a parameter gradient is a method of creating a pressure gradient in the tower by installing an orifice or the like, for example, when the parameter is pressure. This is because the gate phenomenon is unlikely to occur at low pressure parts, so it is possible to prevent the gate phenomenon from becoming difficult by increasing the pressure, and the vibration phenomenon is achieved by homogenizing the pressure distribution in the tower after completion of adsorption. It is a method of stopping. Moreover, as a reverse means, a method of depressurizing a low pressure portion or pressurizing a high pressure portion can be mentioned. Contrary to the method described above, by further reducing the pressure of the low-pressure part where gates are unlikely to occur, the part where active gates are likely to occur and the part where they are less likely to occur are created separately in the tower to suppress pressure fluctuations. This is a method to reduce the vibration phenomenon. Which method is more effective can be determined by the material characteristics of the gate-type porous polymer complex to be used and the actual operating conditions such as the partial pressure, gas flow rate, and temperature of the gas species to be adsorbed.

  The method of pressurizing or depressurizing the adsorption tower may be any method that can substantially increase or decrease the pressure in the tower, and the method is not limited. Preferred methods include a method of forming a pressure distribution by installing an orifice or the like in the tower, and a method of controlling pressure by installing a pressure or pressure reducing valve in the middle of the tower.

  As a pressure control method, in addition to the mechanical pressure operation as described above, by mixing and using a material having a high gas adsorptivity with respect to the gate type porous polymer complex in a portion where the gas pressure is desired to be reduced, A method to lower the gas pressure is also recommended. As a material used by mixing at this time, a non-gate type adsorbent such as an existing zeolite or activated carbon, or a gate type porous polymer complex having a non-gate type and / or another type of gate characteristics can be used.

  As a result of the pressure control as described above, the position where the gate suddenly opens and the pressure fluctuates may move in the tower. In this case, the active pressure control based on the pressure measurement is performed again, and this is repeated to maximize the gas separation efficiency and the like. For example, by using a pressure controller that attaches a pressure sensor to the entire area of the adsorption tower packed with a gate-type porous polymer complex and compares the signal from the pressure sensor with a predetermined signal of the gate phenomenon expression pressure to obtain a difference signal The pressure at a specific position of the adsorption tower can be controlled by controlling the pressurizing device or the decompressing device.

  When there are a plurality of high-pressure parts before or after active pressure control is performed, optimization can be performed by performing pressure control on each part.

  The gas separation device of the present invention can have the same configuration as an existing PSA type gas separation device. An example of the gas separation apparatus of the present invention is shown in FIG. 4 as a schematic diagram. The gas separation apparatus shown in FIG. 4 includes a first adsorption tower 1, a second adsorption tower 11, a first separation gas storage container 2, a second separation gas storage container 3, a gas compression apparatus 4, valves 2 to 4, and valves 12 to 14, valves 7 to 9 and pressure gauges 5 and 6. In this example, there are two adsorption towers. However, in the present invention using the gate type porous polymer complex exhibiting the gate phenomenon, the adsorption mode and the regeneration mode in the adsorption tower can be switched in a short time. There may be one, or three or more. The mixed gas to be separated is supplied to the adsorption towers 1 and 11 from a gas compression device 4 which is a gas supply unit.

  The plurality of adsorption towers are filled with a gate type porous polymer complex. The mixed gas to be treated is compressed by the gas compression device 4 and introduced into the adsorption towers 1 and 11 from the introduction valves 3 and 13 provided at the inlets of the respective adsorption towers. One of the gases separated in the adsorption towers 1 and 11 is sent to the first separated gas storage container 2 through the discharge valves 2 and 12. A pressure regulating valve 7 is provided downstream of the first separation gas storage container 2. The other of the separated gases passes through the discharge valves 4 and 14, and is sent to the second separated gas storage container 3 through the inlet valve 8. A pressure gauge 5 is attached to the second separation gas storage container 3, and the pressure gauge 5 outputs a signal based on the pressure in the second separation gas storage container 3. A pressure regulating valve 9 is provided downstream of the second separation gas storage container 3. A pressure gauge 6 is attached to the pressure regulating valve 9, and the pressure regulating valve 9 is controlled based on signals from the pressure gauges 5 and 6.

  The present invention is a method and apparatus for controlling the characteristics of gas separation by performing parameter control to eliminate or fix the nonuniformity of parameter distribution in the tower caused by the gate phenomenon. Although the temperature and pressure are shown as parameters, it is possible to further improve the gas separation characteristics and the recovery rate by performing positive or negative control in the same manner for other parameters.

Example 1 (invention example)
A gate-type porous polymer complex precursor preELM-11 (Tokyo Chemical Industry Co., Ltd.) is attached to an adsorption tower having an inner diameter of 30 mm and a length of 100 mm, in which a ribbon heater having a width of 2 centimeters is wound around an entrance side, an exit side, and an intermediate point. (Purchased from the company) 10 g was loaded into the tower using a glass filter and a sintered filter so that the powder was not scattered. The adsorption tower was heated with nitrogen gas flow (50 mL / min) at 120 ° C. for 3 hours to convert preELM-11 to ELM-11 having an adsorption action.

At room temperature 25 ° C, energize the ribbon heaters wound at the entrance, exit and intermediate points, set the entrance temperature of the adsorption tower to 50 ° C and the exit temperature to 30 ° C. The intermediate temperature is the entrance temperature. And the average temperature of the outlet side temperature. Nitrogen and CO ₂ mixed gas (mixing ratio 2/1 (v / v), purity> 99.99%) was passed at an outlet flow rate of 2 mL / min. The CO ₂ breakthrough time was 27 minutes.

Examples 2 to 4 (Invention Examples)
The same operation as in Example 1 was performed by changing the gas type used, the inlet side temperature and the outlet side temperature of the adsorption tower.

Example 5 (Invention)
By installing a sintered filter with a thickness of 18 mm at the intermediate point between the entrance side and the exit side of the adsorption tower, when the mixed gas of nitrogen and CO ₂ is circulated at the exit side flow rate of 2 mL / min, before the filter The pressure was adjusted to 1.4 atm, and the pressure after the filter was adjusted to 1.0 atm. Under the conditions shown in Table 1, the same operation as in Example 1 was performed without performing temperature control.

Examples 6 to 9 (invention examples)
C2F5-KGM was used as the adsorbent. The gas types used are shown in Table 1. The same operation as in Example 1 was performed by changing the inlet side temperature and the outlet side temperature of the adsorption tower. The adsorbent “C2F5-KGM” used in Example 6-9 is a PCP having a C ₂ F ₅ group as a side chain described in International Publication No. WO2014 / 069574.

Example 10 (Invention)
The same operation as in Example 5 was performed without performing temperature control under the conditions shown in Table 1 except that C2F5-KGM was used as the adsorbent and the gas type used was N ₂ / CO = 1/2. It was.

Example 11 (Invention)
In an adsorption tower having an inner diameter of 30 mm and a length of 100 mm, a ribbon heater having a width of 2 centimeters was wound around the entry side, the exit side, and the intermediate point. The ribbon heater was energized, and the inlet temperature of the adsorption tower was set to 50 ° C. and the outlet temperature was set to 30 ° C. The intermediate temperature was set to the average temperature of the inlet side temperature and the outlet side temperature. Furthermore, by installing a 18 mm thick sintered filter at the intermediate point between the entrance side and the exit side of the adsorption tower, when the nitrogen and CO ₂ mixed gas is circulated at the exit side flow rate of 2 mL / min, the filter The pressure was adjusted to 1.4 atm in front and 1.0 atm after filter. Using ELM-11 as the adsorbent, nitrogen and CO ₂ mixed gas (mixing ratio 2/1 (v / v), purity> 99.99%) at the outlet flow rate of 2 mL / min under the conditions shown in Table 1 Circulated. The CO ₂ breakthrough time was 33 minutes.

Comparative Example 1-4
In Comparative Example 1-4, the mixed gas shown in Table 2 was circulated at an outlet-side flow rate of 2 mL / min as in the inventive examples, and gas separation was performed under the conditions shown in Table 2.

  As can be seen from the results of the breakthrough times shown in Tables 1 and 2, when the Example and the Comparative Example are compared, the breakthrough time becomes longer under the condition that the parameters (temperature, pressure) are both graded. In other words, it was found that the gas separation is excellent because the target gas species are more strongly adsorbed by suppressing abnormal phenomena such as vibration of the gate phenomenon.

Claims (10)

A gas separation device including an adsorption tower packed with a gate-type porous polymer complex exhibiting a gate phenomenon,
A gas supply means for supplying a mixed gas containing a plurality of gases to the adsorption tower to cause a gate phenomenon in the adsorption tower;
A gas separation apparatus comprising at least means for controlling a parameter distribution for controlling the parameter related to the onset of the gate phenomenon so that the gate phenomenon is uniformly expressed in the adsorption tower.   The gas separation device according to claim 1, wherein the parameter is a temperature and / or a gas pressure in the adsorption tower.   The gas separation device according to claim 1 or 2, wherein the means for controlling the parameter related to the onset of the gate phenomenon includes a temperature sensor, a temperature controller, a heating means, and a cooling means attached to the entire area in the adsorption tower.   The gas separation apparatus according to claim 1 or 2, wherein the means for controlling the parameter related to the onset of the gate phenomenon includes a pressure sensor, a pressure controller, a pressurizing means, and a depressurizing means attached to the entire area in the adsorption tower. .   The means for controlling the parameter related to the onset of the gate phenomenon includes a pressure sensor, a temperature sensor, a pressure controller, a temperature controller, a heating means, a cooling means, a pressurizing means, and a decompressing means attached to the entire area of the adsorption tower. The gas separation device according to claim 1 or 2, comprising the gas separation device.   The gas separation device according to any one of claims 1 to 5, wherein the gate-type porous polymer complex exhibits a gate-type isotherm with respect to at least one of the mixed gases.   The gas separation device according to claim 6, wherein the gate type porous polymer complex is selected from ELMs, kagomes, MILs, and CIDs.   The gas separation device according to claim 7, wherein the gate type porous polymer complex has an adsorption gate coefficient of 0.7 to 75 and a desorption gate coefficient of 0.4 to 80.   The gas separation device according to claim 7, wherein a pressure difference between an adsorption completion gate pressure and a desorption completion gate pressure of the gate type porous polymer complex is 2 kPa to 8000 kPa.   The gas separation according to any one of claims 1 to 9, wherein the gas species is any one of oxygen, nitrogen, argon, carbon dioxide, carbon monoxide, hydrogen, alkanes, alkenes, and alkynes. apparatus.

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