JP2016040214A - Purification system of hydrogen and olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a purification system of hydrogen and olefin which is capable of purifying hydrogen and olefin as useful gas from gas mixture containing at least hydrogen and olefin, and purifying at least one of hydrogen and olefin at higher recovery rate.SOLUTION: Because an olefin separation membrane module 10A is arranged in a previous step of a hydrogen separation membrane module 20A, olefin is separated from gas mixture in the previous step of the hydrogen separation membrane module 20A. In short, in a purification system 1, because hydrogen is separated by a hydrogen separation membrane 21 after hydrogen concentration in first impermeable gas is raised, recovery rate of hydrogen can be increased to a higher level. Thus, the purification system 1 can purify hydrogen and olefin as useful gas from gas mixture containing at least hydrogen and olefin, and purify hydrogen at higher recovery rate.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hydrogen and olefin purification system.

  Conventionally, a technique for purifying a useful gas from a mixed gas containing a plurality of components is known. For example, Patent Document 1 describes a method of refining olefin as a useful gas from FCC offgas generated in a fluid catalytic cracking (FCC) step in an oil refining process.

JP 2006-307133 A

  However, Patent Document 1 does not disclose a method for purifying hydrogen as a useful gas together with olefins from FCC offgas. Accordingly, the present invention provides a hydrogen and olefin purification system capable of purifying hydrogen and olefin as useful gases from a mixed gas containing at least hydrogen and olefin, and purifying at least one of hydrogen and olefin with a higher recovery rate. The purpose is to do.

  In order to solve the above problems, a hydrogen and olefin purification system according to the present invention includes a hydrogen separation unit having a hydrogen separation membrane that selectively separates hydrogen from a mixed gas containing hydrogen and olefin, and hydrogen separation of the hydrogen separation unit. An olefin separation unit having an olefin separation membrane that selectively separates olefins from a non-permeate gas that does not permeate the membrane.

  In the hydrogen and olefin purification system according to the present invention, hydrogen is separated from the mixed gas by the hydrogen separation membrane of the hydrogen separation section, and then the olefin is separated from the non-permeated gas by the olefin separation membrane of the olefin separation section. That is, in this refinement system, since the olefin concentration in the non-permeate gas is increased and then the olefin is separated by the olefin separation membrane, the olefin recovery rate can be further increased. Thereby, this refinement | purification system can refine | purify olefin with a higher recovery rate while refine | purifying hydrogen and olefin as useful gas from the mixed gas containing hydrogen and olefin at least.

  The mixed gas may have a higher hydrogen concentration than the olefin concentration. In this case, by separating the hydrogen having a higher concentration than the olefin before the olefin, the hydrogen can be purified with a higher recovery rate while increasing the recovery rate of the olefin.

  The value obtained by multiplying the hydrogen concentration in the mixed gas by the hydrogen separation factor for methane in the hydrogen separation membrane is greater than the value obtained by multiplying the olefin concentration in the mixed gas by the propylene separation factor for propane in the olefin separation membrane. May be. In this case, by separating hydrogen that is easier to separate than olefin before olefin, hydrogen can be purified at a higher recovery rate while increasing the recovery rate of olefin.

  The hydrogen and olefin purification system according to the present invention includes an olefin separation unit having an olefin separation membrane that selectively separates olefins from a mixed gas containing hydrogen and olefins, and a non-permeating olefin separation membrane. And a hydrogen separation unit having a hydrogen separation membrane that selectively separates hydrogen from the permeate gas.

  In the hydrogen and olefin purification system according to the present invention, the olefin is separated from the mixed gas by the olefin separation membrane of the olefin separation section, and then the hydrogen is separated from the non-permeated gas by the hydrogen separation membrane of the hydrogen separation section. That is, in the present purification system, hydrogen is separated by the hydrogen separation membrane after increasing the hydrogen concentration in the non-permeating gas, so that the hydrogen recovery rate can be further increased. Thereby, this refinement | purification system can refine | purify hydrogen with a higher recovery rate while refine | purifying hydrogen and an olefin as useful gas from the mixed gas containing hydrogen and an olefin at least.

  The mixed gas may have a higher olefin concentration than hydrogen concentration. In this case, by separating the olefin having a higher concentration than hydrogen before the hydrogen, the olefin can be purified at a higher recovery rate while increasing the hydrogen recovery rate.

  The value obtained by multiplying the olefin concentration in the mixed gas by the separation factor of propylene with respect to propane in the olefin separation membrane is larger than the value obtained by multiplying the hydrogen concentration in the mixed gas by the separation factor of hydrogen with respect to methane in the hydrogen separation membrane. May be. In this case, by separating the olefin that is easier to separate than hydrogen before the hydrogen, the olefin can be purified at a higher recovery rate while increasing the recovery rate of hydrogen.

  The separation factor of propylene with respect to propane in the olefin separation membrane may be 90 or more. Thus, by setting the separation factor of propylene to propane of the olefin separation membrane to 90 or more, the concentration of olefin purified (recovery) even when the total pressure of the mixed gas or non-permeated gas is set to a relatively high pressure (for example, 2 MPaG). The olefin concentration can be high (for example, 90 vol% or more).

  Further, the pressure of the mixed gas may be 1.5 MPaG or more. Thus, by setting the pressure of the mixed gas to 1.5 MPaG or more, both the olefin recovery rate and the hydrogen recovery rate can be increased (for example, 50 vol% or more).

  According to the present invention, hydrogen and olefin can be purified as a useful gas from a mixed gas containing at least hydrogen and olefin, and at least one of hydrogen and olefin can be purified with a higher recovery rate.

It is the schematic which shows the structure of the refinement | purification system of hydrogen and an olefin which concerns on 1st Embodiment of this invention. It is the schematic which shows the structure of the refinement | purification system of the hydrogen and olefin which concerns on 2nd Embodiment of this invention. It is the schematic which shows the structure of the refinement | purification system of the hydrogen and olefin which concerns on 3rd Embodiment of this invention. It is the schematic which shows the structure of the refinement | purification system of hydrogen and an olefin which concerns on 4th Embodiment of this invention. It is the schematic which shows the structure of the refinement | purification system of hydrogen and olefin which concerns on 5th Embodiment of this invention. It is the schematic which shows the structure of the refinement | purification system of the hydrogen and olefin which concerns on 6th Embodiment of this invention. It is sectional drawing which shows the example of the internal structure of a hydrogen separation membrane module and an olefin separation membrane module.

  Preferred embodiments of the present invention will be described below with reference to the drawings. In addition, in each drawing, the same code | symbol is attached | subjected to the same or an equivalent part, and the overlapping description may be abbreviate | omitted.

[First Embodiment]
FIG. 1 is a schematic diagram showing the configuration of a hydrogen and olefin purification system 1 according to the first embodiment of the present invention. As shown in FIG. 1, the purification system 1 according to this embodiment is a system that purifies hydrogen and olefins contained in a mixed gas supplied from a mixed gas supply source 100.

  The mixed gas according to the present embodiment is not particularly limited as long as it contains at least hydrogen and olefin. Examples of other components include methane, ethane, propane, carbon monoxide, carbon dioxide, nitrogen, oxygen, and water vapor. It may be. Here, the olefin is a hydrocarbon having at least one double bond between carbons, and examples thereof include ethylene, propylene, butene, and butadiene. More specific examples of the mixed gas include, for example, a by-product gas in a thermal cracking process and a fluid catalytic cracking (FCC) process in an oil refining process (usually a hydrogen concentration of 5 vol% to 30 vol%, and an olefin concentration of 5 vol% to 30 vol). %) Or less, and a product gas in propane dehydrogenation. In the present embodiment, description will be made using a by-product gas (FCC off gas) generated in the FCC process.

  Next, the configuration of the purification system 1 will be described.

  The purification system 1 includes an olefin separation membrane module (olefin separation unit) 10A having an olefin separation membrane 11 that selectively separates olefins, and a hydrogen separation membrane module (hydrogen separation) having a hydrogen separation membrane 21 that selectively separates hydrogen. Part) 20A. In the purification system 1, the olefin separation membrane module 10A is arranged at the front stage (first stage) and the hydrogen separation membrane module 20A at the rear stage (second stage) from upstream to downstream with respect to the flow of the mixed gas. Yes.

  The olefin separation membrane module 10 </ b> A does not permeate the olefin separation membrane 11, the inlet 12 through which the mixed gas flows, the permeate gas outlet 13 through which the permeated gas (high-purity olefin) permeated through the olefin separation membrane 11 is discharged. And a non-permeate gas outlet 14 for discharging the non-permeate gas. The olefin selectively separated from the mixed gas by the olefin separation membrane 11 is discharged from the permeated gas discharge port 13 as the first permeated gas. The mixed gas from which the olefin has been separated is discharged from the non-permeate gas outlet 14 as a first non-permeate gas. The hydrogen separation membrane module 20A includes an inlet 22 through which the first non-permeating gas flows, a permeated gas outlet 23 through which the permeated gas (high-purity hydrogen) that has permeated the hydrogen separation membrane 21 is discharged, and a hydrogen separation membrane. And a non-permeate gas discharge port 24 for discharging the non-permeate gas that has not permeated through 21. The hydrogen selectively separated from the first non-permeate gas by the hydrogen separation membrane 21 is discharged from the permeate gas outlet 23 as the second permeate gas. The first non-permeate gas after the hydrogen is separated is discharged from the non-permeate gas outlet 24 as the second non-permeate gas.

  The inlet 12 of the olefin separation membrane module 10A is connected to a line L1 through which the mixed gas from the mixed gas supply source 100 passes. The inlet 22 of the hydrogen separation membrane module 20A is connected to a line L2 through which the first non-permeate gas from the non-permeate gas discharge port 14 of the olefin separation membrane module 10A passes.

  The non-permeate gas outlet 24 of the hydrogen separation membrane module 20A is connected to the line L5, and the second non-permeate gas passes through the line L5 and is used for a predetermined application as an off-gas. For example, since the second non-permeating gas contains methane, ethane, propane, and the like, it is used as fuel for the heating furnace. Thus, when utilizing as a fuel, since the olefin is isolate | separated by 10 A of olefin separation membrane modules and the density | concentration of an olefin is falling, generation | occurrence | production of the coke which is a residue is suppressed.

  The permeated gas discharge port 13 of the olefin separation membrane module 10A is connected to the olefin recovery line L6. The first permeated gas that has passed through the olefin separation membrane 11 passes through the olefin recovery line L6 and is recovered as a high-purity olefin. The permeate gas outlet 23 of the hydrogen separation membrane module 20A is connected to the hydrogen recovery line L7. The second permeated gas that has permeated the hydrogen separation membrane 21 is recovered as high-purity hydrogen through the hydrogen recovery line L7.

  A compressor 30 is arranged in the line L1. The compressor 30 has a function of pressurizing the total pressure of the mixed gas supplied from the mixed gas supply source 100 and passing through the line L1 to a predetermined pressure (for example, 0.2 MPaG or more). As a result, the mixed gas is pressurized to a predetermined pressure and then supplied to the olefin separation membrane module 10A. In the present embodiment, the pressure (total pressure) of the mixed gas pressurized by the compressor 30 is preferably 1.5 MPaG or more from the viewpoint of increasing the hydrogen recovery rate and the olefin recovery rate. Further, from the viewpoint of maintaining the recovered hydrogen concentration and recovered olefin concentration in a high state, it is preferably 3.0 MPaG or less, and particularly preferably 2.0 MPaG or less. The pressurizing means for pressurizing the mixed gas is not limited to the compressor 30 as long as the gas supplied to the olefin separation membrane module 10A and the hydrogen separation membrane module 20A can be pressurized to a predetermined pressure.

  Next, the structure of the olefin separation membrane module 10A and the hydrogen separation membrane module 20A will be described with reference to FIG. FIG. 7 is a cross-sectional view showing an example of the internal structure of the hydrogen separation membrane module 20A and the olefin separation membrane module 10A.

  The olefin separation membrane module 10A includes at least a supply chamber SP1 to which a mixed gas is supplied, a recovery chamber RC1 that recovers a first permeated gas (high-purity olefin) that has passed through the olefin separation membrane 11, and a supply chamber SP1 and a recovery chamber. The olefin separation membrane 11 that separates the chamber RC1 may be provided. As long as this condition is satisfied, the configuration of the olefin separation membrane module 10A is not limited. The olefin in the supply chamber SP1 is driven by the difference between the partial pressure of the olefin in the mixed gas in the supply chamber SP1 and the partial pressure of the olefin in the first permeate gas in the recovery chamber RC1, and the olefin separation membrane 11 is driven. It passes through and moves to the recovery chamber RC1. Since the first non-permeate gas is supplied to the subsequent hydrogen separation membrane module 20A without greatly reducing the pressure, for example, even if a pressurizing means different from the compressor 30 is not disposed in the line L2, the latter The hydrogen separation membrane module 20A can appropriately purify hydrogen.

  Similarly, the hydrogen separation membrane module 20A includes at least a supply chamber SP2 to which the first non-permeating gas is supplied, and a recovery chamber RC2 that recovers the second permeating gas (high-purity hydrogen) that has permeated the hydrogen separation membrane 21. The hydrogen separation membrane 21 that separates the supply chamber SP2 and the recovery chamber RC2 may be provided. As long as this condition is satisfied, the configuration of the hydrogen separation membrane module 20A is not limited. The hydrogen in the supply chamber SP2 is driven by the difference between the partial pressure of hydrogen in the first non-permeate gas in the supply chamber SP2 and the partial pressure of hydrogen in the second permeate gas in the recovery chamber RC2. It moves through the membrane 21 and moves to the recovery chamber RC2. Note that the second non-permeating gas is discharged to the line L5 without greatly reducing the pressure.

  An olefin separation membrane module 10 </ b> A shown in FIG. 7A is configured by disposing a tubular olefin separation membrane 11 inside a cylindrical body 15. A space inside the olefin separation membrane 11 constitutes a supply chamber SP1 to which a mixed gas is supplied. The space outside the olefin separation membrane 11 (the space between the olefin separation membrane 11 and the cylinder 15) constitutes a recovery chamber RC1 that recovers the first permeated gas that has permeated the olefin separation membrane 11. On one end surface of the cylindrical body 15, an inflow port 12 through which the mixed gas flows and a non-permeate gas discharge port 14 through which the first non-permeate gas is discharged are provided. The inlet 12 and the non-permeate gas outlet 14 are in communication with the supply chamber SP1. On the other end face of the cylinder 15, a permeated gas discharge port 13 for discharging the first permeated gas is provided. The permeate gas discharge port 13 communicates with the recovery chamber RC1. In addition, in the supply chamber SP1, the flow of the mixed gas is formed by providing the inner wall, but the configuration of the inner wall is not particularly limited.

  A hydrogen separation membrane module 20 </ b> A shown in FIG. 7A is configured by disposing a tubular hydrogen separation membrane 21 inside a tubular body 25. A space inside the hydrogen separation membrane 21 constitutes a supply chamber SP2 to which the first non-permeating gas is supplied. The space outside the hydrogen separation membrane 21 (the space between the hydrogen separation membrane 21 and the cylinder 25) constitutes a recovery chamber RC2 that recovers the second permeated gas that has permeated the hydrogen separation membrane 21. On one end face of the cylindrical body 25, an inflow port 22 through which the first non-permeate gas flows and a non-permeate gas discharge port 24 through which the second non-permeate gas is discharged are provided. The inlet 22 and the non-permeate gas outlet 24 are in communication with the supply chamber SP2. On the other end face of the cylindrical body 25, a permeated gas discharge port 23 for discharging the second permeated gas is provided. The permeate gas discharge port 23 communicates with the recovery chamber RC2. In addition, in supply chamber SP2, although the flow of mixed gas is formed by providing an inner wall, the structure of the said inner wall is not specifically limited.

  The olefin separation membrane module 10Aa shown in FIG. 7B is configured by disposing a cylindrical olefin separation membrane 11a inside a cylindrical body 15a. A space outside the olefin separation membrane 11a (a space between the olefin separation membrane 11a and the cylinder 15a) constitutes a supply chamber SP1a to which a mixed gas is supplied. The space inside the olefin separation membrane 11a constitutes a recovery chamber RC1a that recovers the first permeated gas that has passed through the olefin separation membrane 11a. On the outer surface of the cylindrical body 15a, an inflow port 12a through which the mixed gas flows and a non-permeate gas discharge port 14a through which the first non-permeate gas is discharged are provided. The inlet 12a and the non-permeate gas outlet 14a are in communication with the supply chamber SP1a. A permeate gas discharge port 13a for discharging the first permeate gas is provided on one end face of the cylindrical body 15a. The permeate gas discharge port 13a communicates with the recovery chamber RC1a.

  The hydrogen separation membrane module 20Aa shown in FIG. 7B is configured by arranging a cylindrical hydrogen separation membrane 21a inside a cylindrical body 25a. A space outside the hydrogen separation membrane 21a (a space between the hydrogen separation membrane 21a and the cylinder 25a) constitutes a supply chamber SP2a to which the first non-permeating gas is supplied. The space inside the hydrogen separation membrane 21a constitutes a recovery chamber RC2a that recovers the second permeated gas that has permeated the hydrogen separation membrane 21a. On the outer surface of the cylindrical body 25a, an inflow port 22a through which the first non-permeable gas flows and a non-permeable gas discharge port 24a through which the second non-permeable gas is discharged are provided. The inflow port 22a and the non-permeate gas discharge port 24a are in communication with the supply chamber SP2a. A permeate gas discharge port 23a for discharging the second permeate gas is provided on one end surface of the cylindrical body 25a. The permeate gas outlet 23a communicates with the recovery chamber RC2a. In the following description, the olefin separation membrane module 10A and the hydrogen separation membrane module 20A are employed. However, the same effect can be obtained even when the olefin separation membrane module 10Aa and the hydrogen separation membrane module 20Aa are employed.

  The structures of the olefin separation membrane module 10A and the hydrogen separation membrane module 20A are not limited to those shown in FIG. For example, a plurality of cylindrical olefin separation membranes 11 and hydrogen separation membranes 21 may be provided in the cylinders 15 and 25. Moreover, you may use the planar olefin separation membrane 11 and the hydrogen separation membrane 21 instead of a cylinder shape. Moreover, the same structure may be employ | adopted by the olefin separation membrane module 10A and the hydrogen separation membrane module 20A, and a mutually different structure may be employ | adopted.

  Moreover, in order to adjust the operating temperature of the olefin separation membrane 11 and the hydrogen separation membrane 21 in the olefin separation membrane module 10A and the hydrogen separation membrane module 20A, a heating mechanism 40 such as a heater may be provided in the line L1. The heating mechanism 40 heats the mixed gas. By supplying the heated mixed gas, the olefin separation membrane 11 and the hydrogen separation membrane 21 are heated. It is preferable that the heating mechanism 40 can adjust the operating temperature of the olefin separation membrane 11 and the hydrogen separation membrane 21 at least between room temperature and about 100 ° C. The position of the heating mechanism 40 is not limited to the line L1, and may be arranged so that the operating temperatures of the olefin separation membrane 11 and the hydrogen separation membrane 21 are appropriate. For example, the heating mechanism 40 may be disposed around the cylinders 15 and 25 of the olefin separation membrane module 10A and the hydrogen separation membrane module 20A. The heating mechanism 40 is not limited to a heater, and may use a heating medium.

  Subsequently, the olefin separation membrane 11 and the hydrogen separation membrane 21 will be described.

Separation performance (selectivity) of the olefin separation membrane 11 and the hydrogen separation membrane 21 can be expressed by a separation coefficient. The separation factor is expressed as a ratio of gas permeability between the target gas (olefin or hydrogen) and another gas. Here, the permeability (m ³ (STP) / (m ² · sec · kPa)) is represented by a permeated gas volume (standard state) per unit time, unit area, and unit pressure (differential pressure). The separation factor of the olefin separation membrane 11 is defined by the permeability of propylene to the permeability of propane. The separation factor of the hydrogen separation membrane 21 is defined by the hydrogen permeability relative to the methane permeability.

  Any type of separation membrane can be applied to the olefin separation membrane 11 as long as it can selectively separate olefins. As the olefin separation membrane 11, an inorganic membrane such as a zeolite membrane, a polymer membrane such as a polyimide membrane, a facilitated transport membrane, or the like may be applied. For example, as the olefin separation membrane 11, 6FDA-2, 4DAT, 6FDA-2, 6DAT, 6FDA-BAAF, or the like can be adopted. Here, DAT is diaminotoluene, 6FDA is hexafluoroisopropylidene-2,2-bis (phthalic anhydride), and BAAF is 2,2-bis (4-aminophenyl) hexafluoropropane. The separation performance (selectivity) of the olefin separation membrane 11 increases as the separation factor of the olefin separation membrane 11 increases. In this embodiment, the separation factor of the olefin separation membrane 11 is preferably 90 or more from the viewpoint that the recovered olefin concentration can be maintained in a high state even when the total pressure of the target gas is set to a relatively high pressure (for example, 2 MPaG).

  The hydrogen separation membrane 21 has a function of selectively separating hydrogen. For example, a molecular sieving membrane, a polymer membrane (polyimide, triacetate, etc.) and a porous membrane (porous) that separate gases by molecular size. Silica, zeolite, porous carbon, etc.). The hydrogen separation membrane 21 has higher separation performance (selectivity) as the separation factor of the hydrogen separation membrane 21 is larger. The hydrogen separation membrane 21 is not limited to the above as long as it can selectively separate hydrogen, and any type of separation membrane can be applied. In the present embodiment, the separation factor of the hydrogen separation membrane 21 is preferably 100 or more from the viewpoint of increasing the recovered hydrogen concentration.

  The operating temperature of the olefin separation membrane 11 and the hydrogen separation membrane 21 may be not less than room temperature (for example, about 20 ° C.) and not more than 100 ° C. By setting the operating temperature to 100 ° C. or lower, olefin hydrogenation and olefin polymerization reaction due to high temperatures can be suppressed. Even when a polymer membrane or the like is used as the hydrogen separation membrane 21, deterioration of the hydrogen separation membrane 21 due to high temperature can be suppressed. Moreover, it can suppress that the partial pressure of hydrogen and an olefin falls by water in a mixed gas evaporating into water vapor | steam resulting from high temperature, for example, and this water vapor | steam mixing in a mixed gas. On the other hand, by setting the operating temperature to room temperature or higher, it is possible to suppress a decrease in the gas permeation rate of the olefin separation membrane 11 and the hydrogen separation membrane 21 due to low temperature. Further, for example, when the refining system 1 is used in a cold district, freezing of the olefin separation membrane 11 and the hydrogen separation membrane 21 can be suppressed even if the outside air temperature rapidly decreases. Conventionally, a hydrogen separation membrane containing a noble metal such as a Pd—Cu alloy is known, but the use temperature of such a hydrogen separation membrane needs to be a high temperature of, for example, 200 ° C. or higher. On the other hand, since the molecular sieve membrane, the polymer membrane, and the porous membrane described above can be used at a lower operating temperature as compared with a hydrogen separation membrane containing a noble metal, the above-described effects are exhibited.

  Next, the arrangement order of the olefin separation membrane module 10A and the hydrogen separation membrane module 20A in the purification system 1 will be described.

  Of the olefin separation membrane module 10A and the hydrogen separation membrane module 20A, the high recovery rate of olefin and hydrogen from the mixed gas varies depending on which separation membrane module is disposed in the previous stage. In this embodiment, in order to increase the recovery rate of olefin and hydrogen, the olefin separation membrane module is based on the concentration of olefin and hydrogen in the mixed gas and the separation coefficients of the olefin separation membrane 11 and the hydrogen separation membrane 21. The separation membrane module to be arranged in the previous stage is determined among 10A and the hydrogen separation membrane module 20A.

  Specifically, in the purification system 1, a value obtained by multiplying the concentration of olefin in the mixed gas before purification (mixed gas supplied from the mixed gas supply source 100) by the separation factor of the olefin separation membrane 11, and before purification. A value obtained by multiplying the concentration of hydrogen in the mixed gas by the separation factor of the hydrogen separation membrane 21 is compared, and a separation membrane module for separating the gas having the larger value is disposed in the previous stage. At the subsequent stage, a separation membrane module for separating the other gas is arranged. Similarly, the separation membrane modules can be arranged alternately and in multiple stages. In this case, the recovery rate of hydrogen and olefin from the mixed gas can be increased as the number of separation membrane modules arranged alternately is increased.

  Thus, by determining the order of arrangement of the separation membrane modules, the gas recovery rate in the preceding separation membrane module can be increased. Further, since one gas is separated by the preceding separation membrane module, the non-permeating gas discharged from the preceding separation membrane module has a relatively high concentration of the other gas and a high partial pressure. For this reason, the recovery rate of the gas can be increased also in the separation membrane module at the subsequent stage for separating the other gas. Therefore, the purification system 1 can purify hydrogen and olefin from the mixed gas with a higher recovery rate. Next, a case where separation membrane modules are arranged alternately and in multiple stages will be described. Since one gas is separated by the separation membrane module at the first stage (first stage), the first non-permeate gas discharged from the separation membrane module at the first stage is the other of the mixed gas before purification. The gas concentration is higher. For this reason, the recovery rate of the other gas can be increased in the separation membrane module at the subsequent stage (second stage). Similarly, since the other gas is separated by the separation membrane module at the second stage, the recovery rate of one gas can be increased in the separation membrane module at the subsequent stage (third stage). In this way, the gas recovery rate can be increased also in the separation membrane modules in the fourth and subsequent stages.

  A separation membrane module that compares the concentrations of olefin and hydrogen in the mixed gas before purification and separates the gas having the higher concentration may be disposed in the previous stage. In this case, since a gas having a relatively high concentration (relatively easy to separate) can be separated by the separation membrane module in the previous stage, it is suitable for purifying hydrogen and olefin from the mixed gas with a higher recovery rate.

  As described above, as a method for determining the separation membrane module to be arranged in the preceding stage, the method of comparing the value obtained by multiplying the concentration in the mixed gas before purification by the separation factor and the method of comparing the concentration have been described. Either method may not be employed, and at least the hydrogen separation membrane module 20A and the olefin separation membrane module 10A need only be arranged in order with respect to the flow of the mixed gas.

  In the purification system 1 shown in FIG. 1, since the olefin separation membrane module 10A is arranged in the previous stage of the hydrogen separation membrane module 20A provided in the second stage, only the hydrogen separation membrane module 20A is used from the mixed gas. Compared with the case of purifying hydrogen, the hydrogen recovery rate can be increased. In particular, when the concentration of the olefin in the mixed gas is high, or when the value obtained by multiplying the olefin concentration by the separation factor of the olefin separation membrane 11 is large, the olefin recovery rate can be high.

  Then, the effect | action and effect of the refinement | purification system 1 which concern on this embodiment are demonstrated.

  First, a mixed gas (for example, FCC off gas) in the mixed gas supply source 100 passes through the line L1 and is supplied to the olefin separation membrane module 10A of the purification system 1. The mixed gas is pressurized to a predetermined pressure by the compressor 30 provided in the line L1. When the pressurized mixed gas is supplied to the olefin separation membrane module 10A, at least a part of the olefin in the mixed gas permeates the olefin separation membrane 11, and the recovery chamber RC1 serves as the first permeable gas having a high olefin concentration. From the olefin recovery line L6. The first non-permeate gas that has not permeated through the olefin separation membrane 11 passes through the non-permeate gas discharge port 14, the line L2, and the inflow port 22, and is supplied to the subsequent hydrogen separation membrane module 20A. The first non-permeating gas has a higher hydrogen concentration than the mixed gas because the olefin is separated by the olefin separation membrane module 10A. Further, the total pressure of the first non-permeating gas in the line L2 does not greatly decrease as compared with the total pressure of the mixed gas pressurized in the line L1. Therefore, in the first non-permeate gas in the line L2, the partial pressure of olefin is reduced while the partial pressure of hydrogen is increased as compared with the mixed gas before purification.

  Thus, when the first non-permeating gas is supplied to the hydrogen separation membrane module 20A, at least a part of the hydrogen in the first non-permeating gas permeates the hydrogen separation membrane 21 and the second hydrogen having a high hydrogen concentration. The permeated gas is recovered from the hydrogen recovery line L7 via the recovery chamber RC2. Since the partial pressure of hydrogen is increased in the first non-permeating gas in the line L2, hydrogen is likely to pass through the hydrogen separation membrane 21 in the hydrogen separation membrane module 20A. Accordingly, the hydrogen recovery rate is improved as compared with the case where the olefin separation membrane module 10A is not disposed in the preceding stage. The second non-permeating gas that has not permeated the hydrogen separation membrane 21 passes through the line L5 and is recovered as off-gas.

  Thus, in the purification system 1, the olefin can be purified by separating the olefin from the mixed gas by the olefin separation membrane 11 of the olefin separation membrane module 10A. Moreover, hydrogen can be purified by separating hydrogen from the first non-permeating gas by the hydrogen separation membrane 21 of the hydrogen separation membrane module 20A. As described above, hydrogen and olefin can be purified from a mixed gas containing at least hydrogen and olefin. Further, since the olefin separation membrane module 10A is arranged in the previous stage of the hydrogen separation membrane module 20A, the olefin is separated from the mixed gas in the previous stage of the hydrogen separation membrane module 20A. In other words, in the present purification system 1, since the hydrogen separation membrane 21 separates hydrogen after increasing the hydrogen concentration in the first non-permeate gas, the hydrogen recovery rate can be further increased. Thereby, the present purification system 1 can purify hydrogen and olefin as useful gases from a mixed gas containing at least hydrogen and olefin, and purify hydrogen with a higher recovery rate.

  The mixed gas may have a higher olefin concentration than hydrogen concentration. In this case, an olefin having a higher concentration than hydrogen can be separated by the preceding olefin separation membrane module 10A. By separating the olefin having a high concentration in the previous stage, the concentration of hydrogen in the first non-permeate gas flowing into the subsequent hydrogen separation membrane module 20A can be increased. As a result, the hydrogen recovery rate of the subsequent hydrogen separation membrane module 20A can be further increased. As described above, by separating the olefin having a higher concentration than hydrogen and easily separated, the olefin can be purified with a higher recovery rate while increasing the hydrogen recovery rate.

  Further, the value obtained by multiplying the olefin concentration in the mixed gas by the propylene separation factor for propane in the olefin separation membrane 11 is a value obtained by multiplying the hydrogen concentration in the mixed gas by the hydrogen separation factor for methane in the hydrogen separation membrane 21. It may be larger. In this case, olefin is easier to separate than hydrogen. Therefore, the concentration of hydrogen in the first non-permeate gas flowing into the subsequent hydrogen separation membrane module 20A can be increased by separating the olefin that is relatively easy to separate in the previous stage. As a result, the hydrogen recovery rate of the subsequent hydrogen separation membrane module 20A can be further increased. As described above, by separating the olefin that is easier to separate from hydrogen before the hydrogen, the olefin can be purified at a higher recovery rate while increasing the hydrogen recovery rate.

  Further, the separation factor of propylene with respect to propane in the olefin separation membrane 11 may be 90 or more. Thus, by setting the separation factor of propylene to propane in the olefin separation membrane 11 to 90 or more, the concentration of the purified olefin can be made high even when the total pressure of the mixed gas is set to a relatively high pressure.

  Further, the pressure of the mixed gas may be 1.5 MPaG or more. Thus, both the olefin recovery rate and the hydrogen recovery rate can be increased by setting the pressure of the mixed gas to 1.5 MPaG or more. In particular, when the separation factor of the olefin separation membrane 11 is 90 or more, the effect of the separation factor of the olefin separation membrane 11 described above is 90 or more by setting the pressure of the mixed gas before purification to 1.5 MPaG or more. Becomes more prominent.

  As described above, in the purification system 1, the olefin separation membrane module 10A is disposed in the front stage (first stage), and the hydrogen separation membrane module 20A is disposed in the rear stage (second stage), which is useful from the mixed gas. While purifying hydrogen and olefin as gas, hydrogen can be purified particularly at a high recovery rate. Since the olefin separation membrane module 10A is arranged in the previous stage (first stage), the purification system 1 is suitable when the concentration of olefin in the mixed gas is high and when the separation coefficient of the olefin separation membrane 11 is high. is there.

[Second Embodiment]
FIG. 2 is a schematic diagram showing the configuration of the hydrogen and olefin purification system 2 according to the second embodiment of the present invention. As shown in FIG. 2, the purification system 2 according to the second embodiment is different from the purification system 1 according to the first embodiment in that an olefin separation membrane module 10B is provided at the subsequent stage of the hydrogen separation membrane module 20A. It is different.

  The olefin separation membrane module 10B includes an olefin separation membrane 11 that selectively separates olefins, and has the same structure and function as the olefin separation membrane module 10A. The purification system 2 has an olefin separation membrane module 10A at the front stage (first stage), a hydrogen separation membrane module 20A at the rear stage (second stage), and a rear stage with respect to the flow of the mixed gas. The olefin separation membrane module 10B is arranged at (third stage).

  The inlet 12 of the olefin separation membrane module 10A is connected to a line L1 through which the mixed gas from the mixed gas supply source 100 passes. The inlet 22 of the hydrogen separation membrane module 20A is connected to a line L2 through which the first non-permeate gas from the non-permeate gas discharge port 14 of the olefin separation membrane module 10A passes. The inlet 12 of the olefin separation membrane module 10B is connected to a line L3 through which the second non-permeable gas from the non-permeable gas discharge port 24 of the hydrogen separation membrane module 20A passes.

  The non-permeate gas discharge port 14 of the olefin separation membrane module 10B is connected to the line L5, and the third non-permeate gas passes through the line L5 and is used for a predetermined application as an off-gas.

  The permeated gas discharge ports 13 of the olefin separation membrane modules 10A and 10B are connected to the olefin recovery line L6. The 1st permeation | transmission gas and 3rd permeation | transmission gas which permeate | transmitted the olefin separation membrane 11 pass through the olefin collection | recovery line L6 as a high purity olefin, and are collect | recovered. The permeate gas outlet 23 of the hydrogen separation membrane module 20A is connected to the hydrogen recovery line L7. The second permeated gas that has permeated the hydrogen separation membrane 21 is recovered as high-purity hydrogen through the hydrogen recovery line L7.

  Then, the effect | action and effect of the purification system 2 which concern on this embodiment are demonstrated.

  First, the operations of the olefin separation membrane module 10A and the hydrogen separation membrane module 20A with respect to the mixed gas (for example, FCC off gas) in the mixed gas supply source 100 are the same as those of the purification system 1 according to the first embodiment.

  The second non-permeate gas that has not permeated the hydrogen separation membrane 21 of the hydrogen separation membrane module 20A passes through the non-permeate gas outlet 24, the line L3, and the inlet 12 and is supplied to the olefin separation membrane module 10B in the subsequent stage. . The second non-permeating gas has a higher olefin concentration than the first non-permeating gas because hydrogen is separated by the hydrogen separation membrane module 20A. Further, the total pressure of the second non-permeating gas in the line L3 does not greatly decrease as compared with the first non-permeating gas in the line L2. Therefore, in the second non-permeate gas in the line L3, the partial pressure of hydrogen is decreased while the partial pressure of the olefin is increased as compared with the first non-permeate gas in the line L2.

  As described above, when the second non-permeate gas is supplied to the olefin separation membrane module 10B, at least a part of the olefin in the second non-permeate gas passes through the olefin separation membrane 11, and the third olefin concentration is high. The permeated gas is recovered from the olefin recovery line L6 via the recovery chamber RC1. In the second non-permeating gas in the line L3, the partial pressure of the olefin is increased, so that the olefin easily passes through the olefin separation membrane 11 in the olefin separation membrane module 10B. Accordingly, the olefin recovery rate is improved as compared with the case where the hydrogen separation membrane module 20A is not disposed in the preceding stage of the olefin separation membrane module 10B. The third non-permeating gas that has not passed through the olefin separation membrane 11 passes through the line L5 and is recovered as off-gas.

  As described above, in the purification system 2, the olefin separation membrane module 10A is disposed in the previous stage (first stage), the hydrogen separation membrane module 20A is disposed in the subsequent stage (second stage), and the subsequent stage (third stage). By arranging the olefin separation membrane module 10B in the eye), it is possible to purify hydrogen and olefin as useful gases from the mixed gas and to recover both olefin and hydrogen at a high recovery rate. Since the olefin separation membrane module 10A is arranged in the previous stage (first stage), the purification system 2 is suitable when the concentration of olefin in the mixed gas is high and when the separation coefficient of the olefin separation membrane 11 is high. is there.

[Third Embodiment]
FIG. 3 is a schematic diagram showing the configuration of the hydrogen and olefin purification system 3 according to the third embodiment of the present invention. As shown in FIG. 3, the purification system 3 according to the third embodiment is different from the purification system 2 according to the second embodiment in that a hydrogen separation membrane module 20B is provided at the subsequent stage of the olefin separation membrane module 10B. It is different.

  The hydrogen separation membrane module 20B includes a hydrogen separation membrane 21 that selectively separates hydrogen, and has the same structure and function as the hydrogen separation membrane module 20A. The purification system 3 has an olefin separation membrane module 10A at the front stage (first stage) and a hydrogen separation membrane module 20A at the rear stage (second stage) from the upstream to the downstream with respect to the flow of the mixed gas. The olefin separation membrane module 10B is arranged at the (third stage), and the hydrogen separation membrane module 20B is arranged at the subsequent stage (fourth stage).

  The inlet 12 of the olefin separation membrane module 10A is connected to a line L1 through which the mixed gas from the mixed gas supply source 100 passes. The inlet 22 of the hydrogen separation membrane module 20A is connected to a line L2 through which the first non-permeate gas from the non-permeate gas discharge port 14 of the olefin separation membrane module 10A passes. The inlet 12 of the olefin separation membrane module 10B is connected to a line L3 through which the second non-permeable gas from the non-permeable gas discharge port 24 of the hydrogen separation membrane module 20A passes. The inlet 22 of the hydrogen separation membrane module 20B is connected to a line L4 through which the third non-permeate gas from the non-permeate gas outlet 14 of the olefin separation membrane module 10B passes.

  The non-permeate gas outlet 24 of the hydrogen separation membrane module 20B is connected to the line L5, and the fourth non-permeate gas passes through the line L5 and is used for a predetermined application as an off-gas.

  The permeated gas discharge ports 13 of the olefin separation membrane modules 10A and 10B are connected to the olefin recovery line L6. The 1st permeation | transmission gas and 3rd permeation | transmission gas which permeate | transmitted the olefin separation membrane 11 pass through the olefin collection | recovery line L6 as a high purity olefin, and are collect | recovered. The permeated gas discharge ports 23 of the hydrogen separation membrane modules 20A and 20B are connected to the hydrogen recovery line L7. The permeation gas second permeation gas and the fourth permeation gas that have permeated the hydrogen separation membrane 21 are recovered as high-purity hydrogen through the hydrogen recovery line L7.

  Then, the effect | action and effect of the refinement | purification system 3 which concern on this embodiment are demonstrated.

  First, the operations of the olefin separation membrane modules 10A and 10B and the hydrogen separation membrane module 20A with respect to the mixed gas (for example, FCC offgas) in the mixed gas supply source 100 are the same as those of the purification system 2 according to the second embodiment.

  The third non-permeate gas that has not permeated the olefin separation membrane 11 of the olefin separation membrane module 10B passes through the non-permeate gas discharge port 14, the line L4, and the inlet port 22, and is supplied to the subsequent hydrogen separation membrane module 20B. . The third non-permeating gas has a higher hydrogen concentration than the second non-permeating gas because the olefin is separated by the olefin separation membrane module 10B. Further, the total pressure of the third non-permeating gas in the line L4 does not greatly decrease as compared with the second non-permeating gas in the line L3. Therefore, in the third non-permeate gas in the line L4, the partial pressure of olefin is reduced while the partial pressure of hydrogen is increased as compared with the second non-permeate gas in the line L3.

  Thus, when the third non-permeating gas is supplied to the hydrogen separation membrane module 20B, at least a part of the hydrogen in the third non-permeating gas permeates the hydrogen separation membrane 21, and the fourth hydrogen having a high hydrogen concentration. The permeated gas is recovered from the hydrogen recovery line L7 via the recovery chamber RC2. In the third non-permeating gas in the line L4, since the partial pressure of hydrogen is increased, hydrogen easily passes through the hydrogen separation membrane 21 in the hydrogen separation membrane module 20B. Accordingly, the hydrogen recovery rate is improved as compared with the case where the olefin separation membrane module 10B is not arranged in the preceding stage of the hydrogen separation membrane module 20B. The fourth non-permeating gas that has not permeated the hydrogen separation membrane 21 passes through the line L5 and is recovered as off-gas.

  Thus, in the purification system 3 according to the third embodiment, the olefin separation membrane module 10A is disposed in the previous stage (first stage), and the hydrogen separation membrane module 20A is disposed in the subsequent stage (second stage). By arranging the olefin separation membrane module 10B in the subsequent stage (third stage) and the hydrogen separation membrane module 20B in the subsequent stage (fourth stage), hydrogen and olefin are purified as useful gases from the mixed gas. In addition, both olefin and hydrogen can be recovered at a high recovery rate. Further, by arranging the separation membrane modules alternately and in multiple stages, olefin and hydrogen can be recovered at a higher recovery rate. Since the olefin separation membrane module 10A is arranged in the previous stage (first stage), the purification system 3 is suitable when the concentration of olefin in the mixed gas is high and when the separation coefficient of the olefin separation membrane 11 is high. is there.

[Fourth Embodiment]
FIG. 4 is a schematic diagram showing the configuration of the hydrogen and olefin purification system 4 according to the fourth embodiment of the present invention. As shown in FIG. 4, in the purification system 4 according to the fourth embodiment, the olefin separation membrane module 10A and the hydrogen separation membrane module 20A are arranged in the reverse order as compared with the purification system 1 according to the first embodiment. It is different in that it is.

  The purification system 4 includes a hydrogen separation membrane module 20A at the front stage (first stage) and an olefin separation membrane module 10A at the rear stage (second stage) from upstream to downstream with respect to the flow of the mixed gas. Yes.

  The inlet 22 of the hydrogen separation membrane module 20A is connected to a line L1 through which the mixed gas from the mixed gas supply source 100 passes. The inlet 12 of the olefin separation membrane module 10A is connected to a line L2 through which the first non-permeate gas from the non-permeate gas outlet 24 of the hydrogen separation membrane module 20A passes.

  The non-permeate gas discharge port 14 of the olefin separation membrane module 10A is connected to the line L5, and the second non-permeate gas passes through the line L5 and is used for a predetermined application as an off-gas.

  The permeated gas discharge port 13 of the olefin separation membrane module 10A is connected to the olefin recovery line L6. The second permeated gas that has passed through the olefin separation membrane 11 passes through the olefin recovery line L6 and is recovered as a high-purity olefin. The permeate gas outlet 23 of the hydrogen separation membrane module 20A is connected to the hydrogen recovery line L7. The first permeated gas that has permeated the hydrogen separation membrane 21 is recovered as high-purity hydrogen through the hydrogen recovery line L7.

  Then, the effect | action and effect of the purification system 4 which concern on this embodiment are demonstrated.

  First, the mixed gas (for example, FCC off gas) in the mixed gas supply source 100 passes through the line L1 and is supplied to the hydrogen separation membrane module 20A of the purification system 4. The mixed gas is pressurized to a predetermined pressure by the compressor 30 provided in the line L1. When the pressurized mixed gas is supplied to the hydrogen separation membrane module 20A, at least a part of the hydrogen in the mixed gas permeates the hydrogen separation membrane 21, and the recovery chamber RC2 serves as the first permeated gas having a high hydrogen concentration. From the hydrogen recovery line L7. The first non-permeate gas that has not permeated the hydrogen separation membrane 21 passes through the non-permeate gas discharge port 24, the line L2, and the inflow port 12, and is supplied to the subsequent olefin separation membrane module 10A. The first non-permeating gas has a higher olefin concentration than the mixed gas because hydrogen is separated by the hydrogen separation membrane module 20A. Further, the total pressure of the first non-permeating gas in the line L2 does not greatly decrease as compared with the total pressure of the mixed gas pressurized in the line L1. Therefore, in the first non-permeate gas in the line L2, the partial pressure of hydrogen is reduced while the partial pressure of olefin is increased compared to the mixed gas before purification.

  Thus, when the first non-permeate gas is supplied to the olefin separation membrane module 10A, at least a part of the olefin in the first non-permeate gas permeates the olefin separation membrane 11, and the second olefin concentration is high. The permeated gas is recovered from the olefin recovery line L6 via the recovery chamber RC1. Since the partial pressure of olefin is increased in the first non-permeating gas in the line L2, the olefin easily passes through the olefin separation membrane 11 in the olefin separation membrane module 10A. Therefore, the olefin recovery rate is improved as compared with the case where the hydrogen separation membrane module 20A is not disposed in the previous stage. The second non-permeate gas that has not passed through the olefin separation membrane 11 passes through the line L5 and is recovered as off-gas.

  Thus, in the purification system 4, hydrogen can be purified by separating hydrogen from the mixed gas by the hydrogen separation membrane 21 of the hydrogen separation membrane module 20A. Further, by separating the olefin from the first non-permeating gas of the hydrogen separation membrane module 20A by the olefin separation membrane 11, the olefin can be purified. As described above, hydrogen and olefin can be purified from a mixed gas containing at least hydrogen and olefin. Further, since the hydrogen separation membrane module 20A is arranged in the previous stage of the olefin separation membrane module 10A, hydrogen is separated from the mixed gas in the previous stage of the olefin separation membrane module 10A. That is, in the present purification system 4, since the olefin is separated by the olefin separation membrane 11 after increasing the olefin concentration in the first non-permeate gas, the olefin recovery rate can be further increased. Thereby, this refinement | purification system 4 can refine | purify an olefin with a higher recovery rate while refine | purifying hydrogen and an olefin as useful gas from the mixed gas containing hydrogen and an olefin at least.

  The mixed gas may have a higher hydrogen concentration than the olefin concentration. In this case, hydrogen having a higher concentration than that of olefin can be separated by the preceding hydrogen separation membrane module 20A. By separating hydrogen having a high concentration in the front stage, the concentration of the olefin in the first non-permeate gas flowing into the downstream olefin separation membrane module 10A can be increased. Thereby, the recovery rate of the olefin by the latter-stage olefin separation membrane module 10A can be further increased. As described above, hydrogen having a higher concentration than olefin and easily separated is separated before olefin, so that hydrogen can be purified with a higher recovery rate while increasing the olefin recovery rate.

  Further, the value obtained by multiplying the hydrogen concentration in the mixed gas by the hydrogen separation factor for methane in the hydrogen separation membrane 21 is a value obtained by multiplying the olefin concentration in the mixed gas by the propylene separation factor for propane in the olefin separation membrane 11. It may be larger. In this case, hydrogen is easier to separate than olefin. Therefore, the concentration of olefin in the first non-permeate gas flowing into the downstream olefin separation membrane module 10A can be increased by separating hydrogen that is relatively easy to separate in the previous stage. Thereby, the recovery rate of the olefin by the latter-stage olefin separation membrane module 10A can be further increased. As mentioned above, hydrogen can be purified at a higher recovery rate while increasing the recovery rate of olefins by separating hydrogen that is easier to separate from olefins before olefins.

  As described above, in the purification system 4, the hydrogen separation membrane module 20A is arranged at the front stage (first stage), and the olefin separation membrane module 10A is arranged at the rear stage (second stage), which is useful from the mixed gas. While purifying hydrogen and olefins as gases, olefins can be particularly recovered at a high recovery rate. Since the purification system 4 has the hydrogen separation membrane module 20A disposed in the previous stage (first stage), it is suitable when the concentration of hydrogen in the mixed gas is high and when the separation factor of the hydrogen separation membrane 21 is high. is there.

[Fifth Embodiment]
FIG. 5 is a schematic diagram showing the configuration of a hydrogen and olefin purification system 5 according to the fifth embodiment of the present invention. As shown in FIG. 5, the purification system 5 according to the fifth embodiment is different from the purification system 4 according to the fourth embodiment in that a hydrogen separation membrane module 20B is provided at the subsequent stage of the olefin separation membrane module 10A. It is different.

  The hydrogen separation membrane module 20B includes a hydrogen separation membrane 21 that selectively separates hydrogen, and has the same structure and function as the hydrogen separation membrane module 20A. The purification system 5 has a hydrogen separation membrane module 20A at the front stage (first stage) and an olefin separation membrane module 10A at the rear stage (second stage) from the upstream to the downstream with respect to the mixed gas flow. The hydrogen separation membrane module 20B is arranged at the (third stage).

  The inlet 22 of the hydrogen separation membrane module 20A is connected to a line L1 through which the mixed gas from the mixed gas supply source 100 passes. The inlet 12 of the olefin separation membrane module 10A is connected to a line L2 through which the first non-permeate gas from the non-permeate gas outlet 24 of the hydrogen separation membrane module 20A passes. The inlet 22 of the hydrogen separation membrane module 20B is connected to a line L3 through which the second non-permeate gas from the non-permeate gas outlet 14 of the olefin separation membrane module 10A passes.

  The non-permeate gas discharge port 24 of the hydrogen separation membrane module 20B is connected to the line L5, and the third non-permeate gas passes through the line L5 and is used for a predetermined application as an off-gas.

  The permeated gas discharge port 13 of the olefin separation membrane module 10A is connected to the olefin recovery line L6. The second permeated gas that has passed through the olefin separation membrane 11 passes through the olefin recovery line L6 and is recovered as a high-purity olefin. The permeated gas discharge ports 23 of the hydrogen separation membrane modules 20A and 20B are connected to the hydrogen recovery line L7. The 1st permeation gas and the 3rd permeation gas which permeate | transmitted the hydrogen separation membrane 21 pass through the hydrogen recovery line L7, and are collect | recovered as high purity hydrogen.

  Then, the effect | action and effect of the refinement | purification system 5 which concern on this embodiment are demonstrated.

  First, the operations of the olefin separation membrane module 10A and the hydrogen separation membrane module 20A with respect to the mixed gas (for example, FCC off gas) in the mixed gas supply source 100 are the same as those of the purification system 4 according to the fourth embodiment.

  The second non-permeate gas that has not permeated the olefin separation membrane 11 of the olefin separation membrane module 10A passes through the non-permeate gas discharge port 14, the line L3, and the inlet port 22, and is supplied to the subsequent hydrogen separation membrane module 20B. . The second non-permeating gas has a higher hydrogen concentration than the first non-permeating gas because the olefin is separated by the olefin separation membrane module 10A. Further, the total pressure of the second non-permeating gas in the line L3 does not greatly decrease as compared with the first non-permeating gas in the line L2. Therefore, in the second non-permeate gas in the line L3, the partial pressure of olefin is reduced while the partial pressure of hydrogen is increased as compared with the first non-permeate gas in the line L2.

  Thus, when the second non-permeating gas is supplied to the hydrogen separation membrane module 20B, at least part of the hydrogen in the second non-permeating gas permeates the hydrogen separation membrane 21, and the third hydrogen having a high hydrogen concentration. The permeated gas is recovered from the hydrogen recovery line L7 via the recovery chamber RC2. Since the partial pressure of hydrogen is increased in the second non-permeating gas in the line L3, hydrogen easily passes through the hydrogen separation membrane 21 in the hydrogen separation membrane module 20B. Accordingly, the hydrogen recovery rate is improved as compared with the case where the olefin separation membrane module 10A is not arranged in the preceding stage of the hydrogen separation membrane module 20B. The third non-permeating gas that has not permeated the hydrogen separation membrane 21 passes through the line L5 and is recovered as off-gas.

  As described above, in the purification system 5, the hydrogen separation membrane module 20A is disposed in the previous stage (first stage), the olefin separation membrane module 10A is disposed in the subsequent stage (second stage), and the subsequent stage (third stage). By arranging the hydrogen separation membrane module 20B in the eye), it is possible to purify hydrogen and olefin as useful gases from the mixed gas and to recover both olefin and hydrogen at a high recovery rate. Since the purification system 5 has the hydrogen separation membrane module 20A disposed in the previous stage (first stage), it is suitable when the concentration of hydrogen in the mixed gas is high and when the separation factor of the hydrogen separation membrane 21 is high. is there.

[Sixth Embodiment]
FIG. 6 is a schematic diagram showing a configuration of a hydrogen and olefin purification system 6 according to the sixth embodiment of the present invention. As shown in FIG. 6, the purification system 6 according to the sixth embodiment is different from the purification system 5 according to the fifth embodiment in that an olefin separation membrane module 10B is provided at the subsequent stage of the hydrogen separation membrane module 20B. It is different.

  The olefin separation membrane module 10B includes an olefin separation membrane 11 that selectively separates olefins, and has the same structure and function as the olefin separation membrane module 10A. The purification system 6 includes a hydrogen separation membrane module 20A at the front stage (first stage) and an olefin separation membrane module 10A at the rear stage (second stage) from the upstream to the downstream with respect to the mixed gas flow. The hydrogen separation membrane module 20B is disposed in the (third stage), and the olefin separation membrane module 10B is disposed in the subsequent stage (fourth stage).

  The inlet 22 of the hydrogen separation membrane module 20A is connected to a line L1 through which the mixed gas from the mixed gas supply source 100 passes. The inlet 12 of the olefin separation membrane module 10A is connected to a line L2 through which the first non-permeate gas from the non-permeate gas outlet 24 of the hydrogen separation membrane module 20A passes. The inlet 22 of the hydrogen separation membrane module 20B is connected to a line L3 through which the second non-permeate gas from the non-permeate gas outlet 14 of the olefin separation membrane module 10A passes. The inlet 12 of the olefin separation membrane module 10B is connected to a line L4 through which the third non-permeable gas from the non-permeable gas discharge port 24 of the hydrogen separation membrane module 20B passes.

  The non-permeate gas outlet 14 of the olefin separation membrane module 10B is connected to the line L5, and the fourth non-permeate gas passes through the line L5 and is used for a predetermined application as an off-gas.

  The permeated gas discharge ports 13 of the olefin separation membrane modules 10A and 10B are connected to the olefin recovery line L6. The 2nd permeation | transmission gas and 4th permeation | transmission gas which permeate | transmitted the olefin separation membrane 11 pass through the olefin collection | recovery line L6 as a high purity olefin, and are collect | recovered. The permeated gas discharge ports 23 of the hydrogen separation membrane modules 20A and 20B are connected to the hydrogen recovery line L7. The 1st permeation gas and the 3rd permeation gas which permeate | transmitted the hydrogen separation membrane 21 pass through the hydrogen recovery line L7, and are collect | recovered as high purity hydrogen.

  Then, the effect | action and effect of the purification system 6 which concern on this embodiment are demonstrated.

  First, the operations of the olefin separation membrane module 10A and the hydrogen separation membrane modules 20A and 20B with respect to the mixed gas (for example, FCC off gas) in the mixed gas supply source 100 are the same as those of the purification system 5 according to the fifth embodiment.

  The third non-permeate gas that has not permeated the hydrogen separation membrane 21 of the hydrogen separation membrane module 20B passes through the non-permeate gas outlet 24, the line L4, and the inlet 12 and is supplied to the olefin separation membrane module 10B in the subsequent stage. . The third non-permeating gas has a higher olefin concentration than the second non-permeating gas because hydrogen is separated by the hydrogen separation membrane module 20B. Further, the total pressure of the third non-permeating gas in the line L4 does not greatly decrease as compared with the second non-permeating gas in the line L3. Therefore, in the third non-permeate gas in the line L4, the partial pressure of hydrogen is reduced while the partial pressure of the olefin is increased as compared with the second non-permeate gas in the line L3.

  Thus, when the third non-permeate gas is supplied to the olefin separation membrane module 10B, at least a part of the olefin in the third non-permeate gas passes through the olefin separation membrane 11, and the fourth olefin concentration is high. The permeated gas is recovered from the olefin recovery line L6 via the recovery chamber RC1. In the third non-permeating gas in the line L4, the partial pressure of the olefin is increased, so that the olefin easily passes through the olefin separation membrane 11 in the olefin separation membrane module 10B. Accordingly, the olefin recovery rate is improved as compared with the case where the hydrogen separation membrane module 20B is not arranged in the preceding stage of the olefin separation membrane module 10B. The fourth non-permeating gas that has not passed through the olefin separation membrane 11 passes through the line L5 and is recovered as off-gas.

  Thus, in the purification system 6 according to the sixth embodiment, the hydrogen separation membrane module 20A is arranged in the previous stage (first stage), and the olefin separation membrane module 10A is arranged in the subsequent stage (second stage). The hydrogen separation membrane module 20B is arranged at the subsequent stage (third stage) and the olefin separation membrane module 10B is arranged at the subsequent stage (fourth stage), thereby purifying hydrogen and olefin as useful gases from the mixed gas. In addition, both olefin and hydrogen can be recovered at a high recovery rate. Further, by arranging the separation membrane modules alternately and in multiple stages, olefin and hydrogen can be recovered at a higher recovery rate. Since the purification system 6 has the hydrogen separation membrane module 20B disposed in the previous stage (first stage), it is suitable when the concentration of hydrogen in the mixed gas is high and when the separation factor of the hydrogen separation membrane 21 is high. is there.

  In the above-described embodiment, the olefin separation membrane module and the hydrogen separation membrane module are illustrated as being alternately replaced one by one. However, the “hydrogen separation unit” in the claims includes a set of a plurality of hydrogen separation membrane modules arranged in succession. Further, the “olefin separation section” in the claims includes a set of a plurality of olefin separation membrane modules arranged in succession. For example, a configuration in which one olefin separation membrane module is arranged in the front stage and two or more hydrogen separation membrane modules are arranged in the rear stage, or two or more olefin separation membrane modules are arranged in the front stage, and one in the rear stage. Even in the form where the hydrogen separation membrane module is arranged, “permeate the olefin separation section having an olefin separation membrane for selectively separating olefin from the mixed gas containing hydrogen and olefin, and the olefin separation membrane of the olefin separation section. And a hydrogen separation part having a hydrogen separation membrane that selectively separates hydrogen from the non-permeating gas. In addition, for example, one hydrogen separation membrane module is arranged in the front stage and two or more olefin separation membrane modules are arranged in the rear stage, or two or more hydrogen separation membrane modules are arranged in the front stage, and Even in a form in which one olefin separation membrane module is arranged, “a hydrogen separation unit having a hydrogen separation membrane that selectively separates hydrogen from a mixed gas containing hydrogen and olefin, and a hydrogen separation membrane of the hydrogen separation unit” And an olefin separation part having an olefin separation membrane that selectively separates olefins from a non-permeate gas that does not permeate.

[Example]
Subsequently, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. In Examples 1 to 8 below, simulations were performed by changing the separation factor of the olefin separation membrane 11, the separation factor of the hydrogen separation membrane 21, and the pressure (total pressure) of the mixed gas in the hydrogen and olefin purification system. It is. The separation factor of the olefin separation membrane 11 is a separation factor of propylene with respect to propane. The separation factor of the hydrogen separation membrane 21 is a separation factor of hydrogen with respect to methane. The mixed gas had a composition that assumed FCC off gas. That is, the mixed gas contains 20.7 vol% of hydrogen, and contains 14.5 vol% of ethylene and 5.2 vol% of propylene as olefins. In addition, the mixed gas was methane 25.9 vol%, ethane 10.4 vol%, propane 3.1 vol%, carbon monoxide 2.1 vol%, carbon dioxide 2.1 vol%, nitrogen 15.5 vol%, oxygen 0. 5 vol% is included.

  In Examples 1 to 5, the configuration of the purification system 1 shown in FIG. 1 was adopted. In Example 1, the separation factor of the olefin separation membrane 11 was set to 15, and the separation factor of the hydrogen separation membrane 21 was set to 250. In Example 2, the separation factor of the olefin separation membrane 11 was set to 30, and the separation factor of the hydrogen separation membrane 21 was set to 250. In Example 3, the separation factor of the olefin separation membrane 11 was 60, and the separation factor of the hydrogen separation membrane 21 was 250. In Example 4, the separation factor of the olefin separation membrane 11 was 90, and the separation factor of the hydrogen separation membrane 21 was 250. In Example 5, the separation factor of the olefin separation membrane 11 was 90, and the separation factor of the hydrogen separation membrane 21 was 100.

  In Examples 6 and 7, the configuration of the purification system 4 shown in FIG. 4 was adopted. In Example 6, the separation factor of the olefin separation membrane 11 was set to 15, and the separation factor of the hydrogen separation membrane 21 was set to 250. In Example 7, the separation factor of the olefin separation membrane 11 was 30, and the separation factor of the hydrogen separation membrane 21 was 250.

  In Example 8, the configuration of the purification system 5 shown in FIG. 5 was adopted. In Example 8, the separation factor of the olefin separation membrane 11 was set to 30, and the separation factor of the hydrogen separation membrane 21 was set to 250.

  In each example, the pressure of the mixed gas was 1 MPaG, 1.5 MPaG, and 2 MPaG. The operating temperature was set to 40 ° C. Under the above pressure conditions, the recovered hydrogen concentration (vol%), the hydrogen recovery rate (vol%), the recovered olefin concentration (vol%), and the olefin recovery rate (vol%) were calculated. The result about Examples 1-8 is shown to Tables 1-8, respectively.

  In Examples 1 and 6, the recovered olefin concentration and the olefin recovery rate are compared. In Example 1, the olefin was separated from the mixed gas in the olefin separation membrane module 10A. On the other hand, in Example 6, the olefin was separated in the olefin separation membrane module 10A from the non-permeated gas that did not permeate the hydrogen separation membrane 21 in the preceding hydrogen separation membrane module 20A. As a result, in Example 6, compared with Example 1, the olefin recovery concentration and the olefin recovery rate increased under the total pressure conditions of the mixed gas. In Examples 2 and 7, the recovered olefin concentration and the olefin recovery rate are compared. In contrast to Example 2, in Example 7, the recovered olefin concentration and the olefin recovery rate increased under the total pressure conditions of the mixed gas. In Examples 1 and 2, the olefin recovery rate was 50 vol% or more under the condition that the pressure of the mixed gas was 2 MPaG. On the other hand, in Examples 7 and 8, the olefin recovery rate was 50 vol% or more under the condition where the pressure of the mixed gas was 1.5 MPaG. This suggests that the pressure of the mixed gas can be reduced by arranging the hydrogen separation membrane module 20A in the previous stage in order to obtain a predetermined olefin recovery rate.

  In Examples 1 and 6, the hydrogen recovery rate and the olefin recovery rate are compared. Here, the hydrogen concentration of 20.7 vol% is higher than the olefin concentration of 19.7 vol% (a value obtained by adding the ethylene concentration and the propylene concentration) of the mixed gas. In Example 6, hydrogen having a relatively high concentration was separated from the mixed gas in the hydrogen separation membrane module 20A located in the previous stage. As a result, in Example 6, compared with Example 1, the olefin recovery rate could be further increased without significantly reducing the hydrogen recovery rate.

  In Examples 2 and 7, the hydrogen recovery rate and the olefin recovery rate are compared. Here, the hydrogen separation membrane has a hydrogen concentration of 20.7 vol% with respect to a value obtained by multiplying the olefin concentration of the mixed gas by 19.7 vol% (a value obtained by adding the ethylene concentration and the propylene concentration) to the separation factor of the olefin separation membrane 11. The value multiplied by the separation factor of 21 is higher. In Example 7, hydrogen having a relatively high value obtained by multiplying the concentration and the separation coefficient was separated from the mixed gas in the hydrogen separation membrane module 20A. As a result, in Example 7, compared with Example 2, the olefin recovery rate could be increased without significantly reducing the hydrogen recovery rate. In Examples 1 and 6, the hydrogen recovery rate and the olefin recovery rate are compared. In Example 6, compared to Example 1, the olefin recovery rate could be increased without significantly reducing the hydrogen recovery rate. Here, the hydrogen recovery rate decrease amount of Example 6 relative to Example 1 was smaller than the hydrogen recovery rate decrease amount of Example 7 relative to Example 2. That is, in Example 6 compared to Example 7, the effect of arranging the hydrogen separation membrane module 20A in the previous stage was great. Regarding the difference between the value obtained by multiplying the hydrogen concentration of the mixed gas and the separation factor of the hydrogen separation membrane 21 and the value obtained by multiplying the concentration of the olefin and the separation factor of the olefin separation membrane 11 in Examples 2 and 7. In Examples 1 and 6, the difference between the value obtained by multiplying the hydrogen concentration of the mixed gas and the separation factor of the hydrogen separation membrane 21 and the value obtained by multiplying the concentration of the olefin and the separation factor of the olefin separation membrane 11 are large. For this reason, it is considered that the effect of disposing the hydrogen separation membrane 21 in the preceding stage appears remarkably.

  In Examples 1 to 5, the recovered olefin concentration is compared. In Example 4 with respect to Examples 1 to 3, the recovered olefin concentration was maintained at a high level of 90 vol% or more under the total pressure condition of the mixed gas. Furthermore, in Example 5, even when the separation factor of the hydrogen separation membrane 21 was reduced to 100, the recovered hydrogen concentration was maintained at a high level of 90 vol% or more under the total pressure condition of the mixed gas. As described above, by increasing the separation factor of the olefin separation membrane 11 to 90, the recovered olefin concentration and the recovered hydrogen concentration are maintained at a high level of 90 vol% or higher even under the condition of 2 MPaG where the pressure of the mixed gas is relatively high. The effect of being able to be confirmed.

  In Examples 1 to 7, when the pressure of the mixed gas was 1.5 MPaG or more, the olefin recovery rate and the hydrogen recovery rate increased to almost 50 vol% or more.

  In Examples 7 and 8, the hydrogen recovery rates are compared. Compared to Example 7, in Example 8, the hydrogen recovery rate was significantly increased. In Example 7, the pressure of the mixed gas for obtaining a hydrogen recovery rate of 62 vol% was 2 MPaG, whereas in Example 8, the pressure of the mixed gas was 1 MPaG. This suggests that the pressure of the mixed gas can be greatly reduced by arranging the separation membrane modules alternately and in multiple stages in order to obtain a predetermined hydrogen recovery rate.

  DESCRIPTION OF SYMBOLS 1-6 ... Hydrogen and olefin purification system, 10A, 10B ... Olefin separation membrane module (olefin separation part), 11 ... Olefin separation membrane, 20A, 20B ... Hydrogen separation membrane module (hydrogen separation part), 21 ... Hydrogen separation membrane .

Claims (8)

A hydrogen separation part having a hydrogen separation membrane for selectively separating hydrogen from a mixed gas containing hydrogen and olefin;
An olefin separation unit having an olefin separation membrane that selectively separates olefins from a non-permeating gas that does not permeate the hydrogen separation membrane of the hydrogen separation unit;
A system for purifying hydrogen and olefins.   The hydrogen and olefin purification system according to claim 1, wherein the mixed gas has a hydrogen concentration higher than an olefin concentration.   The value obtained by multiplying the hydrogen concentration in the mixed gas by the hydrogen separation factor for methane in the hydrogen separation membrane is a value obtained by multiplying the olefin concentration in the mixed gas and the propylene separation factor for propane in the olefin separation membrane. The hydrogen and olefin purification system of claim 1, which is larger. An olefin separation part having an olefin separation membrane for selectively separating olefins from a mixed gas containing hydrogen and olefins;
A hydrogen separation part having a hydrogen separation membrane for selectively separating hydrogen from a non-permeating gas that does not permeate the olefin separation membrane of the olefin separation part;
A system for purifying hydrogen and olefins.   The hydrogen and olefin purification system according to claim 4, wherein the mixed gas has an olefin concentration higher than a hydrogen concentration.   The value obtained by multiplying the olefin concentration in the mixed gas by the separation factor of propylene with respect to propane in the olefin separation membrane is a value obtained by multiplying the hydrogen concentration in the mixed gas and the separation factor of hydrogen with respect to methane in the hydrogen separation membrane. 5. The hydrogen and olefin purification system of claim 4, which is larger.   The hydrogen and olefin purification system according to any one of claims 1 to 6, wherein a separation factor of propylene with respect to propane in the olefin separation membrane is 90 or more.   The hydrogen and olefin purification system according to any one of claims 1 to 7, wherein the pressure of the mixed gas is 1.5 MPaG or more.

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