WO2013191097A1 - ガス分離装置およびガス分離方法 - Google Patents

ガス分離装置およびガス分離方法 Download PDF

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Publication number
WO2013191097A1
WO2013191097A1 PCT/JP2013/066448 JP2013066448W WO2013191097A1 WO 2013191097 A1 WO2013191097 A1 WO 2013191097A1 JP 2013066448 W JP2013066448 W JP 2013066448W WO 2013191097 A1 WO2013191097 A1 WO 2013191097A1
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Prior art keywords
gas
adsorption tower
separation
adsorption
adsorbent
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PCT/JP2013/066448
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English (en)
French (fr)
Japanese (ja)
Inventor
藤峰智也
中島良文
泉順
三浦則雄
谷内正
黒木学
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JNC Engineering Co Ltd
Kyushu University NUC
Tokyo Gas Co Ltd
Adsorption Technology Industries Co Ltd
Original Assignee
JNC Engineering Co Ltd
Kyushu University NUC
Tokyo Gas Co Ltd
Adsorption Technology Industries Co Ltd
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Application filed by JNC Engineering Co Ltd, Kyushu University NUC, Tokyo Gas Co Ltd, Adsorption Technology Industries Co Ltd filed Critical JNC Engineering Co Ltd
Priority to IN10865DEN2014 priority Critical patent/IN2014DN10865A/en
Priority to US14/407,558 priority patent/US9216374B2/en
Priority to EP13806229.4A priority patent/EP2862618B1/en
Publication of WO2013191097A1 publication Critical patent/WO2013191097A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B01D53/0423—Beds in columns
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    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
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    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0454—Controlling adsorption
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    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
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    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0259—Physical processing only by adsorption on solids
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/04—Purification or separation of nitrogen
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    • C01—INORGANIC CHEMISTRY
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    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/04—Purification or separation of nitrogen
    • C01B21/0405—Purification or separation processes
    • C01B21/0433—Physical processing only
    • C01B21/045—Physical processing only by adsorption in solids
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    • C01B23/00—Noble gases; Compounds thereof
    • C01B23/001—Purification or separation processes of noble gases
    • C01B23/0036—Physical processing only
    • C01B23/0052—Physical processing only by adsorption in solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/10—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
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    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40007—Controlling pressure or temperature swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/65—Employing advanced heat integration, e.g. Pinch technology
    • B01D2259/655—Employing advanced heat integration, e.g. Pinch technology using heat storage materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
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    • C01B2210/0034—Argon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0029—Obtaining noble gases
    • C01B2210/0037—Xenon

Definitions

  • the present invention relates to a gas separation device and a gas separation method for separating a predetermined gas from a mixed gas.
  • a pressure swing adsorption (PSA) method is known as a technique for separating a predetermined gas from a mixed gas.
  • the PSA method is a separation method that utilizes the fact that the amount of gas adsorbed on the adsorbent varies depending on the type of gas and the partial pressure of each substance (gas).
  • a mixed gas is introduced into an adsorption tower filled with an adsorbent, a predetermined gas contained in the mixed gas is selectively adsorbed by the adsorbent (adsorption process), and after the predetermined gas is adsorbed
  • the predetermined gas is separated from the mixed gas by applying a pressure difference in the step of desorbing the predetermined gas from the adsorbent (regeneration step).
  • the present invention has been made in view of such problems, and an object thereof is to provide a simple and low-cost gas separation device and gas separation method.
  • a gas separation apparatus includes an adsorption tower at least partially exposed to an atmosphere at a temperature higher or lower than room temperature, and a mixed gas containing a plurality of substances in the adsorption tower.
  • a mixed gas supply unit for supplying the gas and adsorbing the substance contained in the mixed gas when contacting the mixed gas under a predetermined pressure and temperature environment, and the substance in the mixed gas
  • An adsorbed gas discharge unit that desorbs the adsorbed adsorbed gas from the adsorbent and discharges the adsorbed gas from the adsorbent tower, and the adsorber tower has an upstream side and a downstream side in the supply direction of the mixed gas from the adsorbent.
  • the mixed gas supply unit of the present invention can supply the mixed gas from both one end side and the other end side of the adsorption tower, and the separation gas discharge unit includes one end side and the other end of the adsorption tower.
  • the separation gas may be discharged from both sides.
  • a supply process for supplying a mixed gas into the adsorption tower of the present invention a separation gas discharge process for discharging a separation gas from the adsorption tower, and an adsorption gas discharge process for discharging the adsorption gas from the adsorption tower.
  • Control means for controlling gas separation processing performed in time series wherein the control means discharges the separation gas in the previous separation gas discharge processing among the one end side and the other end side of the adsorption tower in the supply processing;
  • the mixed gas may be supplied from the finished side.
  • control means of the present invention may discharge the separation gas from a side different from the side where the separation gas was discharged in the previous separation gas discharge process in the adsorption tower.
  • control means of the present invention may discharge the separation gas from one end side of the adsorption tower and discharge the adsorption gas from the other end side of the adsorption tower in one gas separation process.
  • the heat storage body of the present invention comes into contact with the mixed gas under a predetermined pressure and a temperature environment closer to room temperature than the adsorbent, the substance contained in the mixed gas is adsorbed, and the substance of the mixed gas May be separated.
  • the heat storage body of the present invention may be composed of the same member as the adsorbent.
  • the adsorption tower of the present invention is configured by a tubular member having a plurality of extending portions extending linearly and a curved or bent folded portion connecting the two extending portions. It is good.
  • the plurality of extending portions of the present invention are arranged in parallel to each other, and the two heat storage bodies arranged on the upstream side and the downstream side in the supply direction of the mixed gas are respectively connected to the two extending portions. It is good also as arrange
  • the adsorbent of the present invention may be a perovskite oxide that adsorbs oxygen.
  • the gas separation method of the present invention has a predetermined pressure and temperature environment applied to an adsorbent provided in an adsorption tower at least partially exposed to an atmosphere at a temperature higher or lower than room temperature.
  • a gas separation method in which a substance contained in the mixed gas is adsorbed on an adsorbent by contacting the mixed gas under the gas, and the substance in the mixed gas is separated, and the mixed gas is supplied into the adsorption tower
  • a supply step an adsorption step in which the inside of the adsorption tower is maintained at the predetermined pressure and temperature environment, and a substance contained in the mixed gas is adsorbed by the adsorbent; and the adsorbent is adsorbed from the mixed gas
  • a separation gas discharge step for discharging the separation gas from which the substance has been removed from the adsorption tower, and an adsorption for desorbing the adsorption gas adsorbed on the adsorbent by depressurizing the inside of the adsorption tower and discharging it from the adsorption tower.
  • the supplying step supplying the mixed gas from one end side and the other end side of the adsorption tower from the side where the separation gas was discharged in the previous separation gas discharging
  • the cost required for gas separation can be reduced while having a simple configuration.
  • FIG. 1 is a diagram for explaining a gas separation device 100 according to the first embodiment.
  • the gas separation apparatus 100 according to the present embodiment is a gas separation apparatus using the PSA method.
  • a configuration for separating oxygen and nitrogen from air will be described as an example.
  • the gas separation device 100 includes an adsorption tower 110 (indicated by 110a and 110b in FIG. 1).
  • the adsorption tower 110 is configured in a cylindrical shape.
  • a portion of the adsorption tower 110 where the adsorbent 130 described later is provided is accommodated in the heat insulating chamber 102, and the heat insulating chamber 102 allows the adsorbent 130 to be placed in an atmosphere of 250 ° C. to 900 ° C. (higher than normal temperature). It is kept warm so as to be exposed to the atmosphere.
  • the normal temperature is, for example, 5 ° C. to 30 ° C.
  • the heat supplied to the heat insulating chamber 102 may use electric heating, gas combustion heating, or exhaust heat of a plant in which the gas separation device 100 is installed.
  • the mixed gas supply unit 120 is composed of a blower, and supplies a mixed gas (in this case, air) containing a plurality of substances into the adsorption tower 110. More specifically, the mixed gas supply unit 120 supplies room temperature air into the adsorption tower 110 through the supply pipe 122 and the valves 124a to 124d.
  • a mixed gas in this case, air
  • the adsorbent 130 (shown by cross-hatching in FIG. 1) is provided (filled) in the adsorption tower 110, and when it comes into contact with the mixed gas under a predetermined pressure and temperature environment, the substance contained in the mixed gas is reduced. Adsorb to separate the mixed gas material.
  • the adsorbent 130 is, for example, a perovskite oxide represented by a structural formula A 1-x B x C 1-y D y O 3-z .
  • A is a lanthanoid element or an alkaline earth metal element
  • B is an element dopant in the group of a lanthanoid element, an alkaline earth metal element, and an alkali metal element
  • C is titanium (Ti) or vanadium.
  • the perovskite oxide selectively adsorbs oxygen (physical adsorption) at a predetermined temperature (for example, 250 ° C. to 900 ° C.). Therefore, by using a perovskite oxide as the adsorbent 130, oxygen can be selectively adsorbed from the air. In addition, the perovskite oxide can easily adsorb and desorb oxygen (the adsorbed substance is separated from the interface) by changing the pressure at 250 ° C. to 900 ° C.
  • the separation gas discharge unit 140 discharges nitrogen from the adsorption tower 110 from the air from which oxygen is removed by being adsorbed by the adsorbent 130. More specifically, the separation gas discharge unit 140 discharges nitrogen from the adsorption tower 110 through valves 144a to 144d. Then, the nitrogen discharged by the separation gas discharge unit 140 is sent to the nitrogen tank 146. Nitrogen stored in the nitrogen tank 146 is sequentially sent to a subsequent process.
  • the adsorption gas discharge unit 150 is constituted by a vacuum pump, depressurizes the adsorption tower 110, desorbs the oxygen adsorbed on the adsorbent 130 from the adsorbent 130, and discharges it from the adsorption tower 110. More specifically, the adsorption gas discharge unit 150 discharges oxygen from the adsorption tower 110 through the discharge pipe 152 and the valves 154a to 154d. Then, the oxygen discharged by the adsorption gas discharge unit 150 is sent to the oxygen tank 156. The oxygen stored in the oxygen tank 156 is sequentially sent to the subsequent process.
  • the heat storage body 160 (indicated by 160a, 160b and hatching in FIG. 1) is arranged on both the upstream side and the downstream side in the air supply direction from the adsorbent 130 in the adsorption tower 110, and the mixed gas supply unit 120
  • the air supplied into the adsorption tower 110, the nitrogen discharged from the adsorption tower 110 by the separation gas discharge section 140, and the oxygen discharged from the adsorption tower 110 by the adsorption gas discharge section 150 pass through.
  • the adsorbent 130 is sandwiched between the two heat storage bodies 160 in the adsorption tower 110.
  • the portion of the adsorption tower 110 where the heat storage body 160 is disposed is not accommodated in the heat insulating chamber 102, and the heat storage body 160 is exposed to room temperature.
  • the heat storage bodies 160a and 160b By arranging the heat storage bodies 160a and 160b on both sides of the adsorbent 130 in the flow direction of the fluid (air, nitrogen, oxygen), the heat outflow from the adsorbent 130 to the outside and the heat from the outside to the adsorbent 130 are transferred. Inflow can be reduced, for example, to less than 10%. Therefore, the energy required for heating the adsorbent 130 can be reduced, and the power consumption required for heating the adsorbent 130 can be reduced. That is, nitrogen and oxygen can be produced at low cost.
  • heat storage body 160 that has a small pressure loss when a fluid passes and has a large amount of heat storage.
  • the heat storage body 160 include a stainless steel heat storage material honeycomb having a liner pitch of about 2 mm and a flat plate thickness of about 0.5 mm.
  • the heat storage body 160 may be composed of the same member as the adsorbent 130. With this configuration, oxygen and nitrogen can be separated also in the heat storage body 160.
  • the heat storage body 160 when the heat storage body 160 comes into contact with air under a predetermined pressure and a temperature environment closer to room temperature than the adsorbent 130, the heat storage body 160 adsorbs oxygen and separates nitrogen (for example, activated carbon (MSC) or low temperature). It may be composed of an adsorbent such as a complex oxide that operates. Thereby, in the heat storage body 160, it becomes possible to isolate
  • nitrogen for example, activated carbon (MSC) or low temperature.
  • FIG. 2 is a flowchart for explaining the processing flow of the gas separation method
  • FIG. 3 is a diagram for explaining the open / close state of the valve in each step of the gas separation method.
  • the control means keeps the valves 124a to 124d, 144a to 144d, and 154a to 154d closed, and exposes the adsorbent 130 in the adsorption tower 110 to an atmosphere of 250 ° C. to 900 ° C. Keep it.
  • the first regeneration process S220 is performed in parallel in the adsorption tower 110b, and the first regeneration process S220 is performed in the adsorption tower 110a.
  • the first adsorption step S210 is performed in parallel in the adsorption tower 110b.
  • the second adsorption step S230 is performed in the adsorption tower 110a
  • the second regeneration step S240 is performed in parallel in the adsorption tower 110b
  • the second regeneration step S240 is performed in the adsorption tower 110a
  • the second adsorption step S230 is performed in parallel in the adsorption tower 110b.
  • the adsorption tower 110a and the adsorption tower 110b can alternately generate the nitrogen and oxygen continuously by alternately repeating the adsorption process and the regeneration process.
  • FIG. 4 is a flowchart for explaining the processing flow of the first adsorption step S210.
  • Step S210-1 The control means (not shown) drives the mixed gas supply unit 120, opens the valve 124a (see FIG. 3), and supplies air into the adsorption tower 110a (supply process). That is, air at normal temperature reaches the adsorbent 130 through the heat storage body 160a.
  • Step S210-2 the control means determines whether or not the pressure P in the adsorption tower 110a is equal to or higher than a predetermined pressure P1 (for example, 100 kPa to 200 kPa).
  • the control means performs the supplying step S210-1 until the pressure P in the adsorption tower 110a becomes equal to or higher than the predetermined pressure P1 (NO in S210-2). While the control means performs the supply process and raises the pressure in the adsorption tower 110a to a predetermined pressure P1, oxygen in the air is adsorbed on the adsorbent 130.
  • the pressure P in the adsorption tower 110a becomes equal to or higher than the predetermined pressure P1 (YES in S210-2)
  • the mixed gas supply unit 120 is stopped, and the process proceeds to the separation gas discharge step S210-3 described later.
  • Step S210-3 When the pressure P in the adsorption tower 110a becomes equal to or higher than the predetermined pressure P1 (YES in S210-2), the control means closes the valve 124a and opens the valve 144b (see FIG. 3). As a result, the separation gas discharge unit 140 discharges nitrogen from which the oxygen adsorbed by the adsorbent 130 has been removed from the air from the adsorption tower 110a (separation gas discharge processing). That is, high temperature (250 ° C. to 900 ° C.) nitrogen is discharged through the heat storage body 160b, and the normal temperature heat storage body 160b is heated by the high temperature nitrogen. On the other hand, high temperature nitrogen can be cooled by the normal temperature heat storage body 160b. Then, the nitrogen discharged from the adsorption tower 110a is sent to the nitrogen tank 146.
  • the control means closes the valve 124a and opens the valve 144b (see FIG. 3).
  • the separation gas discharge unit 140 discharges nitrogen from which the oxygen adsorbed by the
  • Step S210-4 a control means determines whether the pressure P in the adsorption tower 110a became less than predetermined pressure P2 (for example, 60 kPa).
  • the control means performs the separation gas discharge step S210-3 until the pressure P in the adsorption tower 110a becomes less than the predetermined pressure P2 (NO in S210-4).
  • the pressure P in the adsorption tower 110a becomes less than the predetermined pressure P2 (YES in S210-4)
  • it is considered that the first adsorption step S210 has been completed, and the process proceeds to a first regeneration step S220 described later.
  • FIG. 5 is a flowchart for explaining the processing flow of the first regeneration step S220.
  • Step S220-1 In the separation gas discharge determination step S210-4 described above, when the pressure P in the adsorption tower 110a becomes less than the predetermined pressure P2 (YES in S210-4), the control means closes the valve 144b and opens the valve 154a. At the same time (see FIG. 3), the adsorbed gas discharge unit 150 is driven. Thereby, the pressure in the adsorption tower 110a is reduced and oxygen adsorbed on the adsorbent 130 is desorbed from the adsorbent 130, and oxygen is discharged from the adsorption tower 110a (adsorption gas discharge processing). That is, high-temperature (250 ° C.
  • oxygen is discharged through the heat storage body 160a, and the room temperature heat storage body 160a is heated by the high-temperature oxygen.
  • high temperature oxygen can be cooled by the normal temperature heat storage body 160a. Then, the oxygen discharged from the adsorption tower 110a is sent to the oxygen tank 156.
  • Step S220-2 the control means determines whether or not the pressure P in the adsorption tower 110a is less than a predetermined pressure P3 (for example, 2 kPa to 20 kPa).
  • the control means performs the adsorption gas discharge step S220-1 until the pressure P in the adsorption tower 110a becomes less than the predetermined pressure P3 (NO in S220-2).
  • the control means closes the valve 154a (see FIG. 3).
  • the process proceeds to the second adsorption step S230 described later.
  • control means discharges nitrogen from one end side of the adsorption tower 110a and performs the other end side of the adsorption tower 110a in one gas separation process (first adsorption step S210 and first regeneration step S220). Exhausts oxygen from the water.
  • both the heat storage bodies 160a and 160b distribute
  • Step S230 The control means performs the adsorption process shown in FIG.
  • the valves that are opened and closed by the control means are different in steps S210-1 and S210-3, the valve opening and closing control by the control means is as described above. Are described in detail, and other detailed description is omitted.
  • the control means drives the mixed gas supply unit 120, opens the valve 124b, and supplies air into the adsorption tower 110a. That is, air at normal temperature reaches the adsorbent 130 through the heat storage body 160b.
  • the control means performs the previous separation gas discharge step S210-3 (the separation gas in the first adsorption step S210) of the one end side and the other end side of the adsorption tower 110a.
  • the discharge step S210-3 air is supplied from the side where nitrogen is discharged.
  • the control means heats the air at normal temperature to reach the adsorbent 130 by passing it through the heat storage body 160b heated by the previous high-temperature nitrogen. Therefore, the air reaching the adsorbent 130 can be heated without requiring a separate heating device, and the amount of heating in the adsorbent 130 can be reduced.
  • the control unit closes the valve 124b and opens the valve 144a.
  • the separation gas discharge unit 140 discharges nitrogen from which the oxygen adsorbed by the adsorbent 130 has been removed from the adsorption tower 110a. That is, high temperature (250 ° C. to 900 ° C.) nitrogen is discharged through the heat storage body 160a, and the heat storage body 160a is heated by the high temperature nitrogen.
  • control means alternately changes the route for supplying high-temperature nitrogen in the first adsorption step S210 and the second adsorption step S230.
  • high-temperature nitrogen passes through the heat storage body 160b in the first adsorption step S210, that is, the heat storage body 160b is heated in the first adsorption step S210, and the heat storage body 160a is heated in the second adsorption step S230.
  • High-temperature nitrogen passes, that is, the heat storage body 160a is heated in the second adsorption step S230.
  • the heat storage body 160a is heated by high-temperature oxygen, and the heat storage body 160b is heated by high-temperature nitrogen. .
  • the ratio of nitrogen and oxygen in the air is about 8: 2
  • the control means in the separation gas discharge step S210-3 (separation gas discharge processing) in the second adsorption step S230, the previous separation gas discharge step S210-3 (separation gas discharge step S210-3 in the first adsorption step S210).
  • the heat storage bodies 160a and 160b can be heated substantially uniformly.
  • Step S240 The control means performs the reproduction process shown in FIG.
  • the valve that the control means opens and closes in step S220-1 is the same as described above, the valve opening and closing control by the control means will be described in detail. Other detailed explanation is omitted.
  • the control means closes the valve 144a, opens the valve 154b, and drives the adsorption gas discharge unit 150.
  • the inside of the adsorption tower 110a is depressurized, and the oxygen adsorbed on the adsorbent 130 is desorbed from the adsorbent 130 and discharged from the adsorption tower 110a. That is, high-temperature (250 ° C. to 900 ° C.) oxygen is discharged through the heat storage body 160b, and the heat storage body 160b is heated by the high-temperature oxygen.
  • control means discharges nitrogen from one end side of the adsorption tower 110a and performs the other end side of the adsorption tower 110a in one gas separation process (second adsorption step S230 and second regeneration step S240). Exhausts oxygen from the water.
  • both the heat storage bodies 160a and 160b distribute
  • a mixed gas at normal temperature (100%) passes in the adsorption process, and high-temperature oxygen (20%) passes in the regeneration process performed next, followed by the adsorption process performed.
  • the process of passing hot nitrogen (80%) is repeated. Therefore, in one heat storage body, the heat held when high-temperature oxygen and high-temperature nitrogen are discharged can be made substantially equal to the heat applied when the mixed gas is supplied.
  • the heat applied from the outside in this heat storage body can theoretically be zero.
  • the adsorption tower 110 of the gas separation device 100 has been described as an example in which the adsorption tower 110 is configured in a cylindrical shape having a substantially straight central axis.
  • the shape of the adsorption tower is not limited.
  • a gas separation device 300 having an adsorption tower of another shape will be described.
  • FIG. 6 is a view for explaining a gas separation device 300 according to the second embodiment.
  • the gas separation device 300 includes a heat insulating chamber 302, an adsorption tower 310, a mixed gas supply unit 120, a supply pipe 122, an adsorbent 130, a separation gas discharge unit 140, and a nitrogen tank 146. And an adsorbed gas discharge unit 150, a discharge pipe 152, an oxygen tank 156, a heat storage body 160, and valves 124a to 124d, 144a to 144d, and 154a to 154d.
  • the mixed gas supply unit 120, the supply pipe 122, the adsorbent 130, the separation gas discharge unit 140, the nitrogen tank 146, the adsorption gas discharge unit 150, the discharge pipe 152 which have already been described as the components in the first embodiment described above. Since the oxygen tank 156, the heat storage body 160, and the valves 124a to 124d, 144a to 144d, and 154a to 154d have substantially the same functions, a duplicate description is omitted. Here, the heat insulating chamber 302 and the adsorption tower 310 having different configurations are omitted. And will be mainly described.
  • the heat storage chamber 302 accommodates at least a portion of the adsorption tower 310 filled with the adsorbent 130 and exposes the adsorbent 130 to an atmosphere of 250 ° C. to 900 ° C.
  • the adsorption tower 310 is configured by a tubular member having a plurality of (here, two) extending portions 312 and 314 extending linearly and a folded portion 320 connecting the extending portions 312 and 314. .
  • returning part 320 is curved shape, ie, the adsorption tower 310 is comprised by the U-shaped tubular member.
  • the extending portion 312 includes a first extending portion 312a and a second extending portion 312b, and the first extending portion 312a and the second extending portion 312b are connected by a flange 330.
  • the extending part 314 includes a first extending part 314a and a second extending part 314b, and the first extending part 314a and the second extending part 314b are connected by a flange 330.
  • the adsorbent 130 is disposed (filled) in the second extending portion 312b, the folded portion 320, and the second extending portion 314b, and the second extending portion 312b, the folded portion 320,
  • the 2nd extension part 314b is accommodated in the heat retention box 302.
  • the heat storage body 160 is disposed in the first extending portion 312a and the first extending portion 314a, and the first extending portions 312a and 314a are disposed outside (room temperature).
  • the adsorbent 130 is arranged in the heat insulating chamber 302, and the heat storage body 160 is arranged outside. Therefore, it becomes possible to heat only the adsorbent 130 efficiently.
  • the heat storage body 160 can be easily maintained by arranging the heat storage body 160 outside (room temperature) and connecting the heat storage body 160 and the adsorbent 130 with the flange 330.
  • the valves 124a to 124d, 144a to 144d, and 154a to 154d can be arranged outside, the valves 124a to 124d, 144a to 144d, and 154a to 154d do not need to be expensive valves corresponding to high temperatures. The cost of the separation device 300 itself can be reduced.
  • the extension parts 312 and 314 are arrange
  • the extending portions 312 and 314 are provided at the two extending portions 312 and 314, respectively, and are disposed at the end portions of the extending portions 312 and 314 opposite to the end portions to which the folded portions 320 are connected.
  • Such a fluid supply mechanism and discharge mechanism can be integrated on the same side. Therefore, the gas separation device 300 itself can be made compact.
  • the piston flow can be realized in the adsorption tower 310 by forming the adsorption tower 310 in such a shape that the flow path length / flow path cross-sectional area becomes large. Thereby, it is possible to suppress a situation where oxygen and nitrogen once separated in the adsorption tower 310 are mixed again.
  • the gas separation apparatus 100 including two adsorption towers 110a and 110b has been described as an example, and therefore, the case where the adsorption tower 110a and the adsorption tower 110b perform regeneration and adsorption in parallel.
  • the heat storage body 160 may be disposed on both sides of the adsorbent 130 in the fluid flow direction, and the number of adsorption towers is not limited. That is, the number of adsorption towers may be one, or three or more.
  • the perovskite oxide is used as an example of the adsorbent 130
  • the adsorption towers 110 and 310 are exposed to an atmosphere higher than normal temperature
  • the adsorbent 130 may be exposed to a temperature atmosphere suitable for adsorption of a substance by the adsorbent.
  • the adsorbent is Na-KA zeolite
  • the adsorption tower is exposed to an atmosphere at a temperature lower than room temperature (eg, -30 ° C.) and adsorbs oxygen in a mixed gas composed of dry air. Then, nitrogen and argon (Ar) are separated.
  • the pressure when performing the adsorption step in the adsorption tower is, for example, 120 kPa (absolute pressure), and the pressure when performing the regeneration step is 10 kPa (absolute pressure).
  • the adsorption tower is exposed to an atmosphere at a temperature lower than normal temperature (for example, ⁇ 30 ° C.), adsorbs nitrogen in a mixed gas composed of dry air, Oxygen and argon (Ar) will be separated.
  • the pressure when performing the adsorption step in the adsorption tower is, for example, 120 kPa (absolute pressure), and the pressure when performing the regeneration step is 30 kPa (absolute pressure).
  • the adsorption tower When the adsorbent is Na-X zeolite, the adsorption tower is exposed to an atmosphere at a temperature lower than room temperature (eg, -30 ° C.) and adsorbs xenon in a mixed gas composed of dry air and xenon. Then, the dry air is separated.
  • the pressure when performing the adsorption step in the adsorption tower is, for example, 120 kPa (absolute pressure), and the pressure when performing the regeneration step is 5 kPa (absolute pressure).
  • Ba 1 Fe y Y 1-y O 3-z can be given as a perovskite oxide having a combination of different atoms.
  • the folded portion 320 may have a bent shape.
  • you may be comprised with the tubular member of L shape, V shape, and W shape.
  • the adsorbent 130 and the heat storage body 160 may be formed continuously.
  • the adsorbent 130 and the heat storage body 160 may be formed continuously.
  • a heater may be provided inside the adsorption towers 110 and 310 in order to assist the heat radiation in the heat insulation chambers 102 and 302.
  • the present invention can be used in a gas separation apparatus and a gas separation method for separating a predetermined gas from a mixed gas.

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PCT/JP2013/066448 2012-06-19 2013-06-14 ガス分離装置およびガス分離方法 Ceased WO2013191097A1 (ja)

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CN105692570A (zh) * 2016-03-11 2016-06-22 北京市飞达捷能气体分离技术有限公司 一种可替代膜分离制氮的变压吸附制氮装置
WO2018075933A1 (en) 2016-10-21 2018-04-26 Corning Incorporated Sorbent structures with resistive heating capability and methods of making the same
US10315152B2 (en) 2017-06-08 2019-06-11 DK Engineering Consulting LLC Method and system for pressure swing adsorption
CN109289515B (zh) * 2018-11-29 2024-01-19 国电环境保护研究院有限公司 一种再生塔停机防腐蚀系统和停机操作方法
CN113731103A (zh) * 2021-09-07 2021-12-03 福建师范大学 一种挥发性有机物高效节能处理装备

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JP5600336B2 (ja) 2014-10-01
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