WO2022230096A1 - Système de séparation de gaz - Google Patents

Système de séparation de gaz Download PDF

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Publication number
WO2022230096A1
WO2022230096A1 PCT/JP2021/016936 JP2021016936W WO2022230096A1 WO 2022230096 A1 WO2022230096 A1 WO 2022230096A1 JP 2021016936 W JP2021016936 W JP 2021016936W WO 2022230096 A1 WO2022230096 A1 WO 2022230096A1
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WO
WIPO (PCT)
Prior art keywords
gas
separation membrane
separation
separation system
permeated
Prior art date
Application number
PCT/JP2021/016936
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English (en)
Japanese (ja)
Inventor
直行 石田
明紀 田村
順一 三輪
秀宏 飯塚
祐子 可児
崇 佐々木
貴彰 水上
晋士 藤田
亜由美 渡部
良平 稲垣
Original Assignee
株式会社日立製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社日立製作所 filed Critical 株式会社日立製作所
Priority to PCT/JP2021/016936 priority Critical patent/WO2022230096A1/fr
Publication of WO2022230096A1 publication Critical patent/WO2022230096A1/fr

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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
    • B01D53/22—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 diffusion

Definitions

  • the present disclosure relates to a gas separation system that allows specific gas users to separate and use the specific gas at the place of use, for example, when supplying a specific gas different from natural gas using an existing pipeline such as natural gas. .
  • a separation membrane that selectively permeates the gas.
  • a molecular sieve membrane that separates based on the difference in molecular diameter, represented by ceramic membranes and polymer membranes, and a metal membrane that adsorbs hydrogen, separates it into atoms and permeates them, and the like.
  • Molecular sieve membranes are capable of separating gases, but they also permeate a certain amount of gases other than the specific gases to be permeated. will be Separation is possible at room temperature, but there is a tendency for the amount of permeation to increase when the temperature is raised.
  • only hydrogen is allowed to pass through the metal film, so when hydrogen is used as the specific gas, high-purity hydrogen can be obtained, but the film is heated to 300 to 400.degree.
  • Patent Document 1 describes a method of using a separation membrane for a mixed gas of two components and heating the gas to improve the purity of the separated gas.
  • heated gas is supplied to the metal membrane.
  • the hot non-permeate gas it is preferable to cool the hot non-permeate gas as it returns to the pipeline so as not to thermally load the pipeline.
  • gases have lower density and thermal conductivity than liquids, and a large heat transfer area is preferred for heat exchange, which can result in large gas heaters and coolers in the gas separation system.
  • Patent Document 1 after pressurizing the mixed gas with a compressor, the permeated gas is recovered in the first separation stage, and the gas that did not permeate in the first separation stage (non-permeated gas) is heated to about 50 ° C.
  • Two separation stages separate the permeate gas from the non-permeate gas to improve the purity of the non-permeate gas.
  • the concentration of the permeating gas is lower than in the first separation stage, so the gas temperature is raised to increase the permeation amount. It is assumed that a polymer membrane will be used as the separation membrane, and the upper limit of the purity of the separated gas is about 98%.
  • the permeating gas side may be permeated with a separation membrane in several stages, which may increase the size of the device. Furthermore, since a differential pressure is provided across the membrane for gas permeation, a large pressure is applied in the first separation stage in the case of multiple stages, which may also lead to an increase in the size of the apparatus.
  • the purpose of the present disclosure is to significantly reduce the amount of gas heating required to separate a specific gas with high purity, and to downsize the heat exchangers for heating and cooling the gas or eliminate the cooler. to provide an efficient gas separation system.
  • a first separation membrane branched from a pipeline through which a mixed gas containing a specific gas flows, the pressure of the branched mixed gas is increased by a compressor, and the first separation membrane has selective permeability to the specific gas;
  • a first discharge pipe that returns the mixed gas that has not permeated the separation membrane to the pipeline, a heater that heats the permeated gas that has permeated the first separation membrane, and a heater for the specific gas contained in the heated permeated gas.
  • a second separation membrane having higher permselectivity than the first separation membrane.
  • the amount of heating of the mixed gas required for extracting the specific gas with high purity from the mixed gas can be significantly reduced, and the cooling equipment for the mixed gas that has not permeated can be greatly simplified. Significant cost reduction of the separation system is possible.
  • FIG. 1 is a schematic diagram of a first embodiment of a gas separation system of the present disclosure
  • FIG. 1 is a schematic diagram showing a gas separation system using a metal membrane for obtaining high-purity hydrogen gas
  • FIG. 2 is a schematic diagram illustrating a second embodiment of the gas separation system of the present disclosure
  • FIG. 3 is a schematic diagram illustrating a third embodiment of the gas separation system of the present disclosure
  • FIG. 4 is a schematic diagram of a fourth embodiment of the gas separation system of the present disclosure
  • FIG. 1 is a schematic diagram illustrating a gas separation system 100 (first embodiment) of the present disclosure.
  • FIG. 2 is a schematic diagram showing a gas separation system 200 using metal membranes for obtaining high-purity hydrogen gas.
  • the pipeline is a city gas pipe whose main component is methane, and hydrogen is used as the specific gas.
  • hydrogen is used as the specific gas.
  • the specific gas is not limited to hydrogen, for example.
  • the hydrogen purity required by hydrogen consumers is 99.99%, and it is preferable to increase the hydrogen purity to the required specification by separating the mixed gas from the hydrogen concentration of 20% in the pipeline.
  • a pipe branches off from a pipeline 1 through which a mixed gas containing hydrogen flows, and the mixed gas is pressurized by a first compressor 2 .
  • the temperature of the mixed gas is raised to about 350° C. by the heater 13 , and the mixed gas is supplied to the metal membrane, which is the first separation membrane 11 .
  • the metal membrane which is the first separation membrane 11 .
  • the metal film only hydrogen molecules are adsorbed on the metal surface and separated into atoms, the atoms diffuse through the metal film, and the atoms bond on the opposite surface to return to hydrogen molecules.
  • the mixed gas is heated in order to allow hydrogen to permeate through the metal film, which also heats 80% of the methane that does not permeate the mixed gas. If the heated methane is returned to the pipeline 1 through the first discharge pipe 21 as it is, the rise in gas temperature in the pipeline 1 may cause the flow to become unstable or cause structural problems due to expansion of the pipe. there is a possibility. Therefore, it is practical to attach the cooler 14 to the first discharge pipe 21 for the mixed gas. Note that the first discharge pipe 21 has a role of returning the mixed gas that has not permeated the first separation membrane 11 to the pipeline 1 .
  • the first separation membrane 11 is a separation membrane (membrane having selective permeability to hydrogen) selectively permeable to hydrogen at room temperature (for example, 10° C. to 40° C.), for example, a molecular sieve such as a polymer membrane or a ceramic membrane. It is a membrane that separates on the principle of a membrane.
  • the molecular sieve membrane allows molecules with a smaller molecular diameter than the size of the permeable pores in the membrane to pass through, but since there is a distribution in the size of the permeable pores, even a small amount of methane, which has a larger molecular diameter than the average permeable pores, There is, but it is permeable.
  • the permeation ratio of hydrogen and methane is 100:1
  • the hydrogen concentration of the permeated gas that has permeated the first separation membrane 11 is 96%, and almost all methane can be removed.
  • the mixed gas that has not permeated is returned to the pipeline 1 through the first discharge pipe 21 .
  • the permeated gas is heated to a high temperature (for example, 200° C. to 400° C., 350° C.
  • the second separation membrane 12 is a metal membrane and has a higher selective permeability than the first separation membrane 11 for hydrogen contained in the permeated gas heated by the heater 13 .
  • high-purity hydrogen gas high-purity specific gas
  • the mixed gas that has not permeated the second separation membrane 12 is returned to the pipeline 1 through the second discharge pipe 22 .
  • the amount of heat required for heating the mixed gas is compared.
  • the mixed gas is 20% hydrogen and 80% methane, and the hydrogen:methane permeation ratio at the first separation membrane 11 is 100:1.
  • the gas separation system 100 of FIG. 1 assuming that all the hydrogen in the mixed gas sent by the first compressor 2 permeates the first separation membrane 11, the mixed gas 100 flowing into the first separation membrane 11 permeates The amounts are 20 hydrogen and 0.8 methane. Therefore, the amount of heat required to heat the mixed gas after permeation is 20.8% of that in the gas separation system 200 of FIG. For this reason, the heater 13 can be greatly simplified, and the energy supply used for heating the mixed gas can be reduced to about 1/5.
  • the high-temperature methane returned to the pipeline 1 through the second discharge pipe 22 is 0.8% of the mixed gas sent from the first compressor 2. Therefore, the heat quantity of the mixed gas returned to the pipeline 1 can be suppressed to 1/100 compared with the configuration of FIG. For this reason, the cooler 14 installed in the second discharge pipe 22 returning the mixed gas to the pipeline 1 can be greatly simplified or removed as shown in FIG. can be done.
  • a cooler 14 (FIG. 2) is installed in the second discharge line 22 . Therefore, the installed cooler 14 can be greatly simplified, and the entire gas processing system can be downsized.
  • the mixed gas is supplied in an amount that does not significantly change the hydrogen concentration in the first separation membrane 11 in actual operation.
  • the heating amount of the mixed gas in the heater 13 is further increased, so the ratio of the heating energy that can be suppressed with the configuration of the present disclosure is further increased.
  • hydrogen is used as the specific gas
  • a molecular sieve membrane is used as the first separation membrane 11
  • a metal membrane is used as the second separation membrane 12.
  • Specific conditions are arbitrary. Thereby, the heating energy can be suppressed and the high-purity specific gas can be extracted from the mixed gas.
  • FIG. 3 is a schematic diagram illustrating a gas separation system 300 (second embodiment) of the present disclosure.
  • the difference of the second embodiment from the first embodiment is that the second compressor 3 is attached between the first separation membrane 11 and the heater 13 .
  • the second compressor 3 pressurizes the gas between the permeation side of the first separation membrane 11 and the inlet of the second separation membrane 12 .
  • the mixed gas permeates the first separation membrane 11 and the second separation membrane 12 due to the gas partial pressure difference before and after the first separation membrane 11 and the second separation membrane 12 . Therefore, in order to increase the permeation amount, the gas partial pressure before each of the first separation membrane 11 and the second separation membrane 12 should be increased, and the gas partial pressure after each of the first separation membrane 11 and the second separation membrane 12 should be increased. Lowering the gas partial pressure is effective.
  • the second compressor 3 the gas partial pressure after the first separation membrane 11 is reduced, and the gas partial pressure before the second separation membrane 12 is increased, so that the first separation membrane 11 and the second separation membrane It is possible to increase the permeation amount of 12 specific gases.
  • FIG. 4 is a schematic diagram illustrating a gas separation system 400 of the present disclosure.
  • the third embodiment differs from the first embodiment (FIG. 1) in that the second discharge pipe 22 that connects the pipeline 1 and the second separation membrane 12 is not provided, and the second separation membrane 12 is not permeated. It is provided with a third discharge pipe 24 for burning the mixed gas open to the atmosphere or in a part open to the atmosphere. Therefore, in the third embodiment, the mixed gas that has not permeated through the second separation membrane 12 is not returned to the pipeline 1, but is discharged to the atmosphere or burned to be treated. Since the heated gas is not returned to the pipeline 1, the pipeline 1 can be configured so as not to be thermally affected at all.
  • FIG. 5 is a schematic diagram illustrating a gas separation system 500 of the present disclosure.
  • the fourth embodiment differs from the third embodiment (FIG. 4) in that the third discharge pipe 24 is not provided, and the fourth discharge pipe 25 (connecting pipe) connecting the second separation membrane 12 and the combustor 31 is provided. , and a combustion gas transport pipe 32 .
  • the combustion gas transport pipe 32 supplies the heater 13 with high-temperature combustion gas generated by burning the mixed gas that has not permeated the second separation membrane 12 in the combustor 31 .
  • the mixed gas that has not permeated the second separation membrane 12 is not returned to the pipeline 1 and is burned by supplying oxygen to the combustor 31 .
  • the high-temperature combustion gas is used as a heating source for the mixed gas that has permeated the first separation membrane 11 .
  • the gas separation system 500 includes a combustor 31 that combusts the mixed gas that has not permeated through the second separation membrane 12 , and the combustion gas discharged from the combustor 31 serves as a heat source for the heater 13 .
  • the fourth embodiment it is possible to effectively use the mixed gas that was discarded or simply burned in the third embodiment, and to greatly reduce or eliminate the heat source from the outside of the heater 13 . Therefore, it is possible to further reduce the cost.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention permet une réduction considérable des coûts d'un système de séparation de gaz, au moyen de la réduction considérable de la quantité de chauffage d'un gaz de mélange requise pour extraire un gaz spécifique à haute pureté à partir du gaz de mélange, et simplifie considérablement une installation de refroidissement du gaz de mélange qui n'a pas effectué de perméation. À cet effet, le système de séparation de gaz comprend : une première membrane de séparation étant dérivée d'une canalisation à travers laquelle coule un gaz de mélange comprenant un gaz spécifique, et conçue pour élever, à l'aide d'un compresseur, la pression du gaz de mélange ayant été dérivé, et présentant une certaine perméabilité sélective par rapport au gaz spécifique ; un premier tuyau d'évacuation destiné à retourner à la canalisation le gaz de mélange n'ayant pas traversé la première membrane de séparation ; un dispositif de chauffage destiné à chauffer le gaz de perméation ayant traversé la première membrane de séparation ; une seconde membrane de séparation présentant une perméabilité sélective, par rapport au gaz spécifique compris dans le gaz de perméation chauffé, supérieure à celle de la première membrane de séparation ; et un second tuyau d'évacuation destiné à retourner à la canalisation le gaz de mélange qui n'a pas traversé la seconde membrane de séparation.
PCT/JP2021/016936 2021-04-28 2021-04-28 Système de séparation de gaz WO2022230096A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009029676A (ja) * 2007-07-27 2009-02-12 Nippon Oil Corp 水素製造および二酸化炭素回収方法ならびに装置
JP2009280426A (ja) * 2008-05-21 2009-12-03 Nissan Motor Co Ltd 水素生成装置
JP2013255898A (ja) * 2012-06-13 2013-12-26 Mitsubishi Electric Corp ガス回収装置およびガス回収方法
JP2016055276A (ja) * 2014-09-12 2016-04-21 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード ガス製造方法及び製造装置
JP2019520198A (ja) * 2016-05-31 2019-07-18 エボニック スペシャルティ ケミカルズ （シャンハイ） カンパニー リミテッドＥｖｏｎｉｋ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ （Ｓｈａｎｇｈａｉ） Ｃｏ．， Ｌｔｄ． ガス分離のためのプロセスおよび機器

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009029676A (ja) * 2007-07-27 2009-02-12 Nippon Oil Corp 水素製造および二酸化炭素回収方法ならびに装置
JP2009280426A (ja) * 2008-05-21 2009-12-03 Nissan Motor Co Ltd 水素生成装置
JP2013255898A (ja) * 2012-06-13 2013-12-26 Mitsubishi Electric Corp ガス回収装置およびガス回収方法
JP2016055276A (ja) * 2014-09-12 2016-04-21 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード ガス製造方法及び製造装置
JP2019520198A (ja) * 2016-05-31 2019-07-18 エボニック スペシャルティ ケミカルズ （シャンハイ） カンパニー リミテッドＥｖｏｎｉｋ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ （Ｓｈａｎｇｈａｉ） Ｃｏ．， Ｌｔｄ． ガス分離のためのプロセスおよび機器

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