【０００１】[0001]
【発明の属する技術分野】本発明は、選択的透過性を有
するガス分離膜を用いてガス混合物から特定のガス成分
を分離回収するためのガス分離膜の運転方法に関する。
特に、前記膜の透過側の圧力（ゲージ圧）を供給側の圧
力（ゲージ圧）に対して０．１〜５０％の範囲内で調節
することによって、設備費用や運転コストを抑制できる
簡便で経済的なガス分離膜の運転方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for operating a gas separation membrane for separating and recovering a specific gas component from a gas mixture using a gas separation membrane having selective permeability.
In particular, by adjusting the pressure (gauge pressure) on the permeation side of the membrane within the range of 0.1 to 50% with respect to the pressure (gauge pressure) on the supply side, the facility cost and the operation cost can be suppressed easily. The present invention relates to an economical method for operating a gas separation membrane.
【０００２】[0002]
【従来の技術】選択的透過性を有するガス分離膜を用い
て、ガス混合物から特定のガス成分を分離回収する方法
が広く実施されている。例えば、空気から富化窒素ガス
を得る場合、空気から水分を分離除去して除湿空気を得
る場合、油田から採取された天然ガスやランドフィルガ
スから二酸化炭素を分離してメタンガスなどを回収する
場合、有機物蒸気を含むガス混合物から有機物蒸気を分
離回収する場合などにおいて、ガス分離膜を用いた方法
が好適に実施されている。ガス分離膜を用いた分離回収
方法は、装置が小型で簡便であるので設備費が少なくて
済み、運転方法が容易であり、また、運転コストが安価
であるという利点がある。2. Description of the Related Art A method of separating and recovering a specific gas component from a gas mixture using a gas separation membrane having selective permeability has been widely practiced. For example, to obtain nitrogen-enriched gas from air, to remove moisture from air to obtain dehumidified air, to separate carbon dioxide from natural gas or landfill gas collected from oil fields, and to collect methane gas, etc. In the case of separating and recovering an organic vapor from a gas mixture containing an organic vapor, a method using a gas separation membrane is suitably performed. The separation and recovery method using a gas separation membrane has the advantages that the equipment is small and simple, so that equipment costs are low, the operation method is easy, and the operation cost is low.
【０００３】ガス分離膜を用いて分離回収された製品ガ
スは何らかの目的に使用される。目的とする純度や流量
が得られるだけの膜面積を持ったガス分離膜やコンプレ
ッサーなどの付帯設備を整えれば、分離回収によって目
的の製品ガスを得ることは可能になる。ところが、通
常、ガス分離膜はサイズや膜面積の大きさ等によって数
種類のグレードのガス分離膜モジュールとしてラインア
ップされて供給されるので、使用時にはラインアップさ
れたガス分離膜モジュールの中から目的とする要求能力
を満たすようにグレードや個数を選んで用いられる。こ
のために実際のガス分離膜モジュールを用いた分離回収
工程では、要求能力と設備能力を完全一致させることが
できず少なからず過剰な能力を持ったガス分離膜モジュ
ールを用いることになる。そしてこの場合、該ガス分離
膜モジュールに対応してコンプレッサーなどの付帯設備
も過剰な能力のものが必要になるために設備費や運転コ
ストが嵩み経済性において改良する余地があった。The product gas separated and recovered using the gas separation membrane is used for some purpose. By installing auxiliary equipment such as a gas separation membrane or a compressor having a membrane area enough to obtain the desired purity and flow rate, it becomes possible to obtain the desired product gas by separation and recovery. However, gas separation membranes are usually supplied as a lineup of gas separation membrane modules of several grades depending on the size, the size of the membrane area, etc. Grade and number are selected and used so as to satisfy the required capacity. For this reason, in the separation and recovery process using an actual gas separation membrane module, the required capacity and the equipment capacity cannot be completely matched, and a gas separation membrane module having a considerable excess capacity is used. In this case, ancillary equipment such as a compressor corresponding to the gas separation membrane module also needs to have an excessive capacity, so that equipment costs and operation costs are increased, and there is room for improvement in economic efficiency.
【０００４】また、ガス分離膜は常に一定のガス分離性
能を保持できるわけではなく、例えば膜表面にオイルミ
ストが吸着すると膜の透過性は低下する。もちろんその
様な膜性能の低下を防止するために例えば供給ガスをミ
ストセパレータで処理してオイルミストを除去するとい
った前処理がなされるが、環境や運転条件によってはあ
る程度の膜への悪影響を考慮せざるを得ない場合がある
ので、万一性能が低下しても直ちにガス分離膜モジュー
ルが使えなくならないように安全率を加味し過剰な能力
を持つガス分離膜モジュールが採用される。この場合も
該ガス分離膜モジュールに対応したコンプレッサーなど
の付帯設備は過剰な能力のものが必要になるために設備
費や運転コストが嵩み経済性において改良する余地があ
った。Further, the gas separation membrane cannot always maintain a constant gas separation performance. For example, if oil mist is adsorbed on the membrane surface, the permeability of the membrane is reduced. Of course, in order to prevent such a decrease in membrane performance, pretreatment such as removing the oil mist by treating the supply gas with a mist separator is performed, but some adverse effects on the membrane may be considered depending on the environment and operating conditions. In some cases, a gas separation membrane module having an excessive capacity is used in consideration of a safety factor so that the gas separation membrane module cannot be used immediately even if the performance deteriorates. Also in this case, the auxiliary equipment such as a compressor corresponding to the gas separation membrane module needs to have an excessive capacity, so that the equipment cost and the operating cost are increased, and there is room for improvement in economy.
【０００５】さらに、膜の透過性能が低下した場合にそ
の都度膜を取り替えることは経済的ではないから、目的
に適合する純度や流量の製品ガスが得られるように運転
条件などを調節して運転を継続することが好ましい。供
給ガスの圧力を高めて調節する場合には予め過剰な能力
のコンプレッサーなどを準備しておく必要が生じる。圧
力を上げないで同じ純度を保持しようとすると供給ガス
の供給量を減らすことになるので得られる製品ガス量が
減少してしまう。また、透過側の圧力を減圧して調節す
る場合にはエジェクターなどの減圧装置を備える必要が
生じ、運転が複雑になるし運転コストも高くなるので簡
便で経済的な方法とはならない。目的の純度の製品ガス
を一旦バッファタンクに貯えて必要量だけタンクから使
用することも考えられるがそのためにはバッファタンク
などの設備が必要になるしタンクを備えるスペースも必
要になる。更にガス分離の工程とタンクから取り出す工
程を調節する制御システムあるいは複雑な操作が必要に
なり好ましいものではない。このため、膜の透過性能が
低下した場合でも目的に適合する純度や流量の製品ガス
が継続して得ることができ、設備費用や運転コストの増
大を抑制できる簡便で経済的な運転方法が求められてい
た。[0005] Further, it is not economical to replace the membrane each time the permeation performance of the membrane decreases, so that the operating conditions are adjusted so as to obtain a product gas having a purity and a flow rate suitable for the purpose. Is preferably continued. When adjusting the pressure of the supply gas by increasing it, it is necessary to prepare a compressor having an excessive capacity in advance. If the same purity is to be maintained without increasing the pressure, the supply amount of the supply gas will be reduced, so that the amount of product gas obtained will decrease. In addition, when the pressure on the permeate side is adjusted by reducing the pressure, it is necessary to provide a pressure reducing device such as an ejector, which complicates the operation and increases the operation cost, so that it is not a simple and economical method. It is conceivable to temporarily store the product gas of the desired purity in the buffer tank and use only a required amount of the product gas from the tank. However, for this purpose, equipment such as a buffer tank is required, and a space including the tank is also required. Further, a control system or complicated operation for adjusting the gas separation step and the step of taking out from the tank is required, which is not preferable. For this reason, even if the permeability of the membrane is reduced, a product gas having a purity and a flow rate suitable for the purpose can be continuously obtained, and a simple and economical operation method capable of suppressing an increase in equipment cost and operation cost is required. Had been.
【０００６】[0006]
【発明が解決しようとする課題】選択的透過性を有する
ガス分離膜を用いてガス混合物から特定のガス成分を分
離回収するときに、能力的に過剰なガス分離膜に対応し
て加圧装置などの付帯設備も過剰な能力のものが必要に
なり運転コストも高くなるという問題、および、ガス分
離膜の透過性能が低下したときにも継続的に目的とする
純度や流量の製品ガスを得たいという問題を解決し、設
備費用や運転コストを抑制できる簡便で経済的なガス分
離膜の運転方法を提供することが本発明の課題である。When a gas separation membrane having selective permeability is used to separate and recover a specific gas component from a gas mixture, a pressurizing apparatus corresponding to the excess gas separation membrane is required. However, it is also necessary to increase the operating cost because of the need for ancillary equipment with excessive capacity, and to obtain product gas of the desired purity and flow rate continuously even when the permeation performance of the gas separation membrane is reduced. SUMMARY OF THE INVENTION It is an object of the present invention to provide a simple and economical method for operating a gas separation membrane, which can solve the above-mentioned problem and can reduce equipment costs and operation costs.
【０００７】[0007]
【課題を解決するための手段】本発明は、選択的透過性
を有するガス分離膜の供給側にガス混合物を加圧して供
給する工程と、膜の透過側の圧力（ゲージ圧）を供給側
の圧力（ゲージ圧）に対して０．１〜５０％の範囲内で
調節する工程とを含み、前記膜の透過側の圧力調節によ
って膜の供給側に供給するガス混合物の供給流量が調節
されることを特徴とする、ガスを分離回収するためのガ
ス分離膜の運転方法に関する。また、本発明は、選択的
透過性を有するガス分離膜の供給側にガス混合物を加圧
して供給する工程と、膜の透過側の圧力（ゲージ圧）を
供給側の圧力（ゲージ圧）に対して０．１〜５０％の範
囲内で調節する工程とを含み、前記膜の透過側の圧力調
節によって膜の未透過側で得られる製品ガスの純度およ
び／あるいは流量が調節されることを特徴とする、ガス
を分離回収するためのガス分離膜の運転方法に関する。
更に、本発明は、前記膜の透過側の圧力調節が、膜の透
過側からの透過ガス排出流の流量を絞ることによってお
こなわれること、ガス分離膜が非対称ポリイミド中空糸
分離膜であり、供給するガス混合物が空気であり、膜の
未透過側で得られる製品ガスが富化窒素であることを特
徴とするガスを分離回収するためのガス分離膜の運転方
法に関する。SUMMARY OF THE INVENTION The present invention comprises a step of pressurizing and supplying a gas mixture to a supply side of a gas separation membrane having selective permeability; Adjusting the pressure within the range of 0.1 to 50% with respect to the pressure (gauge pressure) of the membrane, whereby the supply flow rate of the gas mixture supplied to the supply side of the membrane is adjusted by adjusting the pressure on the permeation side of the membrane. A method for operating a gas separation membrane for separating and recovering gas. The present invention also provides a step of supplying a gas mixture under pressure to a supply side of a gas separation membrane having selective permeability, and a step of changing the pressure (gauge pressure) on the permeate side of the membrane to the pressure (gauge pressure) on the supply side. Adjusting the pressure on the permeate side of the membrane to adjust the purity and / or flow rate of the product gas obtained on the non-permeate side of the membrane. The present invention relates to a method of operating a gas separation membrane for separating and recovering a gas, which is characterized by the following.
Further, according to the present invention, the pressure adjustment on the permeation side of the membrane is performed by reducing the flow rate of the permeated gas discharge flow from the permeation side of the membrane, the gas separation membrane is an asymmetric polyimide hollow fiber separation membrane, The method for operating a gas separation membrane for separating and recovering a gas is characterized in that the gas mixture to be produced is air and the product gas obtained on the non-permeate side of the membrane is nitrogen-enriched.
【０００８】[0008]
【発明の実施の形態】本発明で用いられるガス分離膜は
ガス選択的透過性を有すれば特に限定はないが、高分子
膜、炭素膜、高分子を部分炭素化した部分炭素化膜、ゼ
オライトなどのセラミック膜が使用できる。また、膜は
平膜でも中空糸膜でもよいが有効膜面積を大きくして分
離効率を高めることが容易な中空糸膜が好適である。中
空糸膜の形態は、均質膜でもよく、複合膜や非対称膜な
どの不均一性のものでもよいが、透過速度が大きい非対
称性膜が好ましい。また、中空糸膜の膜厚は１０〜５０
０μｍで外径は５０〜２０００μｍのものを好適に挙げ
ることができる。BEST MODE FOR CARRYING OUT THE INVENTION The gas separation membrane used in the present invention is not particularly limited as long as it has gas-selective permeability, but includes a polymer membrane, a carbon membrane, a partially carbonized membrane obtained by partially carbonizing a polymer, Ceramic membranes such as zeolites can be used. Further, the membrane may be a flat membrane or a hollow fiber membrane, but a hollow fiber membrane which is easy to increase the effective membrane area and enhance the separation efficiency is preferable. The form of the hollow fiber membrane may be a homogeneous membrane or a non-uniform one such as a composite membrane or an asymmetric membrane, but an asymmetric membrane having a high permeation rate is preferred. The thickness of the hollow fiber membrane is 10 to 50.
Preferable examples are those having a diameter of 0 μm and an outer diameter of 50 to 2000 μm.
【０００９】中空糸膜は分離膜モジュールの形態で好適
に用いることができる。中空糸分離膜モジュールは、数
百本〜数十万本の中空糸を集束させて中空糸束とし、前
記中空糸束と前記中空糸束の少なくとも一方の端部を中
空糸が開口状態を保持するようにして樹脂などで固着し
た管板とを備えて構成した中空糸分離膜エレメントと
し、前記中空糸分離膜エレメントの一つあるいは二つ以
上を少なくとも混合ガス導入口、透過ガス排出口、未透
過ガス排出口を備える容器内に膜の透過側の空間と供給
側（未透過側）の空間が隔絶するように収納して構成さ
れたものである。The hollow fiber membrane can be suitably used in the form of a separation membrane module. The hollow fiber separation membrane module bundles hundreds to hundreds of thousands of hollow fibers into a hollow fiber bundle, and the hollow fiber holds an open state at least one end of the hollow fiber bundle and the hollow fiber bundle. A hollow fiber separation membrane element comprising a tube sheet fixed with a resin or the like as described above, and one or more of the hollow fiber separation membrane elements are provided with at least a mixed gas inlet, a permeated gas outlet, It is configured such that the space on the permeation side of the membrane and the space on the supply side (non-permeation side) are housed in a container having a permeated gas outlet so as to be separated.
【００１０】前記中空糸分離膜モジュールの混合ガス導
入口から混合ガスが供給され、中空糸膜の供給側の空間
（中空糸の内側あるいは外側）へ導入されてガス分離膜
表面と接しながら流れる間に、混合ガス中の膜透過成分
が膜の透過側の空間へ透過して流れ透過ガス排出口から
回収または透過ガス排出流として排出され、膜透過成分
が膜の透過側の空間へ透過したあとの混合ガスは膜透過
成分が減少した未透過ガスとなって未透過ガス排出口か
ら回収または未透過ガス排出流として排出される。[0010] A mixed gas is supplied from the mixed gas inlet of the hollow fiber separation membrane module, is introduced into the space on the supply side of the hollow fiber membrane (inside or outside the hollow fiber), and flows while being in contact with the gas separation membrane surface. Then, the permeated component of the mixed gas permeates into the permeate side space of the membrane and flows through the permeate gas outlet to be recovered or discharged as a permeate gas discharge flow, and the permeated component permeates to the permeate side space of the membrane. Is converted into a non-permeate gas having a reduced membrane permeation component, and is recovered from the non-permeate gas outlet or discharged as a non-permeate gas discharge stream.
【００１１】分離膜によってガスを分離回収する場合、
通常は前記の透過ガスおよび／あるいは未透過ガスが製
品ガスとして回収されるが、本発明のガス分離膜の運転
方法は、未透過ガスを製品ガスとして回収する場合に好
適に用いることができる。When gas is separated and recovered by a separation membrane,
Usually, the above-mentioned permeated gas and / or unpermeated gas is recovered as a product gas, but the method for operating a gas separation membrane of the present invention can be suitably used when recovering an unpermeated gas as a product gas.
【００１２】本発明のガス分離膜の運転方法は、目的の
純度と流量の製品ガスに対して余分な分離能力を持つ単
数又は複数の分離膜モジュールを備えたガス分離システ
ムにおいて、ガス分離膜の供給側にガス混合物を加圧し
て供給し、前記膜の透過側の圧力（ゲージ圧）を供給側
の圧力（ゲージ圧）に対して０．１〜５０％の範囲内で
調節して、前記膜の供給側に供給するガス混合物の供給
流量を調節するガス分離膜の運転方法である。余分な分
離能力を持つ分離膜モジュールを用いて通常の運転方法
で目的の純度の製品ガスを得ようとすると、余分な分離
能力を持つ分離膜モジュールに必要なだけの供給ガスを
供給することになるから、当然加圧装置（例えばコンプ
レッサー）などの付帯装置は過大な能力のものが要求さ
れ運転コストも過大になる。本発明は、膜の透過側を加
圧状態にして供給圧と透過圧との差圧を調節することに
よって膜の選択透過成分の透過量を制御し、それによっ
て過剰な製品ガスを生成せず目的の純度の製品ガスを目
的流量だけ生成するように調節し、過剰な加圧装置など
の付帯設備を必要としないガス分離膜を運転する方法で
ある。The method for operating a gas separation membrane of the present invention is directed to a gas separation system provided with one or more separation membrane modules having extra separation capability for a product gas having a desired purity and flow rate. The gas mixture is supplied under pressure to the supply side, and the pressure (gauge pressure) on the permeate side of the membrane is adjusted within a range of 0.1 to 50% with respect to the pressure (gauge pressure) on the supply side. This is a method for operating a gas separation membrane for adjusting a supply flow rate of a gas mixture supplied to a supply side of the membrane. When trying to obtain a product gas of the desired purity by a normal operation method using a separation membrane module with extra separation capacity, it is necessary to supply as much supply gas as necessary to the separation membrane module with extra separation capacity. Therefore, ancillary devices such as a pressurizing device (for example, a compressor) are required to have an excessive capacity, and the operation cost is also excessive. The present invention controls the permeation amount of the permselective component of the membrane by adjusting the pressure difference between the supply pressure and the permeation pressure while the permeate side of the membrane is in a pressurized state, thereby preventing excess product gas from being generated. This is a method of operating a gas separation membrane that adjusts so that a product gas having a desired purity is generated at a desired flow rate and does not require ancillary equipment such as an excessive pressurizing device.
【００１３】しかも、本発明の膜の透過側の圧力（ゲー
ジ圧）を供給側の圧力（ゲージ圧）に対して０．１〜５
０％の範囲内で調節することは、膜の透過側からの透過
ガス排出流の流量を絞ることによって簡便且つ容易にお
こなうことができる。安価な流量絞り装置（流量調節
弁）を追加するだけで膜の透過側の圧力を加圧状態に調
節できるので、設備費用や運転コストを抑制できる。ま
た操作も簡便である。この方法によれば、目的の純度と
流量の製品ガスに対して過剰な分離能力を持つ分離膜モ
ジュールを備えたガス分離システムにおいて、安価な流
量絞り装置（流量調節弁）を追加するだけでコンプレッ
サーやフィルターなどの前処理装置は大型のものを備え
る必要はなく、比較的小さいコンプレッサーと付帯設備
さえ備えれば目的とする製品ガスを得ることが可能にな
る。Further, the pressure (gauge pressure) on the permeation side of the membrane of the present invention is 0.1 to 5 with respect to the pressure (gauge pressure) on the supply side.
Adjustment within the range of 0% can be easily and easily performed by reducing the flow rate of the permeated gas discharge flow from the permeation side of the membrane. Since the pressure on the permeation side of the membrane can be adjusted to a pressurized state only by adding an inexpensive flow restrictor (flow control valve), equipment costs and operation costs can be suppressed. The operation is also simple. According to this method, in a gas separation system provided with a separation membrane module having an excessive separation capability for a product gas having a target purity and a flow rate, a compressor can be added simply by adding an inexpensive flow restrictor (flow control valve). It is not necessary to provide a large-sized pretreatment device such as a filter and a filter, and a desired product gas can be obtained as long as a relatively small compressor and ancillary equipment are provided.
【００１４】また、本発明のガス分離方法は、目的の純
度と流量の製品ガスに対して過剰な分離能力を持つ単数
又は複数の分離膜モジュールを備えたガス分離システム
において、ガス分離膜の供給側にガス混合物を加圧して
供給し、前記膜の透過側の圧力（ゲージ圧）を供給側の
圧力（ゲージ圧）に対して０．１〜５０％の範囲内で調
節して、前記膜の未透過側で得られる製品ガスの純度お
よび／あるいは流量を調節することを特徴とするガス分
離膜の運転方法である。Further, the gas separation method of the present invention is a method for supplying a gas separation membrane in a gas separation system comprising one or more separation membrane modules having an excessive separation capacity for a product gas having a desired purity and flow rate. The gas mixture is supplied to the membrane under pressure, and the pressure (gauge pressure) on the permeation side of the membrane is adjusted within a range of 0.1 to 50% with respect to the pressure (gauge pressure) on the supply side. A method for operating a gas separation membrane, characterized by adjusting the purity and / or flow rate of a product gas obtained on the non-permeate side of the gas separation membrane.
【００１５】本発明のガス分離膜の運転方法は、分離膜
の透過性能が経時的に低下する場合などにおいて、未透
過側で得られる製品ガスの純度および／あるいは流量を
調節することができるので極めて有効である。すなわ
ち、初期段階で膜の透過側の圧力（ゲージ圧）を供給側
の圧力（ゲージ圧）の０．１〜５０％の範囲内で調節し
ておき、分離膜の透過性能が経時的に低下するに従って
透過側の圧力を下げる。こうすれば、供給量や供給圧力
はほぼ一定のままで目的の純度と流量の製品ガスを得る
ことができる。分離膜の透過性能の経時的低下に対応し
て供給圧力を高くして目的の純度と流量の製品ガスを得
るように調節することも可能であるが、その場合にはコ
ンプレッサー能力をより大きくする必要が生じまた運転
コストも高いものになる。According to the method for operating a gas separation membrane of the present invention, the purity and / or flow rate of the product gas obtained on the non-permeate side can be adjusted when the permeation performance of the separation membrane decreases over time. Extremely effective. That is, in the initial stage, the pressure (gauge pressure) on the permeation side of the membrane is adjusted within the range of 0.1 to 50% of the pressure (gauge pressure) on the supply side, and the permeation performance of the separation membrane decreases with time. The pressure on the permeate side is reduced as required. In this way, it is possible to obtain a product gas having a desired purity and flow rate while keeping the supply amount and the supply pressure almost constant. It is also possible to adjust the supply pressure to obtain the product gas of the desired purity and flow rate in response to the deterioration of the permeation performance of the separation membrane over time, but in that case, increase the compressor capacity. The need arises and the operating costs are high.
【００１６】本発明において、膜の供給側の圧力は０．
５〜３０ｋｇｆ／ｃｍ2（ゲージ圧）が好ましく、特
に、２〜２０ｋｇｆ／ｃｍ2（ゲージ圧）が好ましい。
圧力が０．５ｋｇｆ／ｃｍ2（ゲージ圧）未満では膜を
透過させるドライビングフォースが少ないし、３０ｋｇ
ｆ／ｃｍ2（ゲージ圧）を越えると膜の耐圧性を越えて
しまう可能性があり、また極めて大きな加圧装置やその
他の付帯装置が必要になるので好ましくない。また、温
度は特に限定されないが熱交換器などで−５０〜２００
℃の温度に調温されることが好ましい。また、ガス混合
物がガス分離膜へ供給される前に、膜にとって有害とな
り得る成分を除去することが好ましい。例えば、ダスト
フィルターで浮遊粒子を除去したり、冷凍除湿機で水分
を除去したり、オイルセパレーターやミストセパレータ
ーで油分を除去したり、スクラバーで特定化学成分を除
去するなどの前処理がなされる。In the present invention, the pressure on the supply side of the membrane is 0.1.
The pressure is preferably 5 to 30 kgf / cm2 (gauge pressure), and particularly preferably2 to 20 kgf / cm2 (gauge pressure).
If the pressure is less than 0.5 kgf / cm2 (gauge pressure), the driving force for permeating the membrane is small, and
If f / cm2 (gauge pressure) is exceeded, the pressure resistance of the film may be exceeded, and an extremely large pressurizing device and other auxiliary devices are required, which is not preferable. The temperature is not particularly limited, but may be -50 to 200 with a heat exchanger or the like.
Preferably, the temperature is adjusted to a temperature of ° C. Before the gas mixture is supplied to the gas separation membrane, it is preferable to remove components that may be harmful to the membrane. For example, pretreatment such as removal of suspended particles with a dust filter, removal of moisture with a freeze dehumidifier, removal of oil with an oil separator or mist separator, and removal of specific chemical components with a scrubber is performed.
【００１７】本発明において、ガス混合物は加圧して分
離膜の供給側へ供給される。ガス混合物を加圧して供給
するための加圧装置としてブロワー、コンプレッサーが
用いられる。特に、オイルフリーコンプレッサーは膜に
対して悪影響を有するオイル、オイルミストを供給する
ガス混合物に混入させることがほとんどないので好適で
ある。In the present invention, the gas mixture is supplied under pressure to the supply side of the separation membrane. A blower and a compressor are used as a pressurizing device for pressurizing and supplying the gas mixture. In particular, an oil-free compressor is preferable because it hardly mixes oil and oil mist that have an adverse effect on the membrane into a gas mixture that supplies the oil and oil mist.
【００１８】本発明において、膜の透過側からの排出ガ
スの流量を絞るためには、透過ガスを系外へ排出する排
出流配管の途中に流量を絞る装置例えばニードル弁、グ
ローブ弁などの流量調節弁を配置すればよい。絞りの程
度を大きくすれば透過側の圧力が高くなる。この様な装
置は極めて簡便なものであり安価かつ操作が容易なもの
である。本発明において、膜の透過側の圧力（ゲージ
圧）は供給側の圧力（ゲージ圧）に対して０．１〜５０
％の範囲内で調節される。好ましくは０．１〜２０％の
範囲内であり、特に好ましくは０．１〜７％の範囲内で
ある。０．１％未満では本発明の調節機能を発揮できな
い。また、５０％を越えると膜の供給側と透過側の差圧
が小さくなり透過流量が小さくなり過ぎて効率的なガス
分離ができなくなる。In the present invention, in order to reduce the flow rate of the exhaust gas from the permeation side of the membrane, a device for reducing the flow rate in the middle of a discharge flow pipe for discharging the permeated gas out of the system, for example, a flow rate of a needle valve, a globe valve, etc. What is necessary is just to arrange a control valve. Increasing the degree of aperture increases the pressure on the transmission side. Such a device is very simple, inexpensive and easy to operate. In the present invention, the pressure (gauge pressure) on the permeation side of the membrane is 0.1 to 50 with respect to the pressure (gauge pressure) on the supply side.
It is adjusted within the range of%. Preferably it is in the range of 0.1-20%, particularly preferably in the range of 0.1-7%. If it is less than 0.1%, the regulation function of the present invention cannot be exhibited. On the other hand, if it exceeds 50%, the pressure difference between the supply side and the permeation side of the membrane becomes small, and the permeation flow rate becomes too small, so that efficient gas separation becomes impossible.
【００１９】本発明のガス分離膜の運転方法は、ガス混
合物をガス分離膜へ供給し膜透過成分を膜を透過させる
ことによって除き、膜透過成分が減少した未透過のガス
を未透過ガス排出口から分離回収し製品ガスとして目的
の純度と流量で得る場合に有用である。例えば、空気か
ら富化窒素ガスを得る場合、空気から水分を分離除去し
て除湿空気を得る場合、油田から採取された天然ガスや
ランドフィルガスから二酸化炭素を分離してメタンガス
などを回収する場合、有機物蒸気を含むガス混合物から
有機物蒸気を分離回収する場合などにおいて有用であ
る。特に、空気中の酸素を膜透過によって分離して未透
過ガスとして分離回収される富化窒素ガスは、パージガ
スとして例えばクリーニング装置、洗浄装置、半導体装
置、印刷装置などの他の装置と組み合わせて使われるこ
とが多く、ガス分離膜システムはコンパクトで過剰な設
備を必要としないことや簡便な運転であること、またガ
ス分離システムが継続的に運転できないために組み合わ
されている装置を停止する必要がないことなどが望まれ
ている。このような場合には、本発明のガス分離膜の運
転方法が極めて好適である。In the method for operating a gas separation membrane of the present invention, the gas mixture is supplied to the gas separation membrane, and the membrane-permeable component is removed by permeating the membrane. This is useful when separating and recovering from an outlet to obtain a product gas with the desired purity and flow rate. For example, to obtain nitrogen-enriched gas from air, to remove moisture from air to obtain dehumidified air, to separate carbon dioxide from natural gas or landfill gas collected from oil fields, and to collect methane gas, etc. This is useful in the case of separating and recovering an organic vapor from a gas mixture containing the organic vapor. In particular, nitrogen-enriched gas, which separates oxygen in air by membrane permeation and separates and recovers it as a non-permeated gas, is used as a purge gas in combination with other devices such as a cleaning device, a cleaning device, a semiconductor device, and a printing device. Gas separation membrane systems are often compact, do not require excessive equipment, are simple to operate, and must be shut down due to the inability to operate gas separation systems continuously. It is hoped that there is no such thing. In such a case, the method for operating the gas separation membrane of the present invention is extremely suitable.
【００２０】本発明のガス分離膜の運転方法において、
空気を分離して富化窒素ガスを製品ガスとして生成させ
る場合には、ガス分離膜は非対称ポリイミド中空糸分離
膜を用いることが好ましい。非対称ポリイミド中空糸分
離膜は酸素の透過速度、酸素と窒素の分離度、耐久性、
耐熱性、耐圧性や機械的強度が優れた膜であるので、空
気分離によって富化窒素ガスを生成するのに好適であ
る。In the method for operating a gas separation membrane of the present invention,
When air is separated to generate an enriched nitrogen gas as a product gas, it is preferable to use an asymmetric polyimide hollow fiber separation membrane as the gas separation membrane. Asymmetric polyimide hollow fiber separation membrane has oxygen permeation rate, oxygen and nitrogen separation, durability,
Since the membrane is excellent in heat resistance, pressure resistance and mechanical strength, it is suitable for generating an enriched nitrogen gas by air separation.
【００２１】次に、本発明で使用されるガス分離膜シス
テムの実施形態の一つの概要図である図１によって更に
本発明を説明する。図１のシステムは空気から富化窒素
ガスを分離回収するものである。尚、本発明で使用され
るガス分離膜システムは図１に示された実施形態に限定
されるものではない。空気取入口１から採取された空気
はダストフィルター２で空気中の浮遊粒子などを除去さ
れコンプレッサー３へ供給される。加圧された空気はタ
ンク４で加圧状態で保持され、冷凍除湿機５で比較的低
湿度まで除湿されて圧力調節弁６で圧力調節されてオイ
ルセパレーター７、ミストセパレーター８で空気中のオ
イル分を除去したあと熱交換器１０で必要に応じて加熱
または冷却されて、中空糸ガス分離膜モジュール１２、
１３のガス供給口から膜の供給側へ流される。９は圧力
計、１１は温度計である。ガス混合物が膜に接して流れ
る間に膜を選択的に透過する酸素ガス成分が膜を透過す
る。透過した透過ガスは膜の透過側を流れてモジュール
の透過ガス排出口を経由して透過ガス排出流となり配管
の途中で流量調節弁１６、１７で流量を絞られたのち系
外へ排出される。１４、１５は圧力計である。流量調節
弁１６、１７で流量を絞られて中空糸分離膜モジュール
内の膜の透過側の空間の圧力は膜の供給側の圧力（ゲー
ジ圧）の０．１〜５０％に調節される。膜透過成分の酸
素ガスが除去された富化窒素ガスは膜の未透過側を流れ
て中空糸膜分離膜モジュールの未透過ガス排出口を経て
製品ガス出口２４へ導かれる。１８、１９は酸素濃度
計、２０、２１は流量調節弁、２２、２３は流量計であ
る。図１では２本の中空糸分離膜モジュールが並列で用
いられており、供給ガスは前処理を終わったあと分岐し
てそれぞれのモジュールへ供給され、それぞれの中空糸
分離膜モジュールで得られた富化窒素ガスは合流して製
品ガス出口２４へ導かれている。Next, the present invention will be further described with reference to FIG. 1 which is a schematic view of one embodiment of the gas separation membrane system used in the present invention. The system of FIG. 1 separates and recovers nitrogen-enriched gas from air. The gas separation membrane system used in the present invention is not limited to the embodiment shown in FIG. The air collected from the air intake 1 is supplied to the compressor 3 after removing suspended particles and the like in the air by the dust filter 2. The pressurized air is held in a pressurized state in a tank 4, dehumidified to a relatively low humidity by a refrigerating dehumidifier 5, pressure-controlled by a pressure control valve 6, and oil in the air by an oil separator 7 and a mist separator 8. After removing the components, the hollow fiber gas separation membrane module 12 is heated or cooled as necessary in the heat exchanger 10,
Thirteen gas supply ports flow to the supply side of the membrane. 9 is a pressure gauge and 11 is a thermometer. Oxygen gas components that selectively permeate the membrane while the gas mixture flows in contact with the membrane permeate the membrane. The permeated gas that has passed through flows through the permeate side of the membrane, passes through the permeate gas outlet of the module, becomes a permeate gas discharge flow, and is discharged out of the system after the flow rate is reduced by flow control valves 16 and 17 in the middle of the pipe. . 14 and 15 are pressure gauges. The flow rate is regulated by the flow rate control valves 16 and 17, and the pressure in the space on the permeation side of the membrane in the hollow fiber separation membrane module is adjusted to 0.1 to 50% of the pressure (gauge pressure) on the supply side of the membrane. The nitrogen-enriched gas from which the oxygen gas of the membrane permeable component has been removed flows on the non-permeate side of the membrane, and is led to the product gas outlet 24 via the non-permeate gas outlet of the hollow fiber membrane separation membrane module. Reference numerals 18 and 19 denote oxygen concentration meters, reference numerals 20 and 21 denote flow control valves, and reference numerals 22 and 23 denote flow meters. In FIG. 1, two hollow fiber separation membrane modules are used in parallel. The supply gas is branched and supplied to each module after pretreatment, and the wealth obtained in each hollow fiber separation membrane module is obtained. The nitrogen iodide gas is merged and led to the product gas outlet 24.
【００２２】[0022]
【実施例】以下に実施例によって本発明を更に詳しく説
明する。尚、本発明は以下の実施例に限定されるもので
はない。The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the following embodiments.
【００２３】（比較例１）空気を供給量１３２Ｎｍ3／
ｈ、圧力７ｋｇｆ／ｃｍ2（ゲージ圧）で供給し透過側
を常圧（ゲージ圧が０ｋｇｆ／ｃｍ2）にすると純度９
５体積％の富化窒素ガスが６２Ｎｍ3／ｈ得られる非対
称ポリイミド中空糸ガス分離膜モジュールを用いて、純
度９５体積％の富化窒素ガスを２００Ｎｍ3／ｈ得るこ
とを検討した。目的とする純度９５体積％の富化窒素ガ
スを２００Ｎｍ3／ｈ得るためには（２００Ｎｍ3／ｈ÷
６２Ｎｍ3／ｈ＞３．２本であるので）前記非対称ポリ
イミド中空糸ガス分離膜モジュールが４本必要であり、
供給する空気量は合計で（１３２Ｎｍ3／ｈ×４本）５
２８Ｎｍ3／ｈであるので、コンプレッサーの能力は５
２８Ｎｍ3／ｈ以上の能力を持つコンプレッサーが必要
となった。(Comparative Example 1) Air supply amount 132 Nm3 /
h, when the pressure is supplied at 7 kgf / cm2 (gauge pressure) and the permeate side is at normal pressure (gauge pressure is 0 kgf / cm2 ), the purity is 9
5% by volume of enriched nitrogen gas using a 62 nm3 / h Asymmetric polyimide hollow fiber gas separation membrane module was obtained, consider a purity of 95% by volume of enriched nitrogen gas to obtain 200 Nm3 / h. In order to obtain the desired nitrogen gas with a purity of 95% by volume at 200 Nm3 / h (200 Nm3 / h ÷)
62 Nm3 /h>3.2) 4 asymmetric polyimide hollow fiber gas separation membrane modules are required,
The total amount of air to be supplied is (132 Nm3 / h x 4) 5
28 Nm3 / h, the capacity of the compressor is 5
A compressor having a capacity of 28 Nm3 / h or more was required.
【００２４】（実施例１）比較例１と同様の非対称ポリ
イミド中空糸ガス分離膜モジュールを用い、膜の透過側
の圧力を０．３ｋｇｆ／ｃｍ2（ゲージ圧）になるよう
に透過流量を絞る方法で運転すると、モジュール１本当
たり供給空気量が１２０Ｎｍ3／ｈで純度９５体積％の
富化窒素ガスが５４Ｎｍ3／ｈ得られた。従って、この
運転方法では、目的とする純度９５体積％の富化窒素ガ
スを２００Ｎｍ3／ｈ得るためには（２００Ｎｍ3／ｈ÷
５４Ｎｍ3／ｈ＞３．７本であるので）前記非対称ポリ
イミド中空糸ガス分離膜モジュールが４本必要であり、
供給する空気量は合計で（１２０Ｎｍ3／ｈ×４本）４
８０Ｎｍ3／ｈであるので、コンプレッサーの能力は４
８０Ｎｍ3／ｈ以上の能力を持つコンプレッサーであれ
ば問題がなかった。(Example 1) Using the same asymmetric polyimide hollow fiber gas separation membrane module as in Comparative Example 1, the permeation flow rate was reduced so that the pressure on the permeation side of the membrane became 0.3 kgf / cm2 (gauge pressure). When operated in a way, one per supply air volume module purity 95% by volume of enriched nitrogen gas in 120 Nm3 / h was obtained 54Nm3 / h. Therefore, in this operation method, to obtain 200 Nm3 / h of the desired nitrogen gas having a purity of 95% by volume (200 Nm3 / h ÷)
54 Nm3 /h>3.7) 4 asymmetric polyimide hollow fiber gas separation membrane modules are required,
The total amount of air to be supplied is (120 Nm3 / h x 4) 4
80Nm3 / h, the compressor capacity is 4
There was no problem if the compressor had a capacity of 80 Nm3 / h or more.
【００２５】すなわち比較例１では例えば能力が５００
Ｎｍ3／ｈのコンプレッサーでは要求性能を満たすこと
ができないために、これよりも大型のコンプレッサーを
購入する必要があったが、実施例１では能力が５００Ｎ
ｍ3／ｈのコンプレッサーで充分であり設備費が少なく
てすむことが判る。更に、比較例１で大型のコンプレッ
サーを導入すると当然運転コストが高くなるが、実施例
１では小型のコンプレッサーで済むので運転コストは比
較的少なくなる。That is, in Comparative Example 1, for example, the capacity is 500
Since the required performance cannot be satisfied with a compressor of Nm3 / h, it was necessary to purchase a compressor larger than this, but in Example 1, the capacity was 500 N.
It turns out that a compressor of m3 / h is sufficient and the equipment cost is small. Furthermore, if a large compressor is introduced in Comparative Example 1, the operating cost naturally increases, but in Example 1, the operating cost is relatively small because a small compressor is sufficient.
【００２６】（比較例２）比較例１と同様の非対称ポリ
イミド中空糸ガス分離膜モジュールを用いて、膜の透過
性能の低下が予想される環境下で、純度９５体積％の富
化窒素ガスを２００Ｎｍ3／ｈ得ることを検討した。膜
の透過性能が１５％低下しても継続して使うことができ
るように運転開始時には安全率を加味して過剰な能力を
持つガス分離膜モジュールが配置された。すなわち前記
非対称ポリイミド中空糸ガス分離膜モジュールの性能が
１５％低下した場合、ガス分離膜モジュール１本当たり
目的とする純度９５体積％の富化窒素ガスの発生量が５
３Ｎｍ3／ｈに低下することを考慮すると、目的とする
純度９５体積％の富化窒素２００Ｎｍ3／ｈを得るため
には（２００Ｎｍ3／ｈ÷５３Ｎｍ3／ｈ＞３．７本であ
るので）前記非対称ポリイミド中空糸ガス分離膜モジュ
ールが４本必要であった。(Comparative Example 2) Using the same asymmetric polyimide hollow fiber gas separation membrane module as in Comparative Example 1, under an environment where the permeation performance of the membrane is expected to decrease, 95% by volume of enriched nitrogen gas is purified. It was studied to obtain 200 Nm3 / h. At the start of the operation, a gas separation membrane module having an excessive capacity was added at the start of operation so that the membrane could be used continuously even if the permeation performance of the membrane decreased by 15%. That is, when the performance of the asymmetric polyimide hollow fiber gas separation membrane module is reduced by 15%, the amount of the target nitrogen-enriched gas having a purity of 95% by volume per gas separation membrane module is 5%.
Considering that drops to 3 nm3 / h, so in order to obtain the enriched nitrogen 200 Nm3 / h of pure 95% by volume of interest is(200Nm 3 / h ÷ 53Nm 3 /h>3.7 present 4) Four asymmetric polyimide hollow fiber gas separation membrane modules were required.
【００２７】運転開始時、膜の透過側圧力を調節するこ
となしに常圧（ゲージ圧が０ｋｇｆ／ｃｍ2）で運転す
ると、分離膜モジュール４本での純度９５体積％の富化
窒素ガスは合計（６２Ｎｍ3／ｈ×４本）２４８Ｎｍ3／
ｈ得られる。これは目的とする２００Ｎｍ3／ｈよりも
２４％過剰であり、過剰分を処理するための配管、バル
ブ、タンク、制御装置などの付帯設備が必要になった。
一方、同じ分離膜モジュールで目的とする２００Ｎｍ3
／ｈ（１本当たり５０Ｎｍ3／ｈ）の富化窒素ガスを得
ようとすると、得られる富化窒素ガスの純度は９６．２
体積％となってしまい、純度を９５体積％とするために
はこれを希釈するための付帯設備が必要となった。At the start of the operation, if the operation is carried out at normal pressure (gauge pressure is 0 kgf / cm2 ) without adjusting the pressure on the permeate side of the membrane, the nitrogen gas with a purity of 95% by volume in four separation membrane modules can be obtained. Total (62 Nm3 / h × 4) 248 Nm3 /
h is obtained. This is 24% in excess of the target of 200 Nm3 / h, and additional facilities such as piping, valves, tanks, and control devices for processing the excess are required.
On the other hand, 200 Nm3
/ H (50 Nm3 / h per line), the purity of the obtained nitrogen gas is 96.2.
However, in order to make the purity 95% by volume, additional equipment for diluting the solution was required.
【００２８】（実施例２）比較例２と同様の非対称ポリ
イミド中空糸ガス分離膜モジュールを用い、同じ環境下
同様の富化窒素ガスを得ることを本発明の運転方法によ
って検討した。運転開始時、膜の透過側の圧力を０．４
７ｋｇｆ／ｃｍ2（ゲージ圧）になるように透過流量を
絞る方法で運転すると、分離膜モジュール１本当たり純
度９５体積％の富化窒素ガスが５０Ｎｍ3／ｈ、すなわ
ち分離膜モジュール４本で純度９５体積％の富化窒素ガ
スを２００Ｎｍ3／ｈ得ることができ、目的の純度とガ
ス量を満たすことができた。すなわち、比較例２で必要
とされた付帯設備は必要なかった。Example 2 Using the same asymmetric polyimide hollow fiber gas separation membrane module as in Comparative Example 2 to obtain the same nitrogen-enriched gas under the same environment was examined by the operation method of the present invention. At the start of operation, the pressure on the permeate side of the membrane is 0.4
When operated by a method in which the permeation flow rate is reduced to 7 kgf / cm2 (gauge pressure), nitrogen gas with a purity of 95% by volume per separation membrane module is 50 Nm3 / h, that is, the purity is increased by four separation membrane modules. Nitrogen-enriched gas of 95% by volume was obtained at 200 Nm3 / h, and the desired purity and gas amount were satisfied. That is, the auxiliary equipment required in Comparative Example 2 was not required.
【００２９】また、分離膜の透過性能が１０％低下した
時点では、膜の透過側の圧力を０．２４ｋｇｆ／ｃｍ2
（ゲージ圧）になるように透過流量を絞る方法で運転す
ると、分離膜モジュール４本で純度９５体積％の富化窒
素ガスを２００Ｎｍ3／ｈ得ることができ、目的の純度
とガス量を満たすことができた。すなわち、比較例２で
必要とされた付帯設備は必要なかった。When the permeability of the separation membrane is reduced by 10%, the pressure on the permeation side of the membrane is reduced to 0.24 kgf / cm2.
(Gauge pressure), the operation is performed by reducing the permeation flow rate so that the nitrogen gas with a purity of 95% by volume can be obtained at 200 Nm3 / h with four separation membrane modules, satisfying the desired purity and gas amount. I was able to. That is, the auxiliary equipment required in Comparative Example 2 was not required.
【００３０】更に、分離膜の透過性能が１５％低下した
時点では、膜の透過側の圧力を０．１２ｋｇｆ／ｃｍ2
（ゲージ圧）になるように透過流量を絞る方法で運転す
ると、分離膜モジュール４本で純度９５体積％の富化窒
素ガスを２００Ｎｍ3／ｈ得ることができ、目的の純度
とガス量を満たすことができた。すなわち、比較例２で
必要とされた付帯設備は必要なかった。When the permeation performance of the separation membrane is reduced by 15%, the pressure on the permeation side of the membrane is reduced to 0.12 kgf / cm2.
(Gauge pressure), the operation is performed by reducing the permeation flow rate so that the nitrogen gas with a purity of 95% by volume can be obtained at 200 Nm3 / h with four separation membrane modules, satisfying the desired purity and gas amount. I was able to. That is, the auxiliary equipment required in Comparative Example 2 was not required.
【００３１】[0031]
【発明の効果】本発明は、以上説明したようなものであ
るから、以下に記載されるような効果を奏する。本発明
のガス分離膜の運転方法を用いることによって、過剰な
加圧装置などの付帯設備を必要とすることなく、目的と
する純度と流量の製品ガスを得ることができる。また、
分離膜モジュールの透過性能が劣化するような場合で
も、本発明のガス分離膜の運転方法を用いることによっ
て、過剰な付帯設備を必要とせずまた分離膜モジュール
の取り替えなどの特別な処置なしに目的とする純度と流
量の製品ガスを継続的に得ることができる。すなわち、
本発明のガス分離膜の運転方法を用いることによって、
設備費用や運転コストを抑制して簡便かつ経済的に目的
とする純度と流量の製品ガスを得ることができる。Since the present invention has been described above, it has the following effects. By using the operation method of the gas separation membrane of the present invention, it is possible to obtain a product gas having a desired purity and a flow rate without requiring additional equipment such as an excessive pressurizing device. Also,
Even when the permeation performance of the separation membrane module is deteriorated, the operation method of the gas separation membrane of the present invention does not require excessive auxiliary equipment and can be used without any special treatment such as replacement of the separation membrane module. The product gas having the purity and flow rate can be continuously obtained. That is,
By using the operation method of the gas separation membrane of the present invention,
It is possible to easily and economically obtain a product gas having a desired purity and flow rate while suppressing equipment costs and operation costs.
【図１】本発明で使用されるガス分離膜システムの実施
形態の一つの概要図であるFIG. 1 is a schematic diagram of one embodiment of a gas separation membrane system used in the present invention.
１：空気取入口 ２：ダストフィルター ３：コンプレッサー ４：高圧タンク ５：冷凍除湿機 ６：圧力調節弁 ７：オイルセパレーター ８：ミストセパレーター ９：圧力計 １０：熱交換器 １１：温度計 １２、１３：中空糸ガス分離膜モジュール １４、１５：圧力計 １６、１７：流量調節弁 １８、１９：酸素濃度計 ２０、２１：流量調節弁 ２２、２３：流量計 ２４：製品ガス出口 1: Air intake 2: Dust filter 3: Compressor 4: High pressure tank 5: Refrigeration dehumidifier 6: Pressure control valve 7: Oil separator 8: Mist separator 9: Pressure gauge 10: Heat exchanger 11: Thermometer 12, 13 : Hollow fiber gas separation membrane module 14, 15: pressure gauge 16, 17: flow control valve 18, 19: oxygen concentration meter 20, 21: flow control valve 22, 23: flow meter 24: product gas outlet
フロントページの続き Ｆターム(参考） 4D006 GA41 HA01 KA01 KA12 KB14 KE02Q KE06P KE06Q KE07P KE08Q KE13Q KE16P MA01 MB04 MB15 MB16 MC58 PA03 PB62 PC01 4G042 BA29 BA30 BA41 BB02Continued on front page F-term (reference) 4D006 GA41 HA01 KA01 KA12 KB14 KE02Q KE06P KE06Q KE07P KE08Q KE13Q KE16P MA01 MB04 MB15 MB16 MC58 PA03 PB62 PC01 4G042 BA29 BA30 BA41 BB02
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000228727AJP3951569B2 (en) | 2000-07-28 | 2000-07-28 | Operation method of gas separation membrane |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000228727AJP3951569B2 (en) | 2000-07-28 | 2000-07-28 | Operation method of gas separation membrane |
| Publication Number | Publication Date |
|---|---|
| JP2002035530Atrue JP2002035530A (en) | 2002-02-05 |
| JP3951569B2 JP3951569B2 (en) | 2007-08-01 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000228727AExpired - LifetimeJP3951569B2 (en) | 2000-07-28 | 2000-07-28 | Operation method of gas separation membrane |
| Country | Link |
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| JP (1) | JP3951569B2 (en) |
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| JP2008238099A (en)* | 2007-03-28 | 2008-10-09 | Air Liquide Japan Ltd | Gas manufacturing method and gas manufacturing equipment using gas separation membrane |
| WO2009030777A1 (en)* | 2007-09-07 | 2009-03-12 | L'air Liquide, Société Anonyme pour l'Étude et l'Exploitation des Procédés Georges Claude | Gas production method using gas separation membranes |
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