JPH01176420A - Separation of gas - Google Patents
Separation of gasInfo
- Publication number
- JPH01176420A JPH01176420A JP62334268A JP33426887A JPH01176420A JP H01176420 A JPH01176420 A JP H01176420A JP 62334268 A JP62334268 A JP 62334268A JP 33426887 A JP33426887 A JP 33426887A JP H01176420 A JPH01176420 A JP H01176420A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- gas separation
- membrane
- separation membrane
- gas mixture
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 238000000926 separation method Methods 0.000 title claims abstract description 86
- 239000012528 membrane Substances 0.000 claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000004642 Polyimide Substances 0.000 claims abstract description 17
- 229920001721 polyimide Polymers 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000428 dust Substances 0.000 abstract description 9
- 239000007789 gas Substances 0.000 description 93
- 239000003595 mist Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000004984 aromatic diamines Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NHJNWRVCOATWGF-UHFFFAOYSA-N 3-(3-amino-2-phenoxyphenyl)sulfonyl-2-phenoxyaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C(=C(N)C=CC=2)OC=2C=CC=CC=2)=C1OC1=CC=CC=C1 NHJNWRVCOATWGF-UHFFFAOYSA-N 0.000 description 1
- WRYQQAHYGHCEQE-UHFFFAOYSA-N 3-[(3-amino-2-phenoxyphenyl)methyl]-2-phenoxyaniline Chemical compound C=1C=CC=CC=1OC=1C(N)=CC=CC=1CC1=CC=CC(N)=C1OC1=CC=CC=C1 WRYQQAHYGHCEQE-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Filtering Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、気体分離膜を用いる気体分離方法に関し、さ
らに詳しくは、二種以上の気体成分を含む気体混合物を
気体分離膜に接触させて、該気体分離膜により該気体混
合物中の少なくとも一種の気体成分を透過分離するごと
からなる気体分離方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a gas separation method using a gas separation membrane, and more specifically, to a gas separation method in which a gas mixture containing two or more gas components is brought into contact with a gas separation membrane. , relates to a gas separation method comprising permeating and separating at least one gas component in the gas mixture using the gas separation membrane.
［発明の背景］
気体混合物から有用な気体を分離する方法として、気体
分離膜を用いるプロセスが数多く提案されている。分離
の対象となる気体混合物系には、Ｈ、−Ｃｏ％Ｈ２Ｎ２
、Ｈ２−ＣＨ、、ＣＯ２−Ｎ ２、ＣＯ２ＣＨａあ６
Ｌ、Ｎはｏ２−Ｎ２等多くの気体混合物がある。これら
分離の対象となる気体混合物は、実際の工業プロセスに
おいては、粉塵を少なからぬ量含んでいるのが通例であ
る。[Background of the Invention] Many processes using gas separation membranes have been proposed as methods for separating useful gases from gas mixtures. The gas mixture system to be separated includes H, -Co%H2N2
, H2-CH, , CO2-N 2, CO2CHa6
There are many gas mixtures of L and N, such as o2-N2. In actual industrial processes, these gas mixtures to be separated usually contain a considerable amount of dust.
この、ため、従来の気体分離プロセスにおいては、分離
対象の気体混合物を気体分離操作にかける前に、濾過装
置（フィルター）を利用して、このような粉塵を除去す
ることが行なわれていた。For this reason, in conventional gas separation processes, such dust has been removed using a filtration device (filter) before subjecting the gas mixture to be separated to a gas separation operation.
近年において、気体分離プロセスの用途の拡大のために
、気体分離性能の向上や、分離性能の経時安定性の向上
のための研究が行なわれ、各種の気体分離膜が開発され
てきている。In recent years, in order to expand the applications of gas separation processes, research has been conducted to improve gas separation performance and the stability of separation performance over time, and various gas separation membranes have been developed.
本発明者も、そのような目的の研究開発を行なってきた
が、その過程において、耐久性のある気体分離膜を使用
した場合に、−実験室レベルの気体分離試験では充分°
高い気体分離性能の経時安定性が確かめられたにもかか
わらず、実際の気体混合物の分離にその気体分離膜を利
用した場合に、期待された程の分離性能の経時安定性を
示さないことが多いことを見い出した。そして、その理
由を更に研究した結果、気体分離性能の経時安定性には
、分離対象の気体混合物中の非常に微細な浮遊粒子が影
響を与えることを見い出した。The present inventor has also carried out research and development for such a purpose, but in the process, it was found that when a durable gas separation membrane is used, it is sufficient for laboratory-level gas separation tests.
Although the high stability of gas separation performance over time has been confirmed, when the gas separation membrane is used to separate actual gas mixtures, the stability of separation performance over time is not as expected. I discovered many things. As a result of further research into the reason for this, it was discovered that the stability of gas separation performance over time is affected by extremely fine suspended particles in the gas mixture to be separated.
すなわち、気体混合物中の非常に微細な浮遊粒子（ダス
ト、ミスト等）としては、大気中に含まれる浮遊粒子、
燃料に由来するガス状排出物から生成された粒子および
気体混合物を加圧する際に使用されるコンプレッサーの
オイルミストなどがある。大気中の浮遊粒子としては、
土壌、砂塵、海塩、火山噴出物および植物浸出物由来の
炭化水素などを挙げることができる。また、燃料に由来
するガス状排出物から生成された粒子としては、亜硫酸
ガスから生じた硫酸塩、窒素酸化物ガスから生じた硝酸
塩および炭化水素を挙げることができる。In other words, very fine suspended particles (dust, mist, etc.) in a gas mixture include suspended particles contained in the atmosphere,
These include particles generated from gaseous emissions derived from fuels and oil mist from compressors used in pressurizing gas mixtures. As suspended particles in the atmosphere,
Mention may be made of hydrocarbons derived from soil, dust, sea salt, volcanic ejecta and plant exudates. Particles generated from gaseous emissions derived from fuels may also include sulfates generated from sulfur dioxide gas, nitrates generated from nitrogen oxide gas, and hydrocarbons.
このようなダストおよびミストはまた大きさの点から、
１μｍ以上の巨大粒子、０．１〜１μｍの大粒子および
０．１μｍ以下のエイトケン粒子に分けることができる
が、気体分離プロセスに一般的に用いられているフィル
ターは、平均孔径が５μｍ程度あるいはそれ以上である
ため、気体混合物中の浮遊粒子の内の巨大粒子を除去す
るためには有効であるが、それよりも微細な浮遊粒子を
除去するには適していなかった。Such dust and mist also vary in size,
They can be divided into giant particles of 1 μm or more, large particles of 0.1 to 1 μm, and Aitken particles of 0.1 μm or less, but filters commonly used in gas separation processes have an average pore size of about 5 μm or less. Therefore, although it is effective for removing giant particles among suspended particles in a gas mixture, it is not suitable for removing finer suspended particles.
本発明者の研究によると、気体混合物中の浮遊粒子は、
大粒子のものに限らず、微細な粒子のものであっても、
気体分離膜の分離性能の安定性に少なからずの悪影響を
与えることが確認された。According to the inventor's research, suspended particles in a gas mixture are
Not only large particles but also fine particles,
It was confirmed that this had a considerable negative effect on the stability of the separation performance of the gas separation membrane.
特にコンプレッサーのオイルミストは、量的にも多く、
また微細なものも多いので気体分離膜の性能低下の主要
因ともなフている。In particular, the amount of oil mist from the compressor is large.
In addition, since many of the particles are fine, they are a major factor in the deterioration of the performance of gas separation membranes.
すなわち、気体分離膜を用いて気体混合物を分離するプ
ロセスは年単位の長期間にわたり使用されることが多い
。しかし、長期間にわたり使用した場合、上記のダスト
およびミストが膜表面に付着するために、分離対象とな
る気体の透過速度および分離係数等の該気体分離膜固有
の気体分離性能が見掛上低下するという現象が生じる。That is, the process of separating gas mixtures using gas separation membranes is often used for long periods of time, on the order of years. However, when used for a long period of time, the above-mentioned dust and mist adhere to the membrane surface, resulting in an apparent decrease in the gas separation performance specific to the gas separation membrane, such as the permeation rate and separation coefficient of the gas to be separated. This phenomenon occurs.
特に二酸化炭素分離を目的とする芳香族ポリイミド製気
体分離膜では、上記のダストおよびミストが付着した場
合に致命的な影響を受けることが少なくない。In particular, aromatic polyimide gas separation membranes intended for carbon dioxide separation are often fatally affected by the above-mentioned dust and mist.
気体分離膜の分離性能の低下が顕著になれば、気体分離
膜を交換しなければならないが、気体分離膜を交換する
ために分離プロセスを停止することは工業的に非常に不
利である。If the separation performance of the gas separation membrane becomes noticeably degraded, the gas separation membrane must be replaced, but it is industrially very disadvantageous to stop the separation process to replace the gas separation membrane.
［発明の目的］
本発明は、気体分離膜を用いる気体分離プロセスであっ
て、気体分離膜が高い経時安定性を示すように改良され
た気体分離方法を提供することを目的とする。[Object of the Invention] An object of the present invention is to provide a gas separation process using a gas separation membrane, which is improved so that the gas separation membrane exhibits high stability over time.
［発明の要旨］
本発明は、二種以上の気体成分を含む気体混合物を気体
分離膜に接触させて、該気体分離膜により該気体混合物
中の少なくとも一種の気体成分を透過分離するごとから
なる気体分離方法において、気体分離膜に接触させる前
に、該気体混合物を平均孔径が０．５μｍ以下の多孔質
膜を通過させて、該気体混合物中の浮遊粒子を除去する
ことを特徴とする気体分離方法にある。[Summary of the Invention] The present invention comprises bringing a gas mixture containing two or more types of gas components into contact with a gas separation membrane, and permeating and separating at least one gas component in the gas mixture through the gas separation membrane. In the gas separation method, the gas mixture is passed through a porous membrane having an average pore size of 0.5 μm or less to remove suspended particles in the gas mixture before contacting the gas separation membrane. It's in the separation method.
［発明の詳細な記述］
本発明は、気体分離プロセスにおいて、分離対象の気体
混合物をフィルターを介して濾過したのち気体分離膜に
接触させるに際し、フィルターとして、平均孔径が０．
５μｍ以下、好ましくは０．０５μｍ以上で０．３μｍ
以下の多孔質膜を使用することを特徴とする。[Detailed Description of the Invention] The present invention provides a gas separation process in which a gas mixture to be separated is filtered through a filter and then brought into contact with a gas separation membrane.
5μm or less, preferably 0.05μm or more and 0.3μm
It is characterized by using the following porous membrane.
以下に本発明の気体分離方法について必要に応じて図を
参照しながら詳しく説明する。The gas separation method of the present invention will be explained in detail below with reference to the figures as necessary.
分離の対象となる気体混合物は、第１図のコンプレッサ
ー２で加圧ざわたのち、第１図の導管１により多孔質膜
６に送られる。The gas mixture to be separated is compressed by the compressor 2 shown in FIG. 1, and then sent to the porous membrane 6 through the conduit 1 shown in FIG.
本発明で使用する多孔質膜の平均孔径は、ダストおよび
ミスト除去の目的からは小さいことが望ましく、０．５
μｍ以下、好ましくは０．３μｍ以下である。他方、圧
力損失の面からは０．０５μｍ以上であることが望まし
い。The average pore diameter of the porous membrane used in the present invention is preferably small for the purpose of removing dust and mist, and is 0.5
The thickness is .mu.m or less, preferably 0.3 .mu.m or less. On the other hand, from the viewpoint of pressure loss, it is desirable that the thickness be 0.05 μm or more.
本発明で使用できる多孔質膜としては上記の平均孔径を
有するものであればよく、特に限定はしない。好ましい
多孔質膜の材料としては、ポリイミド、ポリスルホン、
ポリエーテルスルホン、ポリエチレン、ポリプロピレン
、セラミックおよびガラス等を挙げることができる。The porous membrane that can be used in the present invention is not particularly limited as long as it has the above average pore diameter. Preferred porous membrane materials include polyimide, polysulfone,
Mention may be made of polyethersulfone, polyethylene, polypropylene, ceramic and glass.
多孔質膜６を介して濾過された気体混合物は、第１図の
導管３により気体分離膜７に接触させられ、その二次側
導管５に分離された気体を得ることができる。The gas mixture filtered through the porous membrane 6 is brought into contact with the gas separation membrane 7 through the conduit 3 of FIG. 1, and the separated gas can be obtained in the secondary conduit 5 thereof.
気体分離膜は、ポリアミド、セルロース、酢酸セルロー
スおよびポリイミド等からなる膜を用いることができる
が、本発明は芳香族ポリイミド製気体分離膜に適用した
場合に特に有用である。さらに、二酸化炭素分離を目的
とする芳香族ポリイミド製気体分離膜に適用した場合、
特に有用である。As the gas separation membrane, membranes made of polyamide, cellulose, cellulose acetate, polyimide, etc. can be used, but the present invention is particularly useful when applied to a gas separation membrane made of aromatic polyimide. Furthermore, when applied to aromatic polyimide gas separation membranes for the purpose of carbon dioxide separation,
Particularly useful.
芳香族ポリイミド製気体分離膜の形成材料である芳香族
ポリイミドの芳香族テトラカルボン酸骨格としては、３
．３’ 、４．４’ −ベンゾフェノンテトラカルボン
酸、２，３．３’ 、４°−ベンゾフェノンテトラカル
ボン酸、ピロメリット酸、３．３°、４．４’ −ビフ
ェニルテトラカルボン酸および２，３．３’ 、４’−
ビフェニルテトラカルボン酸、そしてこれらの芳香族テ
トラカルボン酸の酸二無水物、エステル、塩などから誘
導されるカルボン酸骨格を挙げることができる。これら
のうち３．３’ 、４．４’−ビフェニルテトラカルボ
ン酸の酸二無水物と２．３．３’ 、４’ −ビフェニ
ルテトラカルボン酸の酸二無水物などにより代表される
ビフェニルテトラカルボン酸二無水物から誘導された酸
骨格を主酸骨格とする芳香族ポリイミド製気体分離膜を
使用した場合に本発明は特に有用である。The aromatic tetracarboxylic acid skeleton of aromatic polyimide, which is the material for forming the aromatic polyimide gas separation membrane, is 3.
．． 3',4.4'-benzophenonetetracarboxylic acid, 2,3.3',4°-benzophenonetetracarboxylic acid, pyromellitic acid, 3.3°,4.4'-biphenyltetracarboxylic acid and 2,3 .3', 4'-
Examples include carboxylic acid skeletons derived from biphenyltetracarboxylic acid, and acid dianhydrides, esters, and salts of these aromatic tetracarboxylic acids. Among these, biphenyltetracarboxylic acids represented by the acid dianhydride of 3.3', 4.4'-biphenyltetracarboxylic acid and the acid dianhydride of 2.3.3', 4'-biphenyltetracarboxylic acid, etc. The present invention is particularly useful when using an aromatic polyimide gas separation membrane whose main acid skeleton is an acid skeleton derived from an acid dianhydride.
芳香族ポリイミドの芳香族ジアミン骨格としては、ｐ−
フェニレンジアミン、ｍ−フェニレンジアミン、２．４
−ジアミノトルエン、４．４’ −ジアミノジフェニル
エーテル、４，４°−ジアミノジフェニルメタン、ｏ−
トリジン、１．４−ビス（４−アミノフェノキシ）ベン
ゼン、０−トリジンスルホン、ビス（アミノフェノキシ
−フェニル）メタンおよびビス（アミノフェノキシ−フ
ェニル）スルホンなどを挙げることができる。The aromatic diamine skeleton of aromatic polyimide is p-
phenylenediamine, m-phenylenediamine, 2.4
-diaminotoluene, 4,4'-diaminodiphenyl ether, 4,4°-diaminodiphenylmethane, o-
Mention may be made of tolidine, 1,4-bis(4-aminophenoxy)benzene, 0-tolidinesulfone, bis(aminophenoxy-phenyl)methane and bis(aminophenoxy-phenyl)sulfone.
例えば、この発明で使用する芳香族ポリイミド製気体分
離膜の製造方法としては、前述の芳香族ジアミン（他の
芳香族ジアミンを含有していてもよい）からなる芳香族
ジアミン成分と前述のビフェニルテトラカルボン酸成分
とを略等モル、フェノール系化合物の有機溶媒中約１４
０℃以上の温度で一段階で重合およびイミド化して芳香
族ポリイミドを生成し、その芳香族ポリイミド溶液（濃
度；約３〜３０重量％）をドープ液として使用して約３
０〜１５０℃の温度の基材上に塗布または流延あるいは
中空糸膜状に押出してドープ液の薄膜（平膜または中空
糸）を形成し、次いでその薄膜を凝固液に浸漬して凝固
膜を形成しその凝固膜から溶媒、凝固液などを洗浄、除
去し、最後に熱処理して芳香族ポリイミド製の非対称性
気体分離膜を形成する製膜方法を挙げることができる。For example, as a method for manufacturing the aromatic polyimide gas separation membrane used in the present invention, an aromatic diamine component consisting of the above-mentioned aromatic diamine (which may contain other aromatic diamines) and the above-mentioned biphenyl tetra Approximately equal moles of carboxylic acid component, approximately 14 moles in the organic solvent of the phenolic compound.
Aromatic polyimide is produced by polymerization and imidization in one step at a temperature of 0°C or higher, and the aromatic polyimide solution (concentration: about 3 to 30% by weight) is used as a dope solution to produce about 3.
A thin film (flat film or hollow fiber) of the dope solution is formed by coating, casting, or extruding into a hollow fiber film on a substrate at a temperature of 0 to 150°C, and then the thin film is immersed in a coagulating liquid to form a coagulating film. A method for forming an asymmetric gas separation membrane made of aromatic polyimide can be mentioned.
該芳香族ポリイミド製気体分離膜は、モジュールに充填
した場合の有効膜面積が大きい中空糸膜が好ましいが、
スパイラル膜、平膜でも使用することができる。The aromatic polyimide gas separation membrane is preferably a hollow fiber membrane that has a large effective membrane area when packed in a module.
Spiral membranes and flat membranes can also be used.
［発明の効果］
本発明は、気体分離プロセスにおいて気体分離膜に顕著
な悪影響を及ぼすことが判明した気体混合物中の、微細
な浮遊粒子を、平均孔径が０．５μｍ以下の多孔質膜に
より濾別除去−したのち、この気体混合物を気体分離膜
に接触させるので、該気体分離プロセスを年単位以上の
長期間にわたって安定して運転することができる。[Effects of the Invention] The present invention is capable of filtering fine suspended particles in a gas mixture, which has been found to have a significant adverse effect on gas separation membranes in gas separation processes, through a porous membrane with an average pore size of 0.5 μm or less. After separate removal, this gas mixture is brought into contact with a gas separation membrane, so that the gas separation process can be operated stably over a long period of time, on the order of years or more.
次に本発明の実施例および比較例を示す。Next, Examples and Comparative Examples of the present invention will be shown.
［実施例１］
第１図は、本発明の気体分離方法を二酸化炭素分離プロ
セスに適用した例の概略をフローシートとして示したも
のである。[Example 1] FIG. 1 is a flow sheet showing an outline of an example in which the gas separation method of the present invention is applied to a carbon dioxide separation process.
第１図の気体分離膜７には、−二酸化炭素を分離対象と
する芳香族ポリイミド製中空糸膜を有効膜面積３２ｃｎ
？のモジュールとして使用した。The gas separation membrane 7 in FIG.
? It was used as a module.
該気体分離膜の初期性能をみるため、多孔質膜を介する
ことなく気体分離膜７に直接、二酸化炭素４０％、メタ
ン６０％の気体混合物を５０℃、圧力１０ ｋ ｇ ／
ｃ ｒｎ”で接触させ、見掛けの透過速度を測定した
ところ、二酸化炭素の透過速度（Ｐ ’ ［ｃｏ２］
’）が７ 、２ ｘ １０−’ｃｒｒ？（ＳＴＰ）／Ｃ
ゴ争秒・ｃｍＨｇであった。In order to check the initial performance of the gas separation membrane, a gas mixture of 40% carbon dioxide and 60% methane was directly applied to the gas separation membrane 7 at 50° C. and a pressure of 10 kg/min without going through a porous membrane.
When the apparent permeation rate was measured, the permeation rate of carbon dioxide (P' [co2]
') is 7, 2 x 10 - 'crr? (STP)/C
The temperature was 2.cmHg.
次に、第１図の多孔質膜６に平均孔径０．２μｍ、膜面
積１ゴのポリプロピレン製多孔質膜を使用し該多孔質膜
を介して、コンプレッサー２で加圧した空気を５０℃、
速度２ＩＬ／分で３８時間、気体分離膜７に接触させた
。Next, a polypropylene porous membrane with an average pore diameter of 0.2 μm and a membrane area of 1 mm was used as the porous membrane 6 shown in FIG.
The gas separation membrane 7 was contacted at a rate of 2 IL/min for 38 hours.
その後、前述と同様にして二酸化炭素の見掛けの透過速
度を測定し、３８時間後の二酸化炭素透過速度の保持率
を算出した。結果を第１表に示す。Thereafter, the apparent permeation rate of carbon dioxide was measured in the same manner as described above, and the retention rate of carbon dioxide permeation rate after 38 hours was calculated. The results are shown in Table 1.
［比較例１］
多孔質膜６に平均孔径２μｍ、膜面積１ゴのポリプロピ
レン製多孔質膜を使用し該多孔質膜を介してコンプレッ
サー空気を流通した外は、実施例１と同様に行なった。[Comparative Example 1] The same procedure as in Example 1 was carried out, except that a polypropylene porous membrane with an average pore diameter of 2 μm and a membrane area of 1 μm was used as the porous membrane 6, and compressed air was circulated through the porous membrane. .
結果を第１表に示す。The results are shown in Table 1.
第１表
Ｐ ’ ［ＣＯ２］ ： ｃ ｍ” （ＳＴＰ）／ ｃ
ｆｆｆｔ・秒−ｃｍＨｇ［実施例２］
コンプレッサー空気を室温で６２時間流通した外は、実
施例１と同様に行なった。結果を第２表に示す。Table 1 P' [CO2]: cm" (STP)/c
ffft·sec-cmHg [Example 2] The same procedure as in Example 1 was conducted except that compressed air was circulated at room temperature for 62 hours. The results are shown in Table 2.
［比較例２］
コンプレッサー空気を室温で６２時間流通した外は、比
較例１と同様に行なった。結果を第２表に示す。[Comparative Example 2] The same procedure as Comparative Example 1 was conducted except that compressed air was circulated at room temperature for 62 hours. The results are shown in Table 2.
第２表
Ｐ ’ ［ＣＯ□］ ： ｃ ｒｎ” （ＳＴＰ）／
ｃ ｒｒｆ−秒−ｃｍＨｇTable 2 P' [CO□] : crn” (STP)/
c rrf-sec-cmHg
第１図は、本発明を二酸化炭素分離プロセスに適用した
例の概略をフローシートとして示したものである。
１：分離対象気体混合物導管、２：コンプレッサー、３
：濾過気体導管、４：気体分離膜の一次・側導管、５：
気体分離膜の二次側導管、６：多孔質膜、７：気体分離
膜FIG. 1 is a flow sheet showing an outline of an example in which the present invention is applied to a carbon dioxide separation process. 1: Gas mixture conduit to be separated, 2: Compressor, 3
: Filtered gas conduit, 4: Primary/side conduit of gas separation membrane, 5:
Secondary side conduit of gas separation membrane, 6: Porous membrane, 7: Gas separation membrane
Claims (1)
に接触させて、該気体分離膜により該気体混合物中の少
なくとも一種の気体成分を透過分離するごとからなる気
体分離方法において、気体分離膜に接触させる前に、該
気体混合物を平均孔径が０．５μｍ以下の多孔質膜を通
過させて、該気体混合物中の浮遊粒子を除去することを
特徴とする気体分離方法。 ２。多孔質膜の平均孔径が、０．０５μｍ以上かつ０．
３μｍ以下であることを特徴とする特許請求の範囲第１
項記載の気体分離方法。 ３。多孔質膜が、ポリイミド、ポリスルホン、ポリエー
テルスルホン、ポリエチレン、ポリプロピレン、セラミ
ックおよびガラスからなる群より選ばれた材料から形成
されたものであることを特徴とする特許請求の範囲第１
項記載の気体分離方法。 ４。気体分離膜が、芳香族ポリイミド製気体分離膜であ
ることを特徴とする特許請求の範囲第１項記載の気体分
離方法。 ５。気体分離膜が、二酸化炭素分離用気体分離膜である
ことを特徴とする特許請求の範囲第１項記載の気体分離
方法。[Claims] 1. A gas separation method comprising bringing a gas mixture containing two or more gas components into contact with a gas separation membrane, and permeating and separating at least one gas component in the gas mixture through the gas separation membrane. A method for separating a gas, which comprises passing the gas mixture through a porous membrane having an average pore size of 0.5 μm or less to remove suspended particles in the gas mixture before contacting the gas mixture. 2. The average pore diameter of the porous membrane is 0.05 μm or more and 0.05 μm or more.
Claim 1 characterized in that it is 3 μm or less
Gas separation method described in section. 3. Claim 1, characterized in that the porous membrane is formed from a material selected from the group consisting of polyimide, polysulfone, polyethersulfone, polyethylene, polypropylene, ceramic, and glass.
Gas separation method described in section. 4. 2. The gas separation method according to claim 1, wherein the gas separation membrane is an aromatic polyimide gas separation membrane. 5. 2. The gas separation method according to claim 1, wherein the gas separation membrane is a gas separation membrane for carbon dioxide separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62334268A JPH01176420A (en) | 1987-12-28 | 1987-12-28 | Separation of gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62334268A JPH01176420A (en) | 1987-12-28 | 1987-12-28 | Separation of gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01176420A true JPH01176420A (en) | 1989-07-12 |
Family
ID=18275441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62334268A Pending JPH01176420A (en) | 1987-12-28 | 1987-12-28 | Separation of gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01176420A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008088190A (en) * | 1997-05-02 | 2008-04-17 | E I Du Pont De Nemours & Co | Separation of co2 from unsaturated fluorinated compound by semipermeable membrane |
| JP2008115191A (en) * | 1997-05-02 | 2008-05-22 | E I Du Pont De Nemours & Co | Co2 removable from fluorocarbon by semipermeable membrane |
| JP2011183370A (en) * | 2010-02-12 | 2011-09-22 | Ube Industries Ltd | Polyimide gas separation membrane and gas separation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6283021A (en) * | 1985-10-07 | 1987-04-16 | Matsushita Electric Ind Co Ltd | Oxygen-enriching unit |
| JPS62279825A (en) * | 1986-05-27 | 1987-12-04 | Nippon Kokan Kk <Nkk> | Method of recovering hydrocarbon vapor from mixed gas |
-
1987
- 1987-12-28 JP JP62334268A patent/JPH01176420A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6283021A (en) * | 1985-10-07 | 1987-04-16 | Matsushita Electric Ind Co Ltd | Oxygen-enriching unit |
| JPS62279825A (en) * | 1986-05-27 | 1987-12-04 | Nippon Kokan Kk <Nkk> | Method of recovering hydrocarbon vapor from mixed gas |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008088190A (en) * | 1997-05-02 | 2008-04-17 | E I Du Pont De Nemours & Co | Separation of co2 from unsaturated fluorinated compound by semipermeable membrane |
| JP2008115191A (en) * | 1997-05-02 | 2008-05-22 | E I Du Pont De Nemours & Co | Co2 removable from fluorocarbon by semipermeable membrane |
| JP2011183370A (en) * | 2010-02-12 | 2011-09-22 | Ube Industries Ltd | Polyimide gas separation membrane and gas separation method |
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