JP2000140558A - Method and device for separating/recovering gas for electrical insulation - Google Patents

Method and device for separating/recovering gas for electrical insulation

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Publication number
JP2000140558A
JP2000140558A JP10321715A JP32171598A JP2000140558A JP 2000140558 A JP2000140558 A JP 2000140558A JP 10321715 A JP10321715 A JP 10321715A JP 32171598 A JP32171598 A JP 32171598A JP 2000140558 A JP2000140558 A JP 2000140558A
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JP
Japan
Prior art keywords
gas
membrane
separation
hollow fiber
recovered
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.)
Granted
Application number
JP10321715A
Other languages
Japanese (ja)
Other versions
JP3890783B2 (en
Inventor
Osamu Yamamoto
修 山本
Tadashi Takuma
董 宅間
Masayuki Kiuchi
政行 木内
Naoki Takada
直己 高田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Ube Industries Ltd
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Filing date
Publication date
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Priority to JP32171598A priority Critical patent/JP3890783B2/en
Publication of JP2000140558A publication Critical patent/JP2000140558A/en
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Publication of JP3890783B2 publication Critical patent/JP3890783B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

PROBLEM TO BE SOLVED: To enable SF6 to be efficiently separated/recovered and thereby reduce the emission amount of the SF6 into an atmosphere by supplying a mixed gas made up of an electrically insulating gas containing a specific amount of the SF6 to a gas separating membrane to establish their mutual contact and recovering a gas containing the SF6 of a specific purity from the impermeable side of the membrane. SOLUTION: When SF6 is efficiently recovered by separation, a mixed gas consisting of the SF6 and another gas is supplied from the mixed gas supply aperture 3 of a gas separation device 1 and is fluidized to an impermeable gas discharge aperture 4 side through the inside of a hollow fiber 2. The gas permeating through a separation membrane is discharged from a permeable gas discharge aperture 5, while the gas not permeating through the separation membrane is discharged from an impermeable gas discharge aperture 4 and thus the SF6 whose permeation velocity is low is recovered by separation. In this case, the concentration of the SF6 in the mixed gas is set to be 6-60 vol.% and the SF6 amount to be discharged from the membrane permeation side is set to be 3 vol.% or less of the mixed gas before separation. Besides, the mixed gas is treated so that the purity of the SF6 in the SF6-rich gas to be recovered to the membrane impermeation side is equivalent to 80 vol.% or more.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】電気絶縁系に使用されるハロ
ゲン化合物を含む混合ガスからハロゲン化合物を分離回
収する方法および装置に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for separating and recovering a halogen compound from a mixed gas containing a halogen compound used in an electric insulation system.

【0002】[0002]

【従来の技術】ガス絶縁開閉装置、ガス遮断機、ガス絶
縁変圧器、管路気中送電等のガス絶縁電気機器の電気絶
縁ガスとして、SF6(六フッ化イオウ)ガス、フロン
ガス、四塩化炭素ガスなどを中心とするハロゲン化合物
が用いられている。特に、SF 6は気圧を上げることに
より優れた絶縁耐力を示し、さらに、液化温度がフロン
12や四塩化炭素よりも低いため、低温でも加圧して使
用できることから電気絶縁ガスとして多用されている。
しかし、最近特に地球規模で課題となっている地球温暖
化ガスとしてその対策が迫られている。その一つの方策
として、SF6の使用量を削減するため、SF6とそれ以
外の電気絶縁性ガスからなる混合ガスをガス絶縁電気機
器に使用する試みがなされている。
2. Description of the Related Art Gas insulated switchgears, gas circuit breakers, gas shutoffs
Electrical insulation of gas-insulated electrical equipment such as edge transformers and pipeline air transmission
SF as an edge gas6(Sulfur hexafluoride) gas, Freon
Halogen compounds such as gas and carbon tetrachloride gas
Is used. In particular, SF 6Is to raise the air pressure
Shows better dielectric strength and has a liquefied
12 and lower than carbon tetrachloride.
Because it can be used, it is widely used as an electric insulating gas.
However, global warming, which has recently become a global issue
There is a pressing need for countermeasures as chemical gas. One measure
As SF6SF to reduce the use of6And beyond
Gas-insulated electric machine
Attempts have been made to use them in vessels.

【0003】この場合、ハロゲン化合物は他のガスから
分離され回収再利用される必要がある。そのための方法
として、従来より加圧冷却法(液化法)が検討されてき
た。
In this case, the halogen compound needs to be separated from other gases, recovered and reused. As a method therefor, a pressure cooling method (liquefaction method) has been conventionally studied.

【0004】しかしながら、加圧冷却法の場合、一般的
に極めて高い圧力及び低い温度が必要で、目的とするハ
ロゲン化合物の分離回収率を上げて回収ロスを減らそう
とすればするほど高圧及び低温が必要とされるため、現
実的にはハロゲン化合物の回収ロスは極めて大きい。例
えば、H. Hama et al., "Application problems of SF6
/N2 mixtures to gas insulated bus", 8th Internatio
nal Symposium on Gaseous Dielectrics, Virginia Bea
ch, June 22-I (1998)には、SF6が7%以下の混合ガ
スでは、3.5MPa、−50℃の低温でも液化するS
6は0%であり、10%以下のSF6の混合ガスでは、
回収は実質困難であることが開示されている。また、5
0%のSF6の混合ガスでも、3.5MPa、−10℃
では、液化率は50%に満たないことが開示されてい
る。このように、通常、加圧冷却法によるSF6の回収
ロスは50%程度と極めて大きいものである。
However, in the case of the pressurized cooling method, an extremely high pressure and a low temperature are generally required, and the higher the pressure and the lower the temperature, the more the separation and recovery of the target halogen compound is to be increased to reduce the recovery loss. Is required, and in practice, the recovery loss of the halogen compound is extremely large. For example, H. Hama et al., "Application problems of SF6
/ N2 mixtures to gas insulated bus ", 8th Internatio
nal Symposium on Gaseous Dielectrics, Virginia Bea
ch, June 22-I (1998) states that a mixed gas containing SF 6 of 7% or less liquefies even at a low temperature of 3.5 MPa and -50 ° C.
F 6 is 0%, and in a mixed gas of SF 6 of 10% or less,
Recovery is disclosed to be substantially difficult. Also, 5
3.5 MPa, -10 ° C. even with a mixed gas of 0% SF 6
Discloses that the liquefaction rate is less than 50%. As described above, normally, the recovery loss of SF 6 by the pressurized cooling method is extremely large, about 50%.

【0005】回収ロス分は大気中に放出されることにな
るため、地球温暖化対策の観点からSF6の回収ロスの
少ない効率的な分離回収方法及び装置が求められてい
る。
[0005] For recovery loss in the that will be released into the atmosphere, recovery loss less efficient separation recovery method and apparatus of SF 6 in view of global warming is demanded.

【0006】[0006]

【発明が解決しようとする課題】本発明は、ガス絶縁電
気機器などに使用される絶縁性の混合ガスから地球環境
に有害なハロゲン化合物ガス、その中でも特に今後の使
用量が増大すると期待されるSF6を効率的に分離回収
し、大気中への放出量を劇的に減少させる方法とその装
置を提供することを目的とする。
SUMMARY OF THE INVENTION The present invention is expected to increase the amount of halogen compound gas harmful to the global environment, especially from the use of insulating mixed gas used for gas-insulated electric equipment and the like. It is an object of the present invention to provide a method and an apparatus for efficiently separating and recovering SF 6 and dramatically reducing the amount of SF 6 released into the atmosphere.

【0007】[0007]

【課題を解決するための手段】本発明は、3〜60体積
%のSF6とその他の少なくとも1種類以上の電気絶縁
性ガスからなる混合ガスをガス分離膜に供給して接触さ
せ、膜の非透過側から、純度80体積%以上のSF6
含んだガスをSF6の回収率80%以上で回収し、ガス
分離膜の透過側に排出するSF6ガス量が全供給混合ガ
ス量の3体積%以下であることを特徴とする電気絶縁用
ガスの分離回収方法に関する。
The present invention SUMMARY OF] is a mixed gas consisting of other at least one or more electrically insulating gas SF 6 of 3 to 60% by volume is contacted with feed to the gas separation membrane, the membrane From the non-permeate side, a gas containing SF 6 with a purity of 80% by volume or more is recovered at a recovery rate of SF 6 of 80% or more, and the amount of SF 6 gas discharged to the permeate side of the gas separation membrane is equal to the total mixed gas amount. The present invention relates to a method for separating and recovering a gas for electric insulation, which is not more than 3% by volume.

【0008】また、本発明は、ガス分離膜が芳香族ポリ
イミド分離膜であることを特徴とする上記の電気絶縁用
ガスの分離回収方法に関する。
[0008] The present invention also relates to the above-mentioned method for separating and recovering a gas for electrical insulation, wherein the gas separation membrane is an aromatic polyimide separation membrane.

【0009】また、本発明は、上記SF6以外の電気絶
縁性ガスが、窒素ガス、炭酸ガス、ヘリウムガス、水素
ガス、二酸化硫黄ガス、空気のうち少なくとも1つであ
ることを特徴とする上記の電気絶縁用ガスの分離回収方
法に関する。
Further, the present invention, the electrically insulating gas other than the SF 6 is nitrogen gas, carbon dioxide gas, helium gas, hydrogen gas, sulfur dioxide gas, characterized in that at least one of the air The present invention relates to a method for separating and recovering an electric insulating gas.

【0010】さらに、本発明は、多数の中空糸の形状を
した分離膜が密封容器内に内蔵されており、中空糸内部
に通じるガス供給口と非透過ガス排出口、さらに、中空
糸の外側に少なくとも1つの透過ガス排出口を有するガ
ス分離装置であり、SF6ガスとその他の少なくとも1
種類以上の電気絶縁性ガスからなる混合ガスをガス分離
装置のガス供給口から中空糸の内側に導入し、SF6
ス量が供給混合ガスの3体積%以下である電気絶縁性ガ
スを透過ガス排出口から排出し、純度80体積%以上の
SF6を含んだガスを非透過ガス排出口より回収するこ
とを特徴とする電気絶縁用ガスの分離回収装置に関す
る。
[0010] Further, the present invention provides a separation membrane in the form of a large number of hollow fibers, which is contained in a sealed container, and has a gas supply port and a non-permeate gas outlet communicating with the inside of the hollow fibers, and further, an outside of the hollow fibers. A gas separation device having at least one permeate gas outlet, wherein SF 6 gas and at least one other
A mixed gas composed of more than one kind of electrically insulating gas is introduced into the inside of the hollow fiber from the gas supply port of the gas separator, and the electrically insulating gas whose SF 6 gas amount is 3% by volume or less of the supplied mixed gas is permeated gas. The present invention relates to a device for separating and recovering a gas for electrical insulation, wherein a gas discharged from an outlet and containing SF 6 having a purity of 80% by volume or more is recovered from a non-permeate gas outlet.

【0011】[0011]

【発明の実施の形態】本発明は、ガス絶縁電気機器の電
気絶縁用ガスとして使用されるSF6とその他の少なく
とも1種類以上の電気絶縁性ガスからなる混合ガスをガ
ス分離膜に接触させ、SF6以外の電気絶縁性ガスに富
むガスを膜の透過側に排出し、膜の非透過側からSF6
に富むガスを分離回収する方法である。
BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a method of contacting a gas mixture comprising SF 6 used as an electric insulating gas of gas-insulated electric equipment and at least one other kind of electric insulating gas with a gas separation membrane, A gas rich in an electrically insulating gas other than SF 6 is discharged to the permeation side of the membrane, and SF 6 is discharged from the non-permeation side of the membrane.
This is a method for separating and recovering a gas rich in water.

【0012】SF6ガスは、無色無臭で無毒の不活性ガ
スであり、気圧を上げることにより優れた絶縁耐力を示
し、かつ、液化温度も低く、低温でも加圧して使用でき
ることから、電気絶縁ガスとして好ましく利用される。
The SF 6 gas is a colorless, odorless and non-toxic inert gas, exhibits excellent dielectric strength by increasing the pressure, has a low liquefaction temperature, and can be used under pressure even at a low temperature. It is preferably used as

【0013】電気絶縁用のSF6を含む混合ガスは、現
在その可能性が検討されており、混合ガスとして使用さ
れるSF6以外のガスの種類としては、窒素ガス、炭酸
ガス、ヘリウムガス、水素ガス、二酸化硫黄ガス、空気
等を挙げることができる。SF6とこれらのガスの組み
合わせは、絶縁耐力が大きく、膜に対する透過速度比が
大きく、本願発明の分離回収に好ましい組み合わせであ
る。特に、窒素ガスは、毒性が無く、入手が容易である
点で、好ましく使用される。混合ガスとしては、上記の
電気絶縁用のガスに限定するものではなく、他の電気絶
縁性のガスが含まれていてもよい。
The possibility of using a mixed gas containing SF 6 for electrical insulation is currently being studied, and types of gases other than SF 6 used as the mixed gas include nitrogen gas, carbon dioxide gas, helium gas, and the like. Examples include hydrogen gas, sulfur dioxide gas, and air. The combination of SF 6 and these gases has a large dielectric strength and a large transmission speed ratio to the membrane, and is a preferable combination for the separation and recovery of the present invention. In particular, nitrogen gas is preferably used because it has no toxicity and is easily available. The mixed gas is not limited to the above-mentioned gas for electric insulation, and may include other electric insulating gas.

【0014】ガス分離膜に供給される電気絶縁用混合ガ
スのSF6の濃度は、3〜60体積%であり、好ましく
は5〜50体積%である。低い濃度では、電気絶縁性が
低下し、高い濃度では、SF6の使用量が増え、また、
SF6のロスが増えるためである。SF6の一部がフロン
ガス、四塩化炭素などのSF6以外の電気絶縁性ハロゲ
ン化合物で50%まで置き換えられたガス組成でもよ
い。
The concentration of SF 6 in the electric insulating mixed gas supplied to the gas separation membrane is 3 to 60% by volume, preferably 5 to 50% by volume. At lower concentrations, the electrical insulation is reduced, at higher concentrations the use of SF 6 increases,
This is because the loss of SF 6 increases. Some of the SF 6 is chlorofluorocarbon, four with an electrically insulating halogen compounds other than SF 6, such as carbon tetrachloride may be a gas composition was replaced by 50%.

【0015】膜透過側に排出されるSF6量は、大気汚
染の問題に直結しており、少ないほどよいが、分離前の
混合ガスの3体積%以下が好ましく、さらに1体積%以
下がより好ましい。
The amount of SF 6 discharged to the permeation side of the membrane is directly related to the problem of air pollution, and the smaller the better, the better. However, the volume of SF 6 is preferably 3% by volume or less of the mixed gas before separation, and more preferably 1% by volume or less. preferable.

【0016】また、非透過側に回収されるSF6に富ん
だガスのSF6の純度は、80体積%以上であることが
好ましい。SF6の純度が高いほどガス状態で保存する
ときの貯蔵タンクが小さくて済むばかりでなく、SF6
の純度が高いほど液化し易いため、液状態で保管する時
も有利である。
Further, the purity of SF 6-rich gas SF 6 recovered on the non-permeate side is preferably 80 vol% or more. Not only it requires only a small storage tank when stored at higher gas state high purity SF 6, SF 6
The higher the purity, the easier it is to liquefy, which is advantageous when stored in a liquid state.

【0017】ガス分離膜としては、SF6以外の電気絶
縁性ガスのいずれの透過速度もSF6の透過速度よりも
大きい膜が使用される。例えば、ポリアミド、セルロー
ス、酢酸セルロース、ポリイミド膜等が挙げられる。中
でも、SF6以外のガス成分とSF6の透過速度比が大き
く、さらに、モジュール化が容易で単位容積あたりの膜
面積を大きくでき、かつ耐熱性、耐久性に優れた芳香族
ポリイミド製ガス分離膜が好ましい。芳香族ポリイミド
膜は、電気絶縁ガス中に存在すると絶縁耐力を低下させ
る原因となる水蒸気の透過速度も極めて大きいため、水
蒸気は混合ガス中の透過速度の大きいガス中に随伴して
行くことによりSF6とは分離される。このため、電気
絶縁ガスに使用されるSF6の分離回収には特に好まし
く使用される。芳香族ポリイミド製ガス分離膜は芳香族
テトラカルボン酸骨格と芳香族ジアミン骨格とを含むも
ので公知の方法により製造することができる。
[0017] As the gas separation membrane, one of the transmission speed greater film than transmission rate of SF 6 of electrically insulating gas other than SF 6 is used. For example, polyamide, cellulose, cellulose acetate, polyimide film and the like can be mentioned. Among these, permeation rate ratio of the gas component and SF 6 except SF 6 is large, further, modularization can be increased membrane area per easy unit volume, and heat resistance, excellent in durability aromatic polyimide gas separation Membranes are preferred. Since the aromatic polyimide film has a very high water vapor transmission rate that causes a decrease in dielectric strength when present in an electric insulating gas, the water vapor accompanies the gas having a high transmission rate in the mixed gas to form a SF. 6 and separated. For this reason, it is particularly preferably used for separating and recovering SF 6 used for an electric insulating gas. The aromatic polyimide gas separation membrane contains an aromatic tetracarboxylic acid skeleton and an aromatic diamine skeleton, and can be manufactured by a known method.

【0018】芳香族テトラカルボン酸骨格の基になる酸
としては、ビフェニルテトラカルボン酸類、例えば3,
3’,4,4’−ビフェニルテトラカルボン酸やその酸
無水物、エステルなど、2,3,3’,4’−ビフェニ
ルテトラカルボン酸やその酸無水物、エステルなど;ビ
ス(ジカルボキシフェニル)プロパン類、例えば2,2
−ビス(3,4−ジカルボキシフェニル)プロパンやそ
の酸無水物、エステルなど、2,2−ビス(3,4−ジ
カルボキシフェニル)ヘキサフルオロプロパンやその酸
無水物、エステルなど;ピロメリット酸類、例えばピロ
メリット酸やその酸無水物、エステルなど;ベンゾフェ
ノンテトラカルボン類、例えば3,3’,4,4’−ベ
ンゾフェノンテトラカルボン酸やその酸無水物、エステ
ルなど、2,3,3’,4’−ベンゾフェノンテトラカ
ルボン酸やその酸無水物、エステルなど;ビス(ジカル
ボキシフェニル)スルホン類、例えばビス(3,4−ジ
カルボキシフェニル)スルホンやその酸無水物、エステ
ルなど;ビス(ジカルボキシフェニル)エーテル類、例
えばビス(3,4−ジカルボキシフェニル)エーテルや
その酸無水物、エステルなどを挙げることができる。
Examples of the acid which forms the group of the aromatic tetracarboxylic acid skeleton include biphenyltetracarboxylic acids, for example, 3,
2,3,3 ', 4'-biphenyltetracarboxylic acid, acid anhydrides, esters, etc., such as 3', 4,4'-biphenyltetracarboxylic acid and acid anhydrides and esters; bis (dicarboxyphenyl) Propanes, such as 2,2
-Bis (3,4-dicarboxyphenyl) propane and acid anhydrides and esters thereof, such as 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane and acid anhydrides and esters thereof; pyromellitic acids Benzophenone tetracarboxylic acids such as 3,3 ′, 4,4′-benzophenonetetracarboxylic acid and acid anhydrides and esters such as 2,3,3 ′, Bis (dicarboxyphenyl) sulfones, for example, bis (3,4-dicarboxyphenyl) sulfone and its acid anhydrides and esters; bis (dicarboxyphenyl) Phenyl) ethers, for example, bis (3,4-dicarboxyphenyl) ether and its anhydrides and esters And the like.

【0019】芳香族ジアミン骨格の基になるジアミンと
しては、ベンゼン環を一個及び又は二個以上有する芳香
族ジアミン化合物が使用される。具体的には、例えば、
4,4’−ジアミノジフェニルエーテル、3,4’−
ジアミノジフェニルエーテル、3,3’−ジアミノジフ
ェニルエーテル、3,3’−ジメチル−4,4’−ジア
ミノジフェニルエーテル、3,3’−ジメトキシ−4,
4’−ジアミノジフェニルエーテルなどのジフェニルエ
ーテル系化合物;4,4’−ジアミノジフェニルメタ
ン、3,3’−ジアミノジフェニルメタン、2,2’−
ジアミノジフェニルメタン、2,4’−ジアミノジフェ
ニルメタンなどのジフェニルメタン系化合物;4,4’
−ジアミノビベンジル、4,4’−ジアミノ−2,2’
−ジメチルビベンジルなどのビベンジル化合物;4,
4’−ジアミノベンゾフェノン、3,3’−ジアミノベ
ンゾフェノン、2,2’−ジアミノベンゾフェノンなど
のベンゾフェノン系化合物;2,2−ビス(3−アミノ
フェニル)プロパン、2,2−ビス〔4−(4’−アミ
ノフェノキシ)フェニル〕プロパンなどの2,2−ビス
(フェニル)プロパン系化合物;3,3’−ジメチルベ
ンチジン、3,3’−ジメトキシベンチジンなどのベン
チジン系化合物;3,3’−ジアミノジフニルスルフィ
ド、4,4’−ジアミノジフェニルスルフィド、3,
3’−ジアミノジフェニルスルホン、4,4’−ジアミ
ノジフェニルスルホンなどのジアミノジフェニルスルフ
ィド系化合物;o−、m−,p−フェニレンジアミンな
どのフェニレンジアミン系化合物;3,5−ジアミノ安
息香酸、2,4−ジアミノ安息香酸、2,3−ジアミノ
安息香酸などのジアミノ安息香酸系化合物;2,6−ジ
アミノピリジン、2,5−ジアミノピリジン、2,3−
ジアミノピリジンなどのジアミノピリジン系化合物など
を挙げることができる。これらの芳香族ジアミンは1種
類でも、また複数併用されてもよい。
As the diamine serving as the group of the aromatic diamine skeleton, an aromatic diamine compound having one and / or two or more benzene rings is used. Specifically, for example,
4,4'-diaminodiphenyl ether, 3,4'-
Diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, 3,3′-dimethoxy-4,
Diphenyl ether compounds such as 4'-diaminodiphenyl ether; 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 2,2'-
Diphenylmethane compounds such as diaminodiphenylmethane and 2,4'-diaminodiphenylmethane; 4,4 '
-Diaminobibenzyl, 4,4'-diamino-2,2 '
Bibenzyl compounds such as dimethylbibenzyl; 4,
Benzophenone compounds such as 4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 2,2'-diaminobenzophenone; 2,2-bis (3-aminophenyl) propane, 2,2-bis [4- (4 2,2-bis (phenyl) propane-based compounds such as' -aminophenoxy) phenyl] propane; benzidine-based compounds such as 3,3'-dimethylbenzidine and 3,3'-dimethoxybenzidine;3,3'- Diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,
Diaminodiphenylsulfide compounds such as 3′-diaminodiphenylsulfone and 4,4′-diaminodiphenylsulfone; phenylenediamine compounds such as o-, m- and p-phenylenediamine; 3,5-diaminobenzoic acid; Diaminobenzoic acid compounds such as 4-diaminobenzoic acid and 2,3-diaminobenzoic acid; 2,6-diaminopyridine, 2,5-diaminopyridine, 2,3-
Examples thereof include diaminopyridine-based compounds such as diaminopyridine. These aromatic diamines may be used alone or in combination of two or more.

【0020】中空糸ポリイミド分離膜は、テトラカルボ
ン酸成分とジアミン成分との略等モルを有機極性溶媒の
存在下に重合及びイミド化して得られたポリイミドが有
機極性溶媒に溶解している溶液をド−プ液として使用
し、これを中空糸形成用ノズルから押し出し中空糸状体
を形成した後、凝固液中で凝固させ、次いで凝固液を除
去して乾燥することによって製造することができる。
The hollow fiber polyimide separation membrane is prepared by dissolving a polyimide solution obtained by polymerizing and imidizing substantially equimolar amounts of a tetracarboxylic acid component and a diamine component in the presence of an organic polar solvent. It is used as a dope liquid, extruded from a hollow fiber forming nozzle to form a hollow fiber, coagulated in a coagulating liquid, then removed and dried.

【0021】中空糸ポリイミド分離膜は、例えば中空糸
を適当な長さに切断して多数(100〜100000)
束ねて形成させた中空糸膜束が、その両端の中空(孔)
が塞がらないように両端をエポキシ樹脂の如き樹脂で一
体的に固着して、モジュ−ル化し、これを少なくとも気
体混合物(原料ガス)の供給口、未透過気体の排出口及
び透過気体の排出口を有する容器に収納し、ガス分離回
収装置として用いられる。ガス混合物を分離する場合、
ガス混合物は中空糸の外側から供給して中空糸の内側
(孔側)から透過ガスを取り出す方法で行っても、また
ガス混合物を中空糸の一方の内側から供給して中空糸内
を流動通過させてもう一方の内側から排出される間に、
透過ガスを中空糸の外側に透過させる方法で行ってもよ
いが、後者の方法の方が効率がよいので好適である。
The hollow fiber polyimide separation membrane is formed, for example, by cutting a hollow fiber into an appropriate length to prepare a large number (100 to 100,000).
Hollow fiber membrane bundles formed by bundling
The two ends are integrally fixed with a resin such as an epoxy resin so as not to be blocked, and are modularized, and this is at least a gas mixture (raw material gas) supply port, a non-permeate gas discharge port, and a permeate gas discharge port. And used as a gas separation and recovery device. When separating gas mixtures,
The gas mixture is supplied from the outside of the hollow fiber and the permeated gas is taken out from the inside (hole side) of the hollow fiber. Alternatively, the gas mixture is supplied from one inside of the hollow fiber and flows through the hollow fiber. And let it drain from the other inside,
The permeation gas may be permeated to the outside of the hollow fiber, but the latter method is preferred because it is more efficient.

【0022】ガス分離装置は中空糸、スパイラル状膜、
平膜など密封容器内に収められているものであれば特に
制限はないが、単位容積あたりの膜面積が大きくできる
点では中空糸膜の使用が好ましい。
The gas separation device includes a hollow fiber, a spiral membrane,
There is no particular limitation as long as it is contained in a sealed container such as a flat membrane, but the use of a hollow fiber membrane is preferred in that the membrane area per unit volume can be increased.

【0023】本発明のガス分離装置の一実施態様を図1
に示した。ガス分離装置1は多数の中空糸2の形状をし
た分離膜が密封容器6内に内蔵されており、SF6と他
の1種類以上のガスからなる混合ガスをガス分離装置1
の混合ガス供給口3から連続的に供給し、中空糸2の内
側を非透過ガス排出口4側に流動させ、分離膜を選択的
に透過したガスは透過ガス排出口5より排出し、分離膜
を透過しなかったガスを非透過ガス排出口4より排出す
ることにより、透過速度の遅いSF6を非透過ガス排出
口4より分離回収することができる。なお、図1の樹脂
壁7は中空糸2の両端部をエラストマ系樹脂、アクリレ
ート系樹脂、エポキシ樹脂、フェノール樹脂などの適当
な熱硬化製樹脂を固化して形成された円板状の樹脂壁
で、樹脂壁内を各中空糸が貫通しており、中空糸内部の
孔が樹脂壁の外に向かって開口している。樹脂壁7は接
着剤などを使用して密封容器6の内壁に密封固着されて
いる。また分離回収効率をより高めるためにガス分離装
置1において透過ガス排出口5に真空ポンプ等を接続し
て透過ガスを減圧して回収することも有効であり、ま
た、透過ガス排出口5のうちの一方から混合ガス中に含
まれない他の種類のガスをパージガスとして供給し、透
過ガス排出口の他方から透過ガスと共に排出することも
できる。
One embodiment of the gas separation device of the present invention is shown in FIG.
It was shown to. The gas separation device 1 has a separation membrane in the form of a large number of hollow fibers 2 incorporated in a sealed container 6. The gas separation device 1 converts a mixed gas composed of SF 6 and at least one other gas into a gas.
Is continuously supplied from the mixed gas supply port 3 to flow the inside of the hollow fiber 2 to the non-permeate gas discharge port 4 side, and the gas selectively permeating the separation membrane is discharged from the permeate gas discharge port 5 and separated. By discharging the gas that has not passed through the membrane from the non-permeate gas outlet 4, SF 6 having a low permeation rate can be separated and recovered from the non-permeate gas outlet 4. The resin wall 7 shown in FIG. 1 is a disc-shaped resin wall formed by solidifying an appropriate thermosetting resin such as an elastomer resin, an acrylate resin, an epoxy resin, or a phenol resin at both ends of the hollow fiber 2. Thus, each hollow fiber penetrates through the resin wall, and a hole in the hollow fiber opens toward the outside of the resin wall. The resin wall 7 is hermetically fixed to the inner wall of the sealed container 6 using an adhesive or the like. In order to further enhance the separation and recovery efficiency, it is effective to connect a vacuum pump or the like to the permeated gas discharge port 5 in the gas separation device 1 to collect and reduce the permeated gas under reduced pressure. Alternatively, another type of gas not contained in the mixed gas may be supplied as a purge gas from one of the outlets and discharged together with the permeated gas from the other of the permeated gas outlets.

【0024】[0024]

【実施例】以下、実施例を示し本願発明を説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments.

【0025】実施例1 中空糸膜として、3,3’,4,4’−ビフェニルテト
ラカルボン酸二無水物(以下、s−BPDA)30ミリ
モル,2,2’−ビス(3,4−ジカルボキシフェニ
ル)ヘキサフルオロプロパン二無水物(以下、6FD
A)55ミリモル、ピロメット酸二無水物(以下、PM
DA)15ミリモルと、3,7−ジアミノ−2,8−ジ
メチルジフェニレンスルホン(以下、TSN)50ミリ
モル,2,2’,5,5’−テトラクロロベンジジン
(以下、TCB)50ミリモルから形成された芳香族ポ
リイミド製のものを用いた。中空糸膜の外径は、410
μm、内径は280μmであり、40℃におけるSF6
ガスの透過速度は4.8×10-7cm3/cm2・sec・c
mHg、窒素ガスの透過速度は2×10-5cm3/cm2
・sec・cmHgであった。この中空糸を用いて糸束を
形成し、その両端部をエポキシ系樹脂で密着して第1図
と同様の形式の密封容器内に内蔵してガス分離装置を製
造した。有効膜面積は60m2であった。
Example 1 As a hollow fiber membrane, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as s-BPDA) 30 mmol, 2,2′-bis (3,4-diphenyl) Carboxyphenyl) hexafluoropropane dianhydride (hereinafter 6FD
A) 55 mmol, pyrometic acid dianhydride (hereinafter referred to as PM
DA) formed from 15 mmol, 50 mmol 3,7-diamino-2,8-dimethyldiphenylene sulfone (hereinafter, TSN), and 50 mmol 2,2,2,5,5'-tetrachlorobenzidine (hereinafter, TCB). Aromatic polyimide made was used. The outer diameter of the hollow fiber membrane is 410
μm, the inner diameter is 280 μm, and SF 6 at 40 ° C.
Gas transmission rate is 4.8 × 10 -7 cm 3 / cm 2 · sec · c
mHg, nitrogen gas permeation rate is 2 × 10 −5 cm 3 / cm 2
· Sec · cmHg. A yarn bundle was formed using this hollow fiber, and both ends were adhered to each other with an epoxy resin, and the resulting bundle was housed in a sealed container of the same type as that shown in FIG. 1 to manufacture a gas separation device. The effective membrane area was 60 m 2 .

【0026】ガス分離装置のガス供給口からSF6ガス
10体積%、窒素ガス90体積%からなる混合ガスを圧
力5kg/cm2G、流量12Nm3/h、温度40℃で供
給した。透過ガスは透過ガス排出口から常圧で回収し、
非透過ガスは非透過ガス排出口から回収した。それぞれ
のガスの流量及びSF6ガス濃度を表1に示した。供給
ガス中のSF6ガスは非透過ガスとして分離回収される
が、供給ガス中のSF6ガスのうち非透過ガス排出口か
ら回収されるものをSF6回収率として表1に同時に示
した。また、透過ガス排出口から排出されたSF6ガス
の全供給混合ガスに対する割合を全混合ガスに対するS
6ロスとして同様に表1に示した。
A mixed gas comprising 10% by volume of SF 6 gas and 90% by volume of nitrogen gas was supplied from the gas supply port of the gas separator at a pressure of 5 kg / cm 2 G, a flow rate of 12 Nm 3 / h and a temperature of 40 ° C. The permeated gas is collected from the permeated gas outlet at normal pressure,
The non-permeate gas was recovered from the non-permeate gas outlet. Table 1 shows the flow rate of each gas and the SF 6 gas concentration. The SF 6 gas in the supply gas is separated and recovered as a non-permeate gas. Of the SF 6 gas in the supply gas, the one recovered from the non-permeate gas outlet is shown in Table 1 at the same time as the SF 6 recovery rate. In addition, the ratio of SF 6 gas discharged from the permeated gas outlet to the total supply mixed gas is expressed by S
It is shown Similarly in Table 1 as F 6 losses.

【0027】実施例2 供給する混合ガスの圧力を6kg/cm2G、温度120
℃とし、有効膜面積を28m2とした以外は実施例1と
同様にして行なった。温度120℃におけるSF6ガス
の透過速度は5.5×10-7cm3/cm2・sec・cmH
g、窒素ガスの透過速度は4.5×10-5cm3/cm2
・sec・cmHgであった。結果を表1に示した。
Example 2 The pressure of the supplied mixed gas was 6 kg / cm 2 G and the temperature was 120.
C. and the same procedure as in Example 1 except that the effective film area was 28 m 2 . The permeation rate of SF 6 gas at a temperature of 120 ° C. is 5.5 × 10 −7 cm 3 / cm 2 · sec · cmH
g, the permeation rate of nitrogen gas is 4.5 × 10 −5 cm 3 / cm 2
· Sec · cmHg. The results are shown in Table 1.

【0028】実施例3 供給する混合ガスをSF6ガス10体積%、炭酸ガスを
90体積%とし、圧力を6kg/cm2Gとし、有効膜面
積を3.7m2とした以外は実施例1と同様にして行な
った。温度40℃における炭酸ガスの透過速度は5×1
-4cm3/cm 2・sec・cmHgであった。結果を表1
に示した。
Example 3 The supplied mixed gas was SF6Gas 10% by volume, carbon dioxide
90 volume%, pressure 6kg / cmTwoG, effective film surface
3.7m productTwoThe procedure was the same as in Example 1 except that
Was. The permeation rate of carbon dioxide gas at a temperature of 40 ° C. is 5 × 1
0-FourcmThree/ cm Two· Sec · cmHg. Table 1 shows the results
It was shown to.

【0029】実施例4 供給する混合ガスをSF6ガス10体積%、ヘリウムガ
ス90体積%とし、圧力を6kg/cm2Gとし、有効膜
面積を2.6m2とした以外は、実施例1と同様にして
行なった。温度40℃におけるヘリウムガスの透過速度
は1×10-3cm3/cm2・sec・cmHgであった。結
果を表1に示した。
Example 4 Example 1 was repeated except that the supplied mixed gas was 10% by volume of SF 6 gas, 90% by volume of helium gas, the pressure was 6 kg / cm 2 G, and the effective film area was 2.6 m 2. Was performed in the same manner as described above. The helium gas permeation rate at a temperature of 40 ° C. was 1 × 10 −3 cm 3 / cm 2 · sec · cmHg. The results are shown in Table 1.

【0030】[0030]

【表1】 [Table 1]

【0031】[0031]

【発明の効果】本願発明により、ガス絶縁電気機器に使
用されるSF6とその他の電気絶縁性ガスの混合物から
なる絶縁用ガスから、高濃度のSF6を回収ロスが少な
く効率的にかつ容易に分離回収することができる。
Industrial Applicability According to the present invention, high-concentration SF 6 can be efficiently and easily recovered from an insulating gas composed of a mixture of SF 6 and other electric insulating gas used for gas-insulated electric equipment with a small recovery loss. Can be separated and recovered.

【図面の簡単な説明】[Brief description of the drawings]

【図1】本願発明のハロゲン化合物ガスを分離回収する
装置の1例を示す断面図である。
FIG. 1 is a sectional view showing an example of an apparatus for separating and recovering a halogen compound gas according to the present invention.

【符号の説明】[Explanation of symbols]

1;ガス分離装置 2;中空糸 3;原料ガス供給口(混合ガス供給口) 4;非透過ガス排出口 5;透過ガス排出口 6;密封容器 7;樹脂壁 DESCRIPTION OF SYMBOLS 1: Gas separation apparatus 2: Hollow fiber 3: Raw material gas supply port (mixed gas supply port) 4: Non-permeate gas discharge port 5: Permeate gas discharge port 6: Sealed container 7: Resin wall

───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4D006 GA41 HA02 HA41 HA61 KE03Q KE03R MA01 MA33 MB04 MC58 NA10 NA12 NA64 NA75 PA04 PB20 PB63 PB64 PB66 PB70  ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D006 GA41 HA02 HA41 HA61 KE03Q KE03R MA01 MA33 MB04 MC58 NA10 NA12 NA64 NA75 PA04 PB20 PB63 PB64 PB66 PB70

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】3〜60体積%のSF6とその他の少なく
とも1種類以上の電気絶縁性ガスからなる混合ガスをガ
ス分離膜に供給して接触させ、膜の非透過側から、純度
80体積%以上のSF6を含んだガスをSF6の回収率8
0%以上で回収し、ガス分離膜の透過側に排出するSF
6ガス量が全供給混合ガス量の3体積%以下であること
を特徴とする電気絶縁用ガスの分離回収方法。
1. A gas mixture comprising 3 to 60% by volume of SF 6 and at least one other electrically insulating gas is supplied to a gas separation membrane and brought into contact with the gas separation membrane. recovery of% more gas containing SF 6 SF 6 8
SF recovered at 0% or more and discharged to the permeate side of the gas separation membrane
(6) A method for separating and recovering a gas for electrical insulation, wherein a gas amount is 3% by volume or less of a total mixed gas amount.
【請求項2】ガス分離膜が芳香族ポリイミド分離膜であ
ることを特徴とする請求項1記載の電気絶縁用ガスの分
離回収方法。
2. The method according to claim 1, wherein the gas separation membrane is an aromatic polyimide separation membrane.
【請求項3】電気絶縁性ガスが、窒素ガス、炭酸ガス、
ヘリウムガス、水素ガス、二酸化硫黄ガス、空気のうち
少なくとも1つであることを特徴とする請求項1または
請求項2記載の電気絶縁用ガスの分離回収方法。
3. The method according to claim 1, wherein the electrically insulating gas is nitrogen gas, carbon dioxide gas,
3. The method according to claim 1, wherein the gas is at least one of helium gas, hydrogen gas, sulfur dioxide gas, and air.
【請求項4】多数の中空糸の形状をした分離膜が密封容
器内に内蔵されており、中空糸内部に通じるガス供給口
と非透過ガス排出口、さらに、中空糸の外側に少なくと
も1つの透過ガス排出口を有するガス分離装置であり、
SF6ガスとその他の少なくとも1種類以上の電気絶縁
性ガスからなる混合ガスをガス分離装置のガス供給口か
ら中空糸の内側に導入し、SF6ガス量が供給混合ガス
の3体積%以下である電気絶縁性ガスを透過ガス排出口
から排出し、純度80体積%以上のSF6を含んだガス
を非透過ガス排出口より回収することを特徴とする電気
絶縁用ガスの分離回収装置。
4. A plurality of hollow fiber-shaped separation membranes are housed in a sealed container, and a gas supply port and a non-permeate gas outlet communicating with the inside of the hollow fiber, and at least one outside of the hollow fiber are provided. A gas separation device having a permeated gas outlet,
A mixed gas consisting of SF 6 gas and at least one other kind of electrically insulating gas is introduced into the hollow fiber from the gas supply port of the gas separator, and the SF 6 gas amount is 3% by volume or less of the supplied mixed gas. An apparatus for separating and recovering a gas for electrical insulation, wherein a certain electrically insulating gas is discharged from a permeated gas outlet, and a gas containing SF 6 having a purity of 80% by volume or more is recovered from a non-permeated gas outlet.
JP32171598A 1998-11-12 1998-11-12 Method and apparatus for separating and collecting gas for electrical insulation Expired - Fee Related JP3890783B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP32171598A JP3890783B2 (en) 1998-11-12 1998-11-12 Method and apparatus for separating and collecting gas for electrical insulation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP32171598A JP3890783B2 (en) 1998-11-12 1998-11-12 Method and apparatus for separating and collecting gas for electrical insulation

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JP2000140558A true JP2000140558A (en) 2000-05-23
JP3890783B2 JP3890783B2 (en) 2007-03-07

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ID=18135640

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Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6921428B2 (en) 2001-01-25 2005-07-26 Ube Industries, Ltd. Device and method for separating and collecting halide gas
JP2011140024A (en) * 2011-03-17 2011-07-21 Ube Industries Ltd Asymmetric hollow fiber membrane for separating gas, and method of separating gas
JP2011140023A (en) * 2011-03-17 2011-07-21 Ube Industries Ltd Asymmetric hollow fiber membrane for separating gas, and method of separating gas
JP2011161442A (en) * 2011-03-17 2011-08-25 Ube Industries Ltd Unsymmetrical hollow fiber gas separation membrane and gas separation method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6921428B2 (en) 2001-01-25 2005-07-26 Ube Industries, Ltd. Device and method for separating and collecting halide gas
JP2011140024A (en) * 2011-03-17 2011-07-21 Ube Industries Ltd Asymmetric hollow fiber membrane for separating gas, and method of separating gas
JP2011140023A (en) * 2011-03-17 2011-07-21 Ube Industries Ltd Asymmetric hollow fiber membrane for separating gas, and method of separating gas
JP2011161442A (en) * 2011-03-17 2011-08-25 Ube Industries Ltd Unsymmetrical hollow fiber gas separation membrane and gas separation method

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