JPH0331641B2 - - Google Patents

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Publication number
JPH0331641B2
JPH0331641B2 JP58048916A JP4891683A JPH0331641B2 JP H0331641 B2 JPH0331641 B2 JP H0331641B2 JP 58048916 A JP58048916 A JP 58048916A JP 4891683 A JP4891683 A JP 4891683A JP H0331641 B2 JPH0331641 B2 JP H0331641B2
Authority
JP
Japan
Prior art keywords
gas
membrane
separation
helium
hydrogen
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.)
Expired - Lifetime
Application number
JP58048916A
Other languages
Japanese (ja)
Other versions
JPS59177117A (en
Inventor
Kuniaki Watanabe
Masao Matsuyama
Hitoshi Myake
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.)
Teijin Ltd
Original Assignee
Teijin Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Teijin Ltd filed Critical Teijin Ltd
Priority to JP58048916A priority Critical patent/JPS59177117A/en
Publication of JPS59177117A publication Critical patent/JPS59177117A/en
Publication of JPH0331641B2 publication Critical patent/JPH0331641B2/ja
Granted legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0221—Group 4 or 5 metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B01D71/02231—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B01D71/02232—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Description

【発明の詳細な説明】 本発明は同位体を含む水素とヘウムとを分離す
る膜分離法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a membrane separation method for separating hydrogen and heum containing isotopes.

エネルギーの需要は年々増加する一方であり、
そのための様々のエネルギー源が探索されてお
り、そのなかで有望なものとして核融合反応があ
る。 Demand for energy continues to increase year by year,
Various energy sources are being explored for this purpose, and one of the most promising is nuclear fusion reactions.

これはデユートリウムとトリチウムとの次式の
核融合反応を利用するものである。 This utilizes the following nuclear fusion reaction between deutorium and tritium.

2H＋ 3H→ 4He＋ｎ これによれば１ｇのトリチウムが重水素と反応
すると約１億Kcalのエネルギーが発生する。 2 H+ 3 H→ 4 He+n According to this, when 1 g of tritium reacts with deuterium, approximately 100 million Kcal of energy is generated.

しかしこの反応転化率はたかだか10％であり、
核融合廃ガス中には未反応原料のデユートリウム
とトリチウムを大量に含み、これを生成したヘリ
ウムから分離し回収する必要がある。 However, the conversion rate of this reaction is only 10%,
Nuclear fusion waste gas contains large amounts of unreacted raw materials deutorium and tritium, which must be separated and recovered from the helium produced.

その分離法の一つに分離にかかるエネルギーが
小さく操作が容易である膜分離法があるが、水素
およびその同位体ならびにヘリウムはいずれも分
子量の小さい気体でかつ分子量の差も小さく一般
に膜分離法では分離しにくい気体である。 One of the separation methods is membrane separation, which requires less energy for separation and is easy to operate. However, hydrogen, its isotopes, and helium are all gases with small molecular weights, and the difference in molecular weight is small, so membrane separation is generally used. It is a gas that is difficult to separate.

そこで、同位体を含む水素とヘリウムとの膜分
離法を実現すべく鋭意研究した結果本発明に到達
したもである。 Therefore, the present invention was achieved as a result of intensive research to realize a membrane separation method for hydrogen and helium containing isotopes.

即ち本発明は ガス透過性支持体に遷移金属又はその合金の連
続膜を形成せしめた分離膜を用いて水素（同位体
を含む）とヘリウムとを分離する方法である。 That is, the present invention is a method for separating hydrogen (including isotopes) and helium using a separation membrane in which a continuous membrane of a transition metal or its alloy is formed on a gas-permeable support.

本発明に用いられるガス透過性支持体として
は、ガスの透過性のあるものであるならば特に限
定されないが、有機高分子フイルム、有機多孔質
体、あるいは無機多孔質体などが用いられる。 The gas-permeable support used in the present invention is not particularly limited as long as it is permeable to gas, but organic polymer films, organic porous materials, inorganic porous materials, and the like can be used.

このうち、気体透過性の大きい有機あるいは無
機多孔質体が好適に用いられる。 Among these, organic or inorganic porous materials with high gas permeability are preferably used.

そのなかでも、膜が金属で高温に耐えるのでガ
ス透過性支持体としても高温に耐える材料である
無機多孔膜例えばセラミツクス多孔膜、ガラス多
孔膜、ステンレス焼結金属多孔体などが好適に用
いられる。 Among these, inorganic porous membranes, such as ceramic porous membranes, glass porous membranes, and stainless steel sintered porous metal bodies, which are materials that can withstand high temperatures as gas-permeable supports, are preferably used because the membranes are metal and can withstand high temperatures.

高温での膜分離は、一般に気体の透過性は温度
があがると高くなるので高温では透過量が多くな
ること、あるいは高温の廃ガスを冷却せずにその
まま処理できるなどの利点がある。 Membrane separation at high temperatures generally has the advantage that gas permeability increases as the temperature rises, so the amount of permeation increases at high temperatures, or that high-temperature waste gas can be treated as is without cooling.

支持体の形状としては、分離モジユールの形状
に応じて決められ、平膜、管状、中空糸等種種の
形状をとり得る。 The shape of the support is determined depending on the shape of the separation module, and can take various shapes such as a flat membrane, a tubular shape, and a hollow fiber.

本発明に用いられる遷移金属は原子番号21〜
30、39〜48、57〜80の元素であり例えばFe、Cr、
Mn、Ni、Ag、Pd、Ti等をあげることができ、
また、これらは種々の合金例えばFe−Cr−Ni、
Ni−Mo、Ni−Cr−Fe−Mo−Coなどでも使用
できる。 The transition metal used in the present invention has an atomic number of 21 to
30, 39-48, 57-80 elements such as Fe, Cr,
Can include Mn, Ni, Ag, Pd, Ti, etc.
In addition, these alloys include various alloys such as Fe-Cr-Ni,
Ni-Mo, Ni-Cr-Fe-Mo-Co, etc. can also be used.

本発明は前述のガス透過性支持体の上に上記金
属又は合金の連続薄膜層を形成せしめて分離膜と
するが薄膜層の形成法としては、スパツタリング
法、蒸着法、イオンプレーテイング法などの従来
公知の物理的沈着法（PVD法）やメツキなどの
化学的沈着法が適用されるが、そのなかで金属膜
とガス透過性支持体との密着性が良好となるスパ
ツタリング、イオンプレーテイング法が好適であ
る。 In the present invention, a continuous thin film layer of the above-mentioned metal or alloy is formed on the above-mentioned gas-permeable support to form a separation membrane. Methods for forming the thin film layer include sputtering method, vapor deposition method, ion plating method, etc. Conventionally known physical deposition methods (PVD method) and chemical deposition methods such as plating are applied, but sputtering and ion plating methods improve the adhesion between the metal film and the gas-permeable support. is suitable.

又、金属膜が形成される過程において該金属が
一部酸化される場合もあるが、酸化物が安定であ
る限り分離膜としてはそのまま使うことができ
る。 Further, in the process of forming a metal film, the metal may be partially oxidized, but as long as the oxide is stable, it can be used as is as a separation film.

本発明の分離方法は該遷移金属膜においておこ
なわれるものであり、その厚さには特に限定はな
いが欠陥部が生じない限りできる限り薄いものが
好ましく、膜厚としては1μｍ以下、好ましくは
1000Å以下である。 The separation method of the present invention is carried out on the transition metal film, and its thickness is not particularly limited, but it is preferably as thin as possible as long as no defects occur, and the film thickness is 1 μm or less, preferably
It is 1000Å or less.

本発明の遷移金属膜としてはコスト及び性能の
面からはFe系の合金例えばFe−Cr−Ni系の合金
であるsus膜が好適に用いられる。 As the transition metal film of the present invention, from the viewpoint of cost and performance, an Fe-based alloy, for example, a sus film that is an Fe-Cr-Ni-based alloy is preferably used.

分離手法としては、分離膜の片側（供給側）に
水素およびその同位体及びヘリウムを含む混合気
体を送り、水素及びその同位体を膜の反対側（透
過側）にヘリウムよりはやく透過させて分離す
る。 The separation method involves sending a gas mixture containing hydrogen, its isotopes, and helium to one side of the separation membrane (the supply side), and allowing the hydrogen and its isotopes to permeate through the other side of the membrane (the permeation side) more quickly than the helium. do.

分離手法としては、膜の供給側を加圧する方
法、あるいは膜の透過側を減圧する方法、あるい
はアルゴンなどの気体をキヤリヤーガスとして流
すことなどにより膜の両側に分圧差をつけて実施
される。 The separation method is carried out by applying pressure on the supply side of the membrane, reducing pressure on the permeate side of the membrane, or creating a partial pressure difference on both sides of the membrane by flowing a gas such as argon as a carrier gas.

本発明の分離膜は核融合廃ガスの分離ばかりで
なく、その水素とヘリウムとの分離性の高いこと
を利用して通常の水素とヘリウムの混合ガスの分
離、例えばヘリウム、水素を含む天然ガスからの
水素分離などにも使用できるのはもちろん、さら
に、水素の透過性がすぐれていることより、水
素、ヘリウムより分子量の大きい気体例えばメタ
ン、アルゴンなどを含む混合気体からの水素分離
にも使うことができる。 The separation membrane of the present invention can be used not only to separate nuclear fusion waste gas, but also to separate ordinary mixed gases of hydrogen and helium, such as helium and natural gas containing hydrogen, by taking advantage of its high separability between hydrogen and helium. Not only can it be used for hydrogen separation from gases, but also because of its excellent hydrogen permeability, it can also be used for hydrogen separation from mixed gases containing gases with larger molecular weights than hydrogen and helium, such as methane and argon. be able to.

以下、実施例により本発明を具体的に説明する
が、本発明は何らこれらの実施例に限定されるも
のではない。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way.

実施例 １ 金属薄膜層の形成 厚さ300μｍのビスフエノールＡ−ポリカーボ
ネートフイルム表面に厚さ100ÅのSUS304から
なる金属薄膜層を形成した。該金属薄膜層は
SUS304板（厚さ３mm）をターゲツトとしArガス
圧力５×10-3TorrにおけるDCマグネトロンスパ
ツタによつて形成した。投入電力はターゲツトの
単位面積当り2W／cm2であり、ターゲツトと基板
となるポリカーボネートフイルムの間の距離は15
cmであつた。Example 1 Formation of a metal thin film layer A metal thin film layer of SUS304 with a thickness of 100 Å was formed on the surface of a bisphenol A-polycarbonate film with a thickness of 300 μm. The metal thin film layer is
A SUS304 plate (thickness: 3 mm) was used as a target and formed by DC magnetron sputtering at an Ar gas pressure of 5 x 10 -3 Torr. The input power was 2 W/cm 2 per unit area of the target, and the distance between the target and the polycarbonate film as the substrate was 15
It was cm.

この膜の分離性能を表１に示す。表１ 各種気体の透過係数（×10-8cm2／sec） H2 18.7 D2 14.4 T2 0.53 He ＜×10-2（測定限界以下） Ne ＜×10-2（測定限界以下） なお気体透過係数の測定は次の方法によつた。 Table 1 shows the separation performance of this membrane. Table 1 Permeability coefficient of various gases (×10 -8 cm 2 /sec) H 2 18.7 D 2 14.4 T 2 0.53 He <×10 -2 (Below measurement limit) Ne <×10 -2 (Below measurement limit) Gas The transmission coefficient was measured by the following method.

透過係数の測定 図−１に測定装置のセル部分を示す。コーンフ
ラツトフランジ１付きのガラス管２個より出来て
おり、このフランジの間にＯ−リングで試料膜２
を保持した。試料膜の有効面積は9.5cm2である。
透過セルの下流側にはトリチウムの透過速度を測
定するための窓なしＧ−Ｍカウンター３が接続さ
れており、上流側には予め一定量のトリチウムを
封入したガラスアンプル４を挿入した。Measurement of transmission coefficient Figure 1 shows the cell part of the measuring device. It is made of two glass tubes with a cone flat flange 1, and an O-ring is used between the flanges to attach the sample membrane 2.
was held. The effective area of the sample membrane is 9.5 cm2 .
A windowless GM counter 3 for measuring the permeation rate of tritium was connected to the downstream side of the permeation cell, and a glass ampoule 4 pre-filled with a certain amount of tritium was inserted into the upstream side.

各気体の透過速度の測定はTime−lag法によつ
て行なわれた。非放射性ガスの透過速度は流通法
で測定し、透過量および電離真空計による排気速
度は毛細管と２個の電離真空計を用いて求めた。 The permeation rate of each gas was measured by the time-lag method. The permeation rate of the non-radioactive gas was measured by the flow method, and the amount of permeation and the pumping rate using an ionization vacuum gauge were determined using a capillary tube and two ionization vacuum gauges.

トリチウムガスの透過速度は閉鎖系でおこな
い、Ｇ−Ｍカウンターで濃度を測定した。透過速
度は〔Torr・c.c.／sec〕の単位で求めており、こ
れから求めた透過係数の単位はcm2／secで表わさ
れる。 The permeation rate of tritium gas was measured in a closed system, and the concentration was measured using a GM counter. The permeation rate is determined in the unit of [Torr·cc/sec], and the unit of the permeation coefficient determined from this is expressed in cm 2 /sec.

実施例 ２ 実施例１のSUS膜表面にデユートリウム、プ
ロチウム及びヘリウムをそれぞれ2vol％づつ含
み、残余はアルゴンである混合気体を流し、膜の
反対側（透過側）にアルゴンキヤリヤーガスを流
した。Example 2 A gas mixture containing 2 vol% each of deutorium, protium, and helium, with the remainder being argon, was flowed onto the surface of the SUS membrane of Example 1, and an argon carrier gas was flowed onto the opposite side (permeation side) of the membrane.

10分後透過側にはデユートリウム及びプロチウ
ムは認められたが、ヘリウムは認められなかつ
た。 After 10 minutes, deutorium and protium were observed on the permeate side, but no helium was observed.

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

図−１はガス透過速度の測定装置である。１は
コーンフラツトフランジ、２は試料膜、３はＧ−
Ｍカウンター、４はガスアンプルを表わす。 Figure 1 shows a gas permeation rate measuring device. 1 is a cone flat flange, 2 is a sample membrane, and 3 is a G-
M counter, 4 represents gas ampoule.

Claims (1)

【特許請求の範囲】[Claims] １ 有機高分子フイルム支持体上に遷移金属又は
その合金の連続膜を形成せしめた分離膜を用い、
水素（その同位体を含む）とヘリウムとを分離す
ることを特徴とする水素−ヘリウム分離方法。1 Using a separation membrane in which a continuous film of a transition metal or its alloy is formed on an organic polymer film support,
A hydrogen-helium separation method characterized by separating hydrogen (including its isotopes) and helium.
JP58048916A 1983-03-25 1983-03-25 Separation of hydrogen-helium Granted JPS59177117A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58048916A JPS59177117A (en) 1983-03-25 1983-03-25 Separation of hydrogen-helium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58048916A JPS59177117A (en) 1983-03-25 1983-03-25 Separation of hydrogen-helium

Publications (2)

Publication Number Publication Date
JPS59177117A JPS59177117A (en) 1984-10-06
JPH0331641B2 true JPH0331641B2 (en) 1991-05-08

Family

ID=12816571

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58048916A Granted JPS59177117A (en) 1983-03-25 1983-03-25 Separation of hydrogen-helium

Country Status (1)

Country Link
JP (1) JPS59177117A (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3434150A1 (en) * 1984-09-18 1986-03-27 Kernforschungsanlage Jülich GmbH, 5170 Jülich METHOD AND DEVICE FOR SEPARATING HYDROGEN FROM A MIXTURE, IN PARTICULAR A GAS MIXTURE
JPS62160121A (en) * 1985-12-28 1987-07-16 Ngk Insulators Ltd Porous diaphragm
US4857080A (en) * 1987-12-02 1989-08-15 Membrane Technology & Research, Inc. Ultrathin composite metal membranes
US5342431A (en) * 1989-10-23 1994-08-30 Wisconsin Alumni Research Foundation Metal oxide membranes for gas separation
US5240473A (en) * 1992-09-01 1993-08-31 Air Products And Chemicals, Inc. Process for restoring permeance of an oxygen-permeable ion transport membrane utilized to recover oxygen from an oxygen-containing gaseous mixture
US5269822A (en) * 1992-09-01 1993-12-14 Air Products And Chemicals, Inc. Process for recovering oxygen from gaseous mixtures containing water or carbon dioxide which process employs barium-containing ion transport membranes
US5261932A (en) * 1992-09-01 1993-11-16 Air Products And Chemicals, Inc. Process for recovering oxygen from gaseous mixtures containing water or carbon dioxide which process employs ion transport membranes
US5487774A (en) * 1993-11-08 1996-01-30 Wisconsin Alumni Research Foundation Gas phase fractionation method using porous ceramic membrane
US5439624A (en) * 1994-02-14 1995-08-08 Wisconsin Alumni Research Foundation Method for forming porous ceramic materials
US5456740A (en) * 1994-06-22 1995-10-10 Millipore Corporation High-efficiency metal membrane getter element and process for making
US5738708A (en) * 1995-06-07 1998-04-14 The Regents Of The University Of California Office Of Technology Transfer Composite metal membrane
JP4668043B2 (en) * 2005-11-22 2011-04-13 財団法人ファインセラミックスセンター Method for manufacturing helium separator
CN107261845A (en) * 2017-08-25 2017-10-20 中国工程物理研究院核物理与化学研究所 A method for separating hydrogen isotope mixed gas
CN107930400A (en) * 2017-12-07 2018-04-20 中国工程物理研究院核物理与化学研究所 A kind of hydrogen helium separation and hydrogen isotope concentration coupled system and method
CN109381941A (en) * 2018-11-30 2019-02-26 西北有色金属研究院 A kind of hydrogen isotope purifying filter

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5235739B2 (en) * 1972-07-21 1977-09-10
JPS5228748A (en) * 1975-08-29 1977-03-03 Matsushita Electric Ind Co Ltd Defrosting control process
JPS55130801A (en) * 1979-02-15 1980-10-11 Hill Eugene Farrell Separation of hydrogen which use coating titaniummzirconium alloy

Also Published As

Publication number Publication date
JPS59177117A (en) 1984-10-06

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