JPS6259184B2 - - Google Patents
Info
- Publication number
- JPS6259184B2 JPS6259184B2 JP58142820A JP14282083A JPS6259184B2 JP S6259184 B2 JPS6259184 B2 JP S6259184B2 JP 58142820 A JP58142820 A JP 58142820A JP 14282083 A JP14282083 A JP 14282083A JP S6259184 B2 JPS6259184 B2 JP S6259184B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- anode
- cathode
- electrochemical
- mixed gas
- 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
Links
- 239000001257 hydrogen Substances 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003456 ion exchange resin Substances 0.000 claims description 8
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 description 9
- 238000000926 separation method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000002848 electrochemical method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- -1 polydimethylsiloxane copolymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明は、電気化学的手法を利用して水素を含
む混合ガスから水素を分離する方法に関するもの
であり、その目的とするところは、電気化学セル
の作動電流密度をより大きくして、水素の分離速
度をより速くせんとするにある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of separating hydrogen from a hydrogen-containing gas mixture using an electrochemical method, and its purpose is to increase the operating current density of an electrochemical cell. The aim is to increase the hydrogen separation rate by increasing the size.
水素を含む混合ガスから水素を分離するという
操作は化学工業においては極めて重要であり、現
在次のような用途を期待して開発あるいは実用化
されている。 The operation of separating hydrogen from a hydrogen-containing gas mixture is extremely important in the chemical industry, and is currently being developed or put into practical use in anticipation of the following uses.
(1) アンモニア合成のパージガスからの水素の回
収。(1) Recovery of hydrogen from purge gas for ammonia synthesis.
(2) 水素製造プラントのパージガス中に含まれる
水素の回収。(2) Recovery of hydrogen contained in purge gas of hydrogen production plants.
(3) 石油脱硫に用いられた廃ガス中の水素の回
収。(3) Recovery of hydrogen from waste gas used in petroleum desulfurization.
これらの水素の回収操作として、従来ポリジメ
チルシロキサン共重合体膜などの高分子非多孔質
膜による水素の選択分離を利用する方法が実用化
されている。しかしこの膜分離法によつて分離さ
れる水素の純度は一般にそれほど高くないという
欠点がみられる。 As a recovery operation for these hydrogens, a method has conventionally been put into practical use that utilizes selective separation of hydrogen using a non-porous polymeric membrane such as a polydimethylsiloxane copolymer membrane. However, a drawback is that the purity of hydrogen separated by this membrane separation method is generally not very high.
分離される水素を高純度にするためには、まだ
実用化はされていないが、電気化学的手法がすで
に提案されている。つまり電気化学的手法では、
陽極として燃料電池のいわゆる水素極といわれる
ガス拡散電極を用い、陰極として水電解に用いら
れるものと同様の電極を配し、電解液として、硫
酸，過塩素酸あるいは水酸化カリウムの水溶液を
用いて電気化学セルを構成し、陽極側に水素を含
む混合ガスを供給しつゝ、陽・陰両極間に直流電
流を通すと陽極側で、
H2＋2OH-→2H2O＋2e-（アルカリ電解液） (1)
あるいは、
H2→2H+＋2e-（酸性電解液） (2)
なる反応により、水素の選択的電解酸化が起り、
陰極側で、上述の(1)式あるいは(2)式の逆方向の反
応が起つて、純度の高い水素ガスが得られる。 Although it has not yet been put to practical use, electrochemical methods have already been proposed to make the hydrogen to be separated highly purified. In other words, in the electrochemical method,
A gas diffusion electrode called the so-called hydrogen electrode of a fuel cell is used as the anode, an electrode similar to that used for water electrolysis is used as the cathode, and an aqueous solution of sulfuric acid, perchloric acid, or potassium hydroxide is used as the electrolyte. When an electrochemical cell is constructed and a mixed gas containing hydrogen is supplied to the anode side, and a direct current is passed between the positive and negative electrodes, H 2 +2OH - →2H 2 O + 2e - (alkaline electrolyte) is generated on the anode side. (1) Alternatively, selective electrolytic oxidation of hydrogen occurs due to the reaction H 2 →2H + +2e - (acidic electrolyte) (2)
On the cathode side, a reaction in the opposite direction of equation (1) or equation (2) above occurs, yielding highly pure hydrogen gas.
この電気化学的手法が従来、実用化されていな
い理由は、上述の如き水溶液電解液を用いる限
り、作動電流密度が高々100〜200mA／cm2であ
り、反応速度が遅かつたためである。 The reason why this electrochemical method has not been put to practical use so far is that, as long as the aqueous electrolyte described above is used, the operating current density is at most 100 to 200 mA/cm 2 and the reaction rate is slow.
これに対し、近年開発されたパーフロロカーボ
ンの如き含フツ素高子をベースにし、これにスル
フオン酸基の如きカチオン交換基を導入したイオ
ン交換樹脂膜を電解質とし、この膜に陰，陽両極
をそれぞれ一体接合した燃料電池の技術を応用す
ると、より高い電流密度で作動し得る水素の電気
化学的分離装置の可能性が出てきた。 In contrast, the electrolyte is an ion-exchange resin membrane based on a recently developed fluorine-containing polymer such as perfluorocarbon, into which cation exchange groups such as sulfonic acid groups are introduced, and this membrane has both negative and anode electrodes. Applying the technology of integrally bonded fuel cells offers the possibility of electrochemical separation devices for hydrogen that can operate at higher current densities.
しかしながら本発明者等は、種々実験をしてみ
た結果、このイオン交換樹脂膜を用いる方法には
ひとつの難点があることを発見した。つまり、イ
オン交換樹脂を用いる電気化学的水素分離装置に
おいては、陽極反応は上述の(2)式のようになるが
(2)式で生成する水素イオン（H+）が陽極側から陰
極側に移動する際、数モルの水分子を随伴するた
めに陽極とイオン交換樹脂膜との界面で水が欠乏
し、その結果として連続的な大電流密度での作動
が困難になるという事実を発見した。 However, as a result of various experiments, the present inventors discovered that this method using an ion exchange resin membrane has one drawback. In other words, in an electrochemical hydrogen separation device using ion exchange resin, the anodic reaction is as shown in equation (2) above.
When the hydrogen ions (H + ) generated in equation (2) move from the anode side to the cathode side, they are accompanied by several moles of water molecules, resulting in a lack of water at the interface between the anode and the ion exchange resin membrane. We discovered that as a result, it becomes difficult to operate at continuous high current densities.
本発明は、かゝる発見にもとづいてなされたも
のであり、陽極側に供給すべき水素を含む混合ガ
スを充分加湿することによつて、大電流密度での
作動を可能にしたものである。 The present invention was made based on this discovery, and enables operation at high current density by sufficiently humidifying the hydrogen-containing mixed gas to be supplied to the anode side. .
以下、本発明の一実施例について詳述する。 An embodiment of the present invention will be described in detail below.
実施例
第１図は本発明の一実施例にかかる電気化学的
水素分離装置の断面構造略図を示す。Embodiment FIG. 1 shows a schematic cross-sectional structure of an electrochemical hydrogen separation apparatus according to an embodiment of the present invention.
１はパーフロロカーボンをベースにし、スルフ
オン酸基を導入してなるイオン交換樹脂膜であ
り、その片面に陽極２が、他面に陰極３が一体に
接合されている。陽極２は白金からなり、無電解
メツキ法により接合され、陰極３は白金ブラツク
粉末とポリ４フツ化エチレンとの混合物層からな
り、ホツトプレス法で接合されている。４は陽極
集電網，５は陰極集電網，６は陽極端子板，７は
陰極端子板，８はセルフレームである。 Reference numeral 1 denotes an ion exchange resin membrane made of perfluorocarbon as a base and into which sulfonic acid groups have been introduced, and an anode 2 is integrally joined to one side of the membrane, and a cathode 3 is integrally joined to the other side. The anode 2 is made of platinum and is bonded by electroless plating, and the cathode 3 is made of a layer of a mixture of platinum black powder and polytetrafluoroethylene and bonded by hot pressing. 4 is an anode current collection network, 5 is a cathode current collection network, 6 is an anode terminal plate, 7 is a cathode terminal plate, and 8 is a cell frame.
水素と窒素との混合比が１：３の混合ガスは加
湿槽９でほヾ飽和になるまで加湿され、混合ガス
入口１０から供給される。陽極２と陰極３との間
に直流電流を通電すると、陽極２で水素の選択イ
オン化反応が起ると同時に陰極３で水素が発生す
る。この発生した水素は水素導出口１１から導出
される。一方、陽極２で水素が除去された残りの
残余ガスは残余ガス導出口１２から導出される。
陰極から発生すると水素の純度は99.99％であ
る。次に本発明の効果について説明する。 A mixed gas containing hydrogen and nitrogen at a mixing ratio of 1:3 is humidified in a humidifying tank 9 until it is almost saturated, and then supplied from a mixed gas inlet 10. When a direct current is passed between the anode 2 and the cathode 3, a selective ionization reaction of hydrogen occurs at the anode 2, and at the same time hydrogen is generated at the cathode 3. This generated hydrogen is led out from the hydrogen outlet 11. On the other hand, the remaining gas from which hydrogen has been removed at the anode 2 is led out from the residual gas outlet 12.
When generated from the cathode, the purity of hydrogen is 99.99%. Next, the effects of the present invention will be explained.
せず上述の実施例で得られた電気化学的水素分
離装置の電流密度とセル電圧との関係Ａと従来の
ように特に加湿しない場合のそれＢとを比較する
と、第２図に示すようになる。 Comparing the relationship A between the current density and cell voltage of the electrochemical hydrogen separator obtained in the above-mentioned example with the relationship B when no particular humidification is performed as in the conventional case, as shown in Figure 2. Become.
つまり、本発明のように加湿によつて初めて、
1000〜1500mA／cm2といつた大電流密度での作動
が可能になることがわかる。 In other words, only through humidification as in the present invention,
It can be seen that operation at high current densities of 1000 to 1500 mA/cm 2 is possible.
以上詳述せる如く、本発明は、イオン交換樹脂
膜を使用する電気化学的水素分離装置において、
水素を含む混合ガスを加湿することによつて大電
流密度での作動、換言するとより効率的な水素の
分離を可能とするもので、その工業的価値極めて
大である。 As detailed above, the present invention provides an electrochemical hydrogen separation device using an ion exchange resin membrane.
By humidifying a mixed gas containing hydrogen, it is possible to operate at a high current density, in other words, to separate hydrogen more efficiently, and its industrial value is extremely high.
第１図は、本発明の一実施例にかかる電気化学
的水素分離装置の断面図、第２図は本発明の一実
施例にかかる電気化学的水素分離装置Ａと従来品
Ｂとの電流密度とセル電圧との関係の比較を示す
図である。
１……イオン交換樹脂膜、２……陽極、３……
陰極、４……陽極集電網、５……陰極集電網、６
……陽極端子板、７……陰極端子板、８……セル
フレーム、９……加湿槽、１０……混合ガス入
口、１１……水素導出口、１２……残余ガス導出
口。
FIG. 1 is a cross-sectional view of an electrochemical hydrogen separator according to an embodiment of the present invention, and FIG. 2 is a current density of an electrochemical hydrogen separator A according to an embodiment of the present invention and a conventional product B. FIG. 3 is a diagram showing a comparison of the relationship between and cell voltage. 1... Ion exchange resin membrane, 2... Anode, 3...
Cathode, 4...Anode current collection network, 5...Cathode current collection network, 6
... Anode terminal plate, 7 ... Cathode terminal plate, 8 ... Cell frame, 9 ... Humidification tank, 10 ... Mixed gas inlet, 11 ... Hydrogen outlet, 12 ... Residual gas outlet.
Claims (1)
基を導入してなる水素イオン移動型のイオン交換
樹脂膜の片面に陰極を、他面に陽極を一体に接合
せしめてなる電気化学セルの陽極側に水素を含む
混合ガスを加湿したものを供給し、陽極と陰極と
の間に直流電圧を印加することにより、陽極にお
いて水素をイオン化せしめると同時に陰極におい
て水素を発生せしめることを特徴とする水素を含
む混合ガスから水素を分離する方法。1 The anode side of an electrochemical cell made by integrally bonding a cathode on one side and an anode on the other side of a hydrogen ion-transfer type ion exchange resin membrane based on a fluorine-containing polymer and having a cation exchange group introduced therein. A method for producing hydrogen characterized by supplying a humidified mixed gas containing hydrogen to a container and applying a DC voltage between the anode and the cathode to ionize hydrogen at the anode and simultaneously generate hydrogen at the cathode. A method of separating hydrogen from a mixed gas containing
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58142820A JPS6036302A (en) | 1983-08-05 | 1983-08-05 | Separation of hydrogen from gaseous mixture containing hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58142820A JPS6036302A (en) | 1983-08-05 | 1983-08-05 | Separation of hydrogen from gaseous mixture containing hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6036302A JPS6036302A (en) | 1985-02-25 |
| JPS6259184B2 true JPS6259184B2 (en) | 1987-12-09 |
Family
ID=15324382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58142820A Granted JPS6036302A (en) | 1983-08-05 | 1983-08-05 | Separation of hydrogen from gaseous mixture containing hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6036302A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013089221A1 (en) * | 2011-12-15 | 2013-06-20 | パナソニック株式会社 | Device for permeation of carbon dioxide and method for transport of carbon dioxide |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62166103U (en) * | 1986-04-12 | 1987-10-22 | ||
| JPS6483501A (en) * | 1987-09-25 | 1989-03-29 | Shirakawa Seisakusho Kk | Hydrogen purifying device |
| JPH02102675A (en) * | 1988-10-12 | 1990-04-16 | Naka Tech Lab | Emergency exit for building |
| JPH0349861U (en) * | 1989-09-21 | 1991-05-15 | ||
| JP4617648B2 (en) * | 2003-02-27 | 2011-01-26 | トヨタ自動車株式会社 | Hydrogen extraction device |
| WO2018049343A1 (en) * | 2016-09-09 | 2018-03-15 | Sustainable Innovations, Inc. | Apparatus and method for concentrating hydrogen isotopes |
| US20180257933A1 (en) | 2017-03-09 | 2018-09-13 | Sustainable Innovations, Inc. | In situ apparatus and method for providing deuterium oxide or tritium oxide in an industrial apparatus or method |
-
1983
- 1983-08-05 JP JP58142820A patent/JPS6036302A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013089221A1 (en) * | 2011-12-15 | 2013-06-20 | パナソニック株式会社 | Device for permeation of carbon dioxide and method for transport of carbon dioxide |
| JP5617048B2 (en) * | 2011-12-15 | 2014-10-29 | パナソニック株式会社 | Carbon dioxide permeation apparatus and carbon dioxide transport method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6036302A (en) | 1985-02-25 |
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