JPH08246177A - Production of hydride for transporting and storing hydrogen and device therefor - Google Patents
Production of hydride for transporting and storing hydrogen and device thereforInfo
- Publication number
- JPH08246177A JPH08246177A JP7047693A JP4769395A JPH08246177A JP H08246177 A JPH08246177 A JP H08246177A JP 7047693 A JP7047693 A JP 7047693A JP 4769395 A JP4769395 A JP 4769395A JP H08246177 A JPH08246177 A JP H08246177A
- Authority
- JP
- Japan
- Prior art keywords
- hydride
- electrolyte membrane
- water
- hydrogen
- chamber
- 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
Links
- 150000004678 hydrides Chemical class 0.000 title claims abstract description 37
- 239000001257 hydrogen Substances 0.000 title claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- -1 hydrogen ions Chemical class 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012466 permeate Substances 0.000 claims abstract description 6
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims description 4
- 239000005518 polymer electrolyte Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水素を輸送、貯蔵する
のに有用な水素化物を、電気化学的に製造する装置及び
方法に関する。FIELD OF THE INVENTION This invention relates to an apparatus and method for electrochemically producing hydrides useful for transporting and storing hydrogen.
【０００２】[0002]
【従来の技術】水素は現在、石油精製工程での副生や天
然ガスの水蒸気改質反応などによって製造されている。
しかし、石油、石炭、天然ガスなどの炭素資源は有限で
あり、将来枯渇することが考えられることから、自然エ
ネルギー、とりわけ水資源を利用した水素製造方法が注
目されている。開発可能な水資源のうち未開発のものは
世界中で８５％近くも残されているが、その水力を利用
して発電を行い、発生した電力で水を電気分解して水素
を製造すれば、水素製造の際に炭素資源に依存する必要
はなくなるうえ、水素自体、燃焼しても水に戻るだけな
ので、環境を汚染しないクリーンなエネルギーとしての
利用が期待できる。しかし、水素は室温で気体であり、
燃焼性や爆発性が高く、そのままでは長距離の輸送や長
期間の貯蔵が困難である。したがって、輸送や貯蔵に際
しては、アンモニア、メタノール、イソプロパノール、
シクロヘキサンのような水素化物として、安全な形に変
換することが必要となるが、これらの水素化物の製造は
従来の方法では高温高圧の反応装置を用いて行われ、多
大なエネルギーを必要とするため、その変換効率につい
て問題があった。2. Description of the Related Art Hydrogen is currently produced by a by-product in a petroleum refining process or a steam reforming reaction of natural gas.
However, since carbon resources such as petroleum, coal, and natural gas are limited and may be exhausted in the future, a hydrogen production method using natural energy, especially water resources, is drawing attention. Nearly 85% of the water resources that can be developed are still undeveloped in the world, but if you use this hydropower to generate electricity and use the generated electricity to electrolyze water to produce hydrogen. When hydrogen is produced, there is no need to rely on carbon resources, and hydrogen itself returns to water when burned, so it can be expected to be used as clean energy that does not pollute the environment. But hydrogen is a gas at room temperature,
It is highly flammable and explosive, making it difficult to transport over long distances or store it for a long time. Therefore, during transportation and storage, ammonia, methanol, isopropanol,
As a hydride such as cyclohexane, it is necessary to convert it into a safe form, but these hydrides are produced by a conventional method using a high-temperature and high-pressure reactor, which requires a large amount of energy. Therefore, there was a problem regarding the conversion efficiency.
【０００３】[0003]
【発明が解決しようとする課題】このようなことから、
水の電気分解による水素の生成と同時に、輸送や貯蔵に
適した水素化物に効率良く変換する方法の開発が望まれ
ていた。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
It has been desired to develop a method of efficiently converting hydrogen into a hydride suitable for transportation and storage while simultaneously producing hydrogen by electrolysis of water.
【０００４】[0004]
【課題を解決するための手段】発明者らは、上記の課題
に鑑み鋭意研究した結果、水素イオンを選択的に透過す
る電解質膜の両側に高い水素化活性を有する金属電極を
取り付けて、この電極に直流電流を印加し、膜の一方の
側で水の電気分解を行って、生成した水素イオンを膜の
反対側へ透過させ、反対側の活性電極面上で水素化の反
応を行わせると、水素の輸送、貯蔵に有用な水素化物が
電気化学的に効率よく得られることを見出した。Means for Solving the Problems As a result of intensive studies in view of the above-mentioned problems, the inventors have attached metal electrodes having high hydrogenation activity to both sides of an electrolyte membrane that selectively permeates hydrogen ions. Applying a direct current to the electrode, electrolyzing water on one side of the membrane to allow the generated hydrogen ions to permeate to the other side of the membrane, causing a hydrogenation reaction on the opposite active electrode surface. And it was found that a hydride useful for transporting and storing hydrogen can be efficiently obtained electrochemically.
【０００５】すなわち本発明は、（１）水素イオン透過
性電解質膜の両面に取り付けた金属電極の正電極側に水
または水蒸気、負電極側に被水素化物を流し、又は満た
して、該電極間に直流電流を印加し、正電極側で水の電
気分解を行って、生成した水素イオンを電解質膜の反対
側へ透過させ、負電極側で被水素化物の水素化反応を行
わせることを特徴とする水素化物の製造方法、（２）被
水素化物が窒素、一酸化炭素もしくは二酸化炭素、アセ
トンまたはベンゼンである（１）項記載の水素化物の製
造方法、（３）水素イオン透過性電解質膜が固体高分子
電解質膜である（１）又は（２）項記載の水素化物の製
造方法、（４）金属電極がスパッタリング法とそれに続
く電気メッキ法によって取り付けられた２種の金属の複
合電極である（１）、（２）又は（３）項記載の水素化
物の製造方法、（５）金属電極が白金−ロジウム複合電
極である（１）、（２）、（３）又は（４）項記載の水
素化物の製造方法、（６）金属電極の正電極側で水の電
気分解、負電極側で被水素化物の水素化反応を行う水素
化物の製造装置において、水の電気分解の反応室と水素
化の反応室とが金属電極を両面に取り付けた水素イオン
透過性電解質膜によって隔てられていることを特徴とす
る水素化物の製造装置、（７）水素イオン透過性電解質
膜が固体高分子電解質膜である（６）項記載の水素化物
の製造装置、及び（８）金属電極が白金−ロジウム複合
電極である請求項６又は７記載の水素化物の製造装置を
提供するものである。That is, according to the present invention, (1) water or water vapor is supplied to the positive electrode side of a metal electrode attached to both sides of a hydrogen ion permeable electrolyte membrane, and a substance to be hydrogenated is supplied to the negative electrode side, or the hydrogen electrode is filled between the electrodes. A direct current is applied to the anode, the water is electrolyzed on the positive electrode side, the generated hydrogen ions are transmitted to the opposite side of the electrolyte membrane, and the hydrogenation reaction of the hydride is performed on the negative electrode side. (2) The method for producing a hydride according to (1), wherein the hydrogenated substance is nitrogen, carbon monoxide or carbon dioxide, acetone or benzene, and (3) a hydrogen ion-permeable electrolyte membrane. Is a solid polymer electrolyte membrane (1) or a method for producing a hydride according to (2), (4) a metal electrode is a composite electrode of two kinds of metals attached by a sputtering method and a subsequent electroplating method. There (1 The method for producing a hydride according to item (2) or (3), (5) the hydride according to item (1), (2), (3) or (4), wherein the metal electrode is a platinum-rhodium composite electrode. (6) In the hydride production apparatus for electrolyzing water on the positive electrode side of a metal electrode and hydrogenating a hydride on the negative electrode side, a reaction chamber for electrolysis of water and hydrogenation An apparatus for producing a hydride, characterized in that it is separated from the reaction chamber by a hydrogen ion permeable electrolyte membrane having metal electrodes attached on both sides, (7) the hydrogen ion permeable electrolyte membrane is a solid polymer electrolyte membrane (6) An apparatus for producing a hydride, and (8) An apparatus for producing a hydride according to claim 6 or 7, wherein the metal electrode is a platinum-rhodium composite electrode.
【０００６】次に、本発明の水素化物の製造装置の一実
施態様を図面に従って説明する。図１は、本発明の装置
の一実施例の断面図である。反応容器９は、金属電極２
を両面に取り付けた水素イオン透過性電解質膜１によっ
て、水素化反応室７と水電解室８に分割されている。電
極２はそれぞれ導線１０によって、直流電源１１の正
極、負極に接続されている。水素化反応室７にはライン
３より被水素化物を、水電解室８にはライン４より水ま
たは水蒸気を導入する。水電解室８で水の電気分解によ
り生じた水素イオンは、イオン透過膜１を透過して、水
素化反応室７側の電極上で被水素化物と反応する。生じ
た水素化物はライン５から抜き出される。また、水電解
室８で生じた酸素はライン６より抜き出される。さら
に、ライン５を被水素化物の導入に、ライン３を水素化
物の抜き出しに変更して使用することで反応効率を向上
させることもできる。Next, one embodiment of the hydride production apparatus of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view of one embodiment of the device of the present invention. The reaction vessel 9 is a metal electrode 2
Is divided into a hydrogenation reaction chamber 7 and a water electrolysis chamber 8 by a hydrogen ion permeable electrolyte membrane 1 attached on both sides. The electrodes 2 are connected to the positive electrode and the negative electrode of the DC power supply 11 by the conductors 10, respectively. A substance to be hydrogenated is introduced into the hydrogenation reaction chamber 7 through the line 3 and water or steam is introduced into the water electrolysis chamber 8 through the line 4. Hydrogen ions generated by the electrolysis of water in the water electrolysis chamber 8 permeate the ion permeable membrane 1 and react with the substance to be hydrogenated on the electrode on the hydrogenation reaction chamber 7 side. The produced hydride is extracted from the line 5. Further, oxygen generated in the water electrolysis chamber 8 is extracted from the line 6. Further, the reaction efficiency can be improved by using the line 5 for introducing the substance to be hydrogenated and the line 3 for extracting the hydride.
【０００７】本発明においては、水素化反応室７と水電
解室８との隔壁が水素イオン透過性電解質膜１で構成さ
れていることから、水電解室８から透過してくる全ての
水素は、水素化反応室７側の金属電極２の表面で水素化
反応に活性なイオン種となっている。したがって、水素
化反応室７側の金属電極２の表面では、きわめて効率良
く、電気化学的に水素化反応が行われることになる。In the present invention, since the partition wall between the hydrogenation reaction chamber 7 and the water electrolysis chamber 8 is composed of the hydrogen ion permeable electrolyte membrane 1, all the hydrogen that permeates from the water electrolysis chamber 8 The surface of the metal electrode 2 on the side of the hydrogenation reaction chamber 7 is an ionic species active in the hydrogenation reaction. Therefore, on the surface of the metal electrode 2 on the hydrogenation reaction chamber 7 side, the hydrogenation reaction is electrochemically performed extremely efficiently.
【０００８】本発明に用いる水素イオン透過性電解質膜
の材料としては、高分子固体電解質膜、例えばポリエチ
レンスルホン酸やテトラフルオロエチレン−ペルフルオ
ロスルホン酸共重合体などを用いることができ、好まし
くはテトラフルオロエチレン−ペルフルオロスルホン酸
共重合体である。膜厚は５０〜５００μｍ、好ましくは
７５〜２００μｍとする。As the material of the hydrogen ion permeable electrolyte membrane used in the present invention, a polymer solid electrolyte membrane such as polyethylene sulfonic acid or tetrafluoroethylene-perfluorosulfonic acid copolymer can be used, preferably tetrafluoroethylene. It is an ethylene-perfluorosulfonic acid copolymer. The film thickness is 50 to 500 μm, preferably 75 to 200 μm.
【０００９】金属電極については、正極と負極の電極は
同じでも異なってもよく、材料としては、パラジウム、
白金、ニッケル、ロジウム等の金属、及びその合金を用
いることができ、このうちの２種の金属の複合電極とし
てもよい。正極は好ましくは白金、ロジウム又はこれら
の複合電極である。負極は２種の金属の複合電極が好ま
しく、特に水素イオン透過性電解質膜の上に第一層（内
層）として白金を積層し、その上に第二層（外層）とし
てロジウムを積層した複合電極が好ましい。電極の厚さ
は０．１〜１００μｍ、好ましくは１〜５０μｍとす
る。この金属電極を水素イオン透過性電解質膜上に密着
するように取り付ける。取り付けの方法は密着性の上か
ら、それ自体公知のスパッタリング法、電気メッキ法、
化学メッキ法などで行うことが好ましく、２種の金属の
複合電極とする場合は、第１層の取り付けをスパッタリ
ング法で行い、その上に第２層を電気メッキ法で取り付
ける方法が特に好ましい。Regarding the metal electrode, the positive electrode and the negative electrode may be the same or different, and the material is palladium,
Metals such as platinum, nickel and rhodium, and alloys thereof can be used, and a composite electrode of two kinds of these metals may be used. The positive electrode is preferably platinum, rhodium or a composite electrode thereof. The negative electrode is preferably a composite electrode of two kinds of metals, and in particular, a composite electrode in which platinum is laminated as a first layer (inner layer) on a hydrogen ion permeable electrolyte membrane and rhodium is laminated as a second layer (outer layer) on it. Is preferred. The thickness of the electrode is 0.1 to 100 μm, preferably 1 to 50 μm. This metal electrode is attached so as to be in close contact with the hydrogen ion permeable electrolyte membrane. From the viewpoint of adhesion, the method of attachment is the sputtering method, the electroplating method, which is known per se.
It is preferable to carry out by a chemical plating method or the like, and in the case of a composite electrode of two kinds of metals, a method of mounting the first layer by a sputtering method, and a method of mounting a second layer thereon by an electroplating method are particularly preferable.
【００１０】本発明で用いる被水素化物は、水素の輸
送、貯蔵に利用するという点から、その水素化反応が可
逆的に生ずるものを用いる。好ましくは、窒素、一酸化
炭素もしくは二酸化炭素、アセトン、ベンゼンである。The substance to be hydrogenated used in the present invention is one which causes a reversible hydrogenation reaction from the viewpoint of being used for transporting and storing hydrogen. Preferred are nitrogen, carbon monoxide or carbon dioxide, acetone and benzene.
【００１１】金属電極への印加電圧は１．５〜２．４
Ｖ、好ましくは１．７〜２．１Ｖとする。電圧が高けれ
ば水素化物の生成速度は速くなるが、高すぎると透過し
た水素イオンの水素化反応への利用率が減少する。水電
解室に、この電圧と水電解室の容量に見合った流速で水
または水蒸気を供給し、通常の方法で水の電気分解を行
う。水素化反応室には、ここで発生する水素イオンの量
や反応速度に対して適正な流速で被水素化物を供給し、
水素化物を製造する。好ましくは、水素化物と水または
水蒸気とを対向供給する。The voltage applied to the metal electrode is 1.5 to 2.4.
V, preferably 1.7 to 2.1V. The higher the voltage, the faster the rate of hydride formation, but if the voltage is too high, the utilization rate of permeated hydrogen ions for the hydrogenation reaction decreases. Water or steam is supplied to the water electrolysis chamber at a flow rate that matches the voltage and the capacity of the water electrolysis chamber, and the water is electrolyzed by a normal method. The hydrogenation reaction chamber is supplied with a substance to be hydrogenated at an appropriate flow rate with respect to the amount of hydrogen ions generated here and the reaction rate,
Produces hydride. Preferably, the hydride and water or water vapor are supplied oppositely.
【００１２】[0012]
【実施例】次に、本発明を実施例に基づいてさらに詳細
に説明する。 実施例１ 水素イオン透過性電解質膜としてテトラフルオロエチレ
ン−ペルフルオロスルホン酸共重合体フィルム（膜厚２
００μｍ）、金属電極として正極、負極ともに白金−ロ
ジウム複合電極（水素イオン透過性電解質膜の上に白金
を５０Ｗ高周波スパッタリングで厚さ０．１μｍ蒸着
し、その上にロジウムを電気メッキで厚さ５μｍ電着）
を用いた図１に示したと同様の水素化物製造装置を使用
して、１気圧、５０℃で水電解と水素化の反応を行っ
た。水電解室（容量５０ｍｌ）には１２ｖｏｌ％の水蒸
気を１９ｍｌ／分の流量で、水素化反応室（容量５０ｍ
ｌ）には１４ｖｏｌ％ベンゼンを５ｍｌ／分の流量で供
給し、電極に１．８Ｖの電圧を印加したところ、水電解
によって０．２５ｍｌ／分の水素が発生し、その３．７
ｖｏｌ％が水素化反応に消費されて３×１０-3ｍｌ／分
のシクロヘキサンが生成した。水素化反応室でシクロヘ
キサン以外の生成物は検出されなかった。EXAMPLES Next, the present invention will be described in more detail based on examples. Example 1 A tetrafluoroethylene-perfluorosulfonic acid copolymer film (thickness 2
00 μm), both the positive electrode and the negative electrode as a metal electrode, a platinum-rhodium composite electrode (platinum was vapor-deposited on a hydrogen ion permeable electrolyte membrane to a thickness of 0.1 μm by 50 W high frequency sputtering, and rhodium was electroplated thereon to a thickness of 5 μm. Electrodeposition)
Using a hydride production apparatus similar to that shown in FIG. 1, the reaction between water electrolysis and hydrogenation was carried out at 1 atm and 50 ° C. In the water electrolysis chamber (capacity 50 ml), 12 vol% of steam was supplied at a flow rate of 19 ml / min, and the hydrogenation reaction chamber (capacity 50 m).
l) was supplied with 14 vol% benzene at a flow rate of 5 ml / min, and when a voltage of 1.8 V was applied to the electrodes, 0.25 ml / min of hydrogen was generated by water electrolysis.
Vol% was consumed in the hydrogenation reaction to produce 3 × 10 −3 ml / min of cyclohexane. No products other than cyclohexane were detected in the hydrogenation reaction chamber.
【００１３】実施例２ 電極に２．２Ｖの電圧を印加した以外は実施例１と全く
同様にして反応を行ったところ、シクロヘキサンの生成
速度は実施例１の１．８倍になった。Example 2 When a reaction was carried out in the same manner as in Example 1 except that a voltage of 2.2 V was applied to the electrode, the production rate of cyclohexane was 1.8 times that in Example 1.
【００１４】実施例３ 水素化反応室に窒素を５ｍｌ／分の流量で供給した以外
は実施例１と全く同様にして反応を行ったところ、１×
１０-4ｍｌ／分のアンモニアが生成した。水素化反応室
でアンモニア以外の生成物は検出されなかった。Example 3 The reaction was carried out in exactly the same manner as in Example 1 except that nitrogen was supplied to the hydrogenation reaction chamber at a flow rate of 5 ml / min.
10 −4 ml / min of ammonia was produced. No products other than ammonia were detected in the hydrogenation reaction chamber.
【００１５】実施例４ 水素化反応室に一酸化炭素を５ｍｌ／分の流量で供給し
た以外は実施例１と全く同様にして反応を行ったとこ
ろ、４×１０-4ｍｌ／分のメタノールが生成した。水素
化反応室でメタノール以外の生成物は検出されなかっ
た。Example 4 The reaction was carried out in exactly the same manner as in Example 1 except that carbon monoxide was supplied to the hydrogenation reaction chamber at a flow rate of 5 ml / min, and 4 × 10 −4 ml / min of methanol was obtained. Generated. No products other than methanol were detected in the hydrogenation reaction chamber.
【００１６】実施例５ 水素化反応室に２０ｖｏｌ％のアセトンを５ｍｌ／分の
流量で供給した以外は実施例１と全く同様にして反応を
行ったところ、６×１０-4ｍｌ／分のイソプロパノール
が生成した。水素化反応室でイソプロパノール以外の生
成物は検出されなかった。Example 5 The reaction was carried out in exactly the same manner as in Example 1 except that 20 vol% of acetone was supplied to the hydrogenation reaction chamber at a flow rate of 5 ml / min. As a result, 6 × 10 −4 ml / min of isopropanol was obtained. Was generated. No products other than isopropanol were detected in the hydrogenation reaction chamber.
【００１７】[0017]
【発明の効果】本発明によれば、水の電気分解によって
水素を発生させるのと同じ反応装置内で、水素の発生と
同時に効率良く、水素の輸送、貯蔵に適した水素化物に
変換することができる。本発明では、水素イオン透過性
電解質膜を介して水の電解反応から水素化反応に受け渡
される水素が反応に活性なイオン種であると同時に、電
極自体が触媒活性を有するため、水素化反応が非常に効
率良く行われる。また、水の電気分解では電力が消費さ
れるのに対し、水素化反応では電力の発生を伴うため、
全体としての電力が本来の水の電気分解に必要な電力よ
りも低減されるという効果を奏する。EFFECTS OF THE INVENTION According to the present invention, it is possible to efficiently convert hydrogen into a hydride suitable for transportation and storage of hydrogen simultaneously with the generation of hydrogen in the same reactor that generates hydrogen by electrolysis of water. You can In the present invention, the hydrogen transferred from the electrolysis reaction of water to the hydrogenation reaction through the hydrogen ion permeable electrolyte membrane is an ionic species active in the reaction, and at the same time, the electrode itself has a catalytic activity. Is done very efficiently. In addition, electricity is consumed in electrolysis of water, while electricity is generated in the hydrogenation reaction.
This has the effect that the electric power as a whole is reduced from the electric power required for the original electrolysis of water.
【図１】本発明の装置の一実施例の断面図である。1 is a cross-sectional view of one embodiment of the device of the present invention.
１ 水素イオン透過性電解質膜 ２ 金属電極 ３ 被水素化物導入ライン ４ 水あるいは水蒸気導入ライン ５ 水素化物放出ライン ６ 酸素放出ライン ７ 水素化反応室 ８ 水電解室 ９ 反応容器 １０ 導線 １１ 直流電源 1 hydrogen ion permeable electrolyte membrane 2 metal electrode 3 hydride introduction line 4 water or steam introduction line 5 hydride release line 6 oxygen release line 7 hydrogenation reaction chamber 8 water electrolysis chamber 9 reaction vessel 10 lead wire 11 DC power supply
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 31/04 9155−4Ｈ Ｃ０７Ｃ 31/04 31/10 9155−4Ｈ 31/10 Ｃ２５Ｂ 1/10 Ｃ２５Ｂ 1/10 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07C 31/04 9155-4H C07C 31/04 31/10 9155-4H 31/10 C25B 1/10 C25B 1/10
Claims (8)
付けた金属電極の正電極側に水または水蒸気、負電極側
に被水素化物を流し、又は満たして、該電極間に直流電
流を印加し、正電極側で水の電気分解を行って、生成し
た水素イオンを電解質膜の反対側へ透過させ、負電極側
で被水素化物の水素化反応を行わせることを特徴とする
水素化物の製造方法。1. A direct current is applied between the electrodes by flowing or filling water or steam on the positive electrode side of the metal electrodes attached to both sides of the hydrogen ion permeable electrolyte membrane and flowing or filling the hydrogenated substance on the negative electrode side. , The electrolysis of water on the positive electrode side, the generated hydrogen ions permeate to the opposite side of the electrolyte membrane, and the hydrogenation reaction of the hydride is performed on the negative electrode side. Method.
二酸化炭素、アセトンまたはベンゼンである請求項１記
載の水素化物の製造方法。2. The method for producing a hydride according to claim 1, wherein the substance to be hydrogenated is nitrogen, carbon monoxide or carbon dioxide, acetone or benzene.
電解質膜である請求項１又は２記載の水素化物の製造方
法。3. The method for producing a hydride according to claim 1, wherein the hydrogen ion permeable electrolyte membrane is a solid polymer electrolyte membrane.
く電気メッキ法によって取り付けられた２種の金属の複
合電極である請求項１、２又は３記載の水素化物の製造
方法。4. The method for producing a hydride according to claim 1, wherein the metal electrode is a composite electrode of two kinds of metals attached by a sputtering method and a subsequent electroplating method.
る請求項１、２、３又は４記載の水素化物の製造方法。5. The method for producing a hydride according to claim 1, 2, 3 or 4, wherein the metal electrode is a platinum-rhodium composite electrode.
電極側で被水素化物の水素化反応を行う水素化物の製造
装置において、水の電気分解の反応室と水素化の反応室
とが金属電極を両面に取り付けた水素イオン透過性電解
質膜によって隔てられていることを特徴とする水素化物
の製造装置。6. A hydride production apparatus for electrolyzing water on a positive electrode side of a metal electrode and hydrogenating a hydrogenation target on a negative electrode side, wherein a reaction chamber for electrolysis of water and a reaction chamber for hydrogenation are provided. An apparatus for producing a hydride, characterized in that and are separated by a hydrogen ion permeable electrolyte membrane having metal electrodes attached to both sides.
電解質膜である請求項６記載の水素化物の製造装置。7. The hydride production apparatus according to claim 6, wherein the hydrogen ion permeable electrolyte membrane is a solid polymer electrolyte membrane.
る請求項６又は７記載の水素化物の製造装置。8. The hydride production apparatus according to claim 6, wherein the metal electrode is a platinum-rhodium composite electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7047693A JP2700052B2 (en) | 1995-03-08 | 1995-03-08 | Hydride production method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7047693A JP2700052B2 (en) | 1995-03-08 | 1995-03-08 | Hydride production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08246177A true JPH08246177A (en) | 1996-09-24 |
| JP2700052B2 JP2700052B2 (en) | 1998-01-19 |
Family
ID=12782371
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7047693A Expired - Lifetime JP2700052B2 (en) | 1995-03-08 | 1995-03-08 | Hydride production method |
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| Country | Link |
|---|---|
| JP (1) | JP2700052B2 (en) |
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|---|---|
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| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |