JP2002012992A - Method for producing hydrogen gas - Google Patents
Method for producing hydrogen gasInfo
- Publication number
- JP2002012992A JP2002012992A JP2000198494A JP2000198494A JP2002012992A JP 2002012992 A JP2002012992 A JP 2002012992A JP 2000198494 A JP2000198494 A JP 2000198494A JP 2000198494 A JP2000198494 A JP 2000198494A JP 2002012992 A JP2002012992 A JP 2002012992A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen gas
- electrolytic solution
- acid
- sulfuric acid
- generated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- QAOWNCQODCNURD-ZSJDYOACSA-N Sulfuric acid-d2 Chemical compound [2H]OS(=O)(=O)O[2H] QAOWNCQODCNURD-ZSJDYOACSA-N 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 5
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 5
- 238000003487 electrochemical reaction Methods 0.000 claims abstract 2
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 2
- 239000002075 main ingredient Substances 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 36
- 239000010949 copper Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000003595 mist Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は水素ガスの製造方法
に関する。詳細には、本発明は異種金属間に発生する電
位差によって重水素硫酸を主成分とする電解液から、水
素ガスを製造する方法で、電気自動車及び家庭規模の電
力を対象とした水素自給型ターボ発電機の安価な水素ガ
スを提供することが出来る。[0001] The present invention relates to a method for producing hydrogen gas. Specifically, the present invention relates to a method for producing hydrogen gas from an electrolyte mainly composed of deuterated sulfuric acid by a potential difference generated between dissimilar metals, and is a hydrogen self-sufficient turbo for electric vehicles and home-scale electric power. Inexpensive hydrogen gas for the generator can be provided.
【０００２】[0002]
【従来の技術】従来、水素ガスの製造方法として省資
源、環境対応性から観て１異種金属起電方法２水ミスト
光触媒法３電気分解法の３方法が検討されている。2. Description of the Related Art Conventionally, as methods for producing hydrogen gas, three methods have been studied from the viewpoint of resource saving and environmental friendliness: (1) a method of generating a different metal, (2) a water mist photocatalytic method, and (3) an electrolytic method.
【０００３】１は異種金属間に発生する電位差によって
クエン酸等の有機酸の電解液から水素ガスを発生させる
もので、天候の如何に拘らず安定的に動作する。しかし
ながら現状では水素ガスの発生量が少なく、所望のレベ
ルにまで高めるためには装置本体が大掛りとなり、コス
ト的にも問題を有している。[0003] Reference numeral 1 denotes a device for generating hydrogen gas from an electrolytic solution of an organic acid such as citric acid by a potential difference generated between different metals, and operates stably irrespective of weather. However, at present, the amount of hydrogen gas generated is small, and in order to increase the amount of hydrogen gas to a desired level, the size of the apparatus main body becomes large and there is a problem in cost.
【０００４】一方２はミストファンで水をミスト状に
し、太陽光から抽出された紫外線域電磁波をTiO2等の表
面に照射することによってヒドロキシラジカルＯＨ等を
生じ、これが光触媒によってＨ2０ミストから水素ガス
を発生させる。この方法は天候に左右されるのと装置が
大きくなり過ぎる等課題を残している。On the other hand, a mist fan 2 converts water into a mist, and irradiates the surface of TiO2 or the like with ultraviolet rays extracted from sunlight to produce hydroxyl radicals OH, which generate hydrogen gas from H20 mist by a photocatalyst. generate. This method has problems such as that the size of the device becomes too large depending on the weather.
【０００５】３の電気分解法は電気を用いて電解液より
水素ガスを発生させる方法であるが、電力を使用する自
体に問題があり、余程効率的な電解法でない限り水素ガ
ス発生法の有力候補とはなり難い。[0005] The electrolysis method 3 is a method of generating hydrogen gas from an electrolytic solution using electricity. However, there is a problem in using electric power itself, and unless the electrolysis method is very efficient, the hydrogen gas generation method is not used. It is unlikely to be a strong candidate.
【０００６】[0006]
【発明が解決しようとする課題】水素ガスの製造には、
いろいろな方法があるが、操作が簡単で小型の装置で、
既存の電気やガスなどの外部エネルギーを使用すること
なく、クリーンで安価に製造することが課題である。本
発明は以上の観点より異種金属間に発生する電位差によ
ってクエン酸等の有機酸の電解液から水素ガスを効率的
に発生させる方法を目的とする。SUMMARY OF THE INVENTION In the production of hydrogen gas,
Although there are various methods, it is an easy-to-use and small device,
The challenge is to produce clean and inexpensive without using external energy such as existing electricity and gas. An object of the present invention is to provide a method for efficiently generating hydrogen gas from an electrolytic solution of an organic acid such as citric acid by a potential difference generated between different metals from the above viewpoints.
【０００７】[0007]
【課題を解決するための手段】本発明によれば、上記問
題点を解決するために、異種金属間に発生する電位差に
よる水素ガスを効率的に製造する方法において、電解液
を中心に鋭意検討した。According to the present invention, in order to solve the above-mentioned problems, a method for efficiently producing hydrogen gas by a potential difference generated between dissimilar metals has been intensively studied focusing on an electrolytic solution. did.
【０００８】その結果、電解液に使用されるクエン酸等
有機酸の全量（請求項３）又は一部（請求項４）を重水
素硫酸に置き換えることにより水素ガスの発生量が著し
く促進された。As a result, the amount of hydrogen gas generated is remarkably promoted by replacing the entire amount (claim 3) or a part (claim 4) of the organic acid such as citric acid used in the electrolytic solution with deuterium sulfuric acid. .
【０００９】[0009]
【発明の実施の形態】本発明の実施の形態を順を追って
説明する。 電解溶液に浸漬した密接した異種金属間に発生する電位
差による水素ガスを発生する方法における電位差は電気
化学順列表で既知である。この順列表により２種の金属
を選定すればよく、電位差は高い方が望ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described step by step. The potential difference in the method of generating hydrogen gas due to the potential difference generated between closely dissimilar metals immersed in an electrolytic solution is known from an electrochemical permutation table. Two metals may be selected according to this permutation table, and a higher potential difference is desirable.
【００１０】例えば、異種の２種の金属として、比較的
安価で豊富で加工が容易なZn（亜鉛）とCu（銅）が一般
に使われる。 一方電解溶液に使用する主剤は本発明のポイントとなる
重水素硫酸である。従来はクエン酸、グリシン、ケイ皮
酸、コハク酸、サリチル酸、ギ酸、グルタミン酸、アス
クロビン酸、シュウ酸、酒石酸、乳酸、酢酸などの有機
酸が使用されるが、中でも解離定数の高いものから毒
性、価格などを評価して選ばれている。For example, as two kinds of different metals, Zn (zinc) and Cu (copper), which are relatively inexpensive, abundant and easy to process, are generally used. On the other hand, the main agent used in the electrolytic solution is deuterated sulfuric acid, which is the point of the present invention. Conventionally, organic acids such as citric acid, glycine, cinnamic acid, succinic acid, salicylic acid, formic acid, glutamic acid, ascrobic acid, oxalic acid, tartaric acid, lactic acid, and acetic acid are used. , Price and so on.
【００１１】[0011]
【実施例】電解溶液の主剤を従来の有機酸から重水素硫
酸に一部又は全量を置換えることにより、電解溶液から
水素ガスの発生が著しく増加する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS By substituting a part or the whole of the main component of the electrolytic solution from the conventional organic acid with deuterated sulfuric acid, the generation of hydrogen gas from the electrolytic solution is significantly increased.
【００１２】異種金属として亜鉛と銅を選び、他の条件
を同一にして、電解溶液の主剤にクエン酸を使用した場
合と本発明による重水素硫酸の場合で水素発生量を比較
した。（図１，２参照） この結果、本発明による重水素硫酸を電解液の主剤とし
て使用することにより、水素発生量が従来法のクエン酸
に比較して５〜６倍増加することが分かる。又クエン酸
と重水素硫酸を同量用いた電解液の場合も上記と同じ条
件で水素発生量を測定したところ，図３の如く従来のク
エン酸単独の場合に比べて、大量の水素発生がみられ
た。[0012] Zinc and copper were selected as dissimilar metals, and the other conditions were the same. The amount of hydrogen generated was compared between the case where citric acid was used as the main component of the electrolytic solution and the case of deuterated sulfuric acid according to the present invention. As a result, it can be seen that the use of deuterated sulfuric acid according to the present invention as a main component of the electrolytic solution increases the amount of generated hydrogen by 5 to 6 times as compared with the conventional citric acid. In addition, when the amount of hydrogen generated was measured under the same conditions as above in the case of the electrolyte using the same amount of citric acid and deuterated sulfuric acid, a large amount of hydrogen was generated as compared to the conventional citric acid alone as shown in FIG. Was seen.
【００１３】異種金属間に発生する電位差によって、電
解溶液から水素ガスを発生する方法において、電解溶液
のＰＨは０.５〜４.０が望ましい。電解溶液のＰＨを重
水素硫酸にて０．６に調整後、亜鉛・銅の異種金属間に
水素ガスが発生し始めるとＰＨは上昇し、一定時間後Ｐ
Ｈ＝０．９に安定してくる。（図４） ＰＨと同時に電解溶液の液温を測定したところ２２．２
℃でスタートして１５００sec（２５分）後では２３．
１℃と逆に温度が上昇した。（図５） 従来より使われているクエン酸による電解溶液の場合２
９℃から２7℃まで約２℃液温が低下した。In a method for generating hydrogen gas from an electrolytic solution by a potential difference generated between dissimilar metals, the pH of the electrolytic solution is preferably 0.5 to 4.0. After adjusting the pH of the electrolytic solution to 0.6 with deuterated sulfuric acid, when hydrogen gas starts to be generated between the different metals of zinc and copper, the PH rises, and after a certain time, the pH rises.
It stabilizes at H = 0.9. (FIG. 4) When the solution temperature of the electrolytic solution was measured at the same time as the PH, 22.2 was obtained.
23 ° C. after 1500 seconds (25 minutes) starting at 25 ° C.
The temperature rose opposite to 1 ° C. (Fig. 5) In the case of a conventional electrolytic solution using citric acid 2
The liquid temperature dropped by about 2 ° C from 9 ° C to 27 ° C.
【００１４】電解溶液の液温は水素ガス発生量に比例す
るので、重水素硫酸を電解溶液の主剤に使用した本発明
の場合、特に電解溶液の温度低下のための加温は特に必
要なく、装置の簡素化のため有利となる。Since the temperature of the electrolytic solution is proportional to the amount of hydrogen gas generated, in the case of the present invention in which deuterated sulfuric acid is used as the main component of the electrolytic solution, no particular heating is required to lower the temperature of the electrolytic solution. This is advantageous for simplifying the device.
【００１５】[0015]
【発明の効果】以上のように、本発明によれば、異種金
属間に発生する電位差による水素ガスを効率的に製造す
る方法において、電解液に使用されるクエン酸等有機酸
の全量又はその一部を重水素硫酸に置換えることにより
水素ガスの発生量が著しく増大することが出来る。又、
電解液の温度も上昇傾向にあるので、装置の保温、加熱
等も必要なく装置の簡素化に優利となる。As described above, according to the present invention, in a method for efficiently producing hydrogen gas by a potential difference generated between dissimilar metals, the total amount of an organic acid such as citric acid or the like used in an electrolytic solution is reduced. By partially substituting deuterated sulfuric acid, the amount of generated hydrogen gas can be significantly increased. or,
Since the temperature of the electrolytic solution also tends to increase, it is not necessary to keep the device warm or heated, which is advantageous for simplifying the device.
【図１】クエン酸を電解溶液の主剤として使用し、亜鉛
・銅間に発生する水素ガス量を経時的にプロットしたも
のである。FIG. 1 is a graph in which the amount of hydrogen gas generated between zinc and copper is plotted with time using citric acid as a main component of an electrolytic solution.
【図２】重水素硫酸を電解溶液の主剤として使用し、亜
鉛・銅間に発生する水素ガス量を経時的にプロットした
ものである。FIG. 2 is a graph in which the amount of hydrogen gas generated between zinc and copper is plotted with time using deuterium sulfuric acid as a main component of an electrolytic solution.
【図３】重水素硫酸／クエン酸＝1／1（重量比）を電解
溶液の主剤として使用し、亜鉛・銅間に発生する水素ガ
ス量を経時的にプロットしたものである。FIG. 3 is a graph in which the amount of hydrogen gas generated between zinc and copper is plotted with time using deuterated sulfuric acid / citric acid = 1/1 (weight ratio) as a main component of an electrolytic solution.
【図４】重水素硫酸を電解溶液の主剤として使用し、亜
鉛・銅間に水素が発生する間ＰＨ変化を経時的にプロッ
トしたものである。FIG. 4 is a graph plotting the change in PH over time while hydrogen is generated between zinc and copper using deuterated sulfuric acid as a main component of an electrolytic solution.
【図５】重水素硫酸を電解溶液の主剤として使用し、亜
鉛・銅間に水素が発生する間液温変化を経時的にプロッ
トしたものである。FIG. 5 is a graph plotting a change in liquid temperature over time while hydrogen is generated between zinc and copper using deuterium sulfuric acid as a main component of an electrolytic solution.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田中 好郎 兵庫県西宮市甲風園１−９−８ Ｆターム(参考） 4K021 AA01 BA06 BC09 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshiro Tanaka 1-9-8 Kofuen, Nishinomiya-shi, Hyogo F-term (reference) 4K021 AA01 BA06 BC09
Claims (2)
気化学反応によって水素ガスを発生させる方法に於い
て、電解液の主剤として重水素硫酸を使用することを特
徴とする水素ガス製造方法。1. A method for producing hydrogen gas by an electrochemical reaction utilizing a potential difference generated between dissimilar metals, wherein deuterated sulfuric acid is used as a main component of an electrolytic solution. .
れている有機酸を併用することを特徴とする水素ガス製
造方法。2. A method for producing hydrogen gas, comprising using the organic acid currently used in deuterium sulfuric acid according to claim 1 together.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000198494A JP2002012992A (en) | 2000-06-30 | 2000-06-30 | Method for producing hydrogen gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000198494A JP2002012992A (en) | 2000-06-30 | 2000-06-30 | Method for producing hydrogen gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002012992A true JP2002012992A (en) | 2002-01-15 |
Family
ID=18696651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000198494A Pending JP2002012992A (en) | 2000-06-30 | 2000-06-30 | Method for producing hydrogen gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002012992A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7166269B2 (en) * | 2001-02-22 | 2007-01-23 | Yoshirou Tanaka | Method for producing hydrogen gas |
-
2000
- 2000-06-30 JP JP2000198494A patent/JP2002012992A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7166269B2 (en) * | 2001-02-22 | 2007-01-23 | Yoshirou Tanaka | Method for producing hydrogen gas |
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