JPS58156503A - Process for preparing hydrogen - Google Patents

Process for preparing hydrogen

Info

Publication number
JPS58156503A
JPS58156503A JP57035204A JP3520482A JPS58156503A JP S58156503 A JPS58156503 A JP S58156503A JP 57035204 A JP57035204 A JP 57035204A JP 3520482 A JP3520482 A JP 3520482A JP S58156503 A JPS58156503 A JP S58156503A
Authority
JP
Japan
Prior art keywords
light
complex
hydrogen
rhodium
visible light
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
JP57035204A
Other languages
Japanese (ja)
Other versions
JPS612602B2 (en
Inventor
Isao Shiojima
塩島　勲
Shiyuri Hosaka
穂坂　朱里
Keiko Tajime
田治米　恵子
Shigero Oishi
茂郎 大石
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.)
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
Agency of Industrial Science and Technology
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 Agency of Industrial Science and Technology filed Critical Agency of Industrial Science and Technology
Priority to JP57035204A priority Critical patent/JPS58156503A/en
Publication of JPS58156503A publication Critical patent/JPS58156503A/en
Publication of JPS612602B2 publication Critical patent/JPS612602B2/ja
Granted legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • 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

Abstract

PURPOSE:To prepare hydrogen with using effectively irradiating light without causing the decomposition of a substrate, by irradiating a mixture of a thiol compound and a rhodium complex with visible light using an organic solvent or neutral water. CONSTITUTION:A mixture of a thiol compound (e.g., thiophenol, propanethiol, etc.) shown by the formula (R is alkyl or aryl) and a rhodium complex e.g., chlorocarbonylbis(triphenylphosphine)rhodium(I), etc. is irradiated with visible light, to prepare hydrogen. According to this method, an organic solvent or neutral water can be used, a substrate is prevented from being decomposed, and the irradiating light is effectively used.

Description

【発明の詳細な説明】 本発明は水素Ｏ製造方法に関する。］Ｉ’に詳しく社、
一般式 （式中、＆紘ア＃中に基又はアリ−に基である。）で表
わされるチオール化合物とロジクム錯体との拠金物に可
視光を照射させることによる水素の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing hydrogen O. ]I' details company,
The present invention relates to a method for producing hydrogen by irradiating visible light to a support of a thiol compound represented by the general formula (wherein &Hiroa is a group or ary) and a Rhodicum complex.

最近、エネルギー変換に関する研究は数多くみられる。Recently, there has been a lot of research on energy conversion.

ｌＩ＃に光エネルギーの熱、化学、あるいは電気エネル
ギーへの変換は科学に課せられた重要な問題として取）
あげられている、そＯ中で、光エネルギーの化学エネル
ギーへの変換Ｏうち、水素生成に関してはエネルギー源
としての水素利用と−う点で多数の研究が進められて−
る。The conversion of light energy into thermal, chemical, or electrical energy is considered an important scientific problem.
Of these, many studies have been carried out regarding the conversion of light energy into chemical energy, and the use of hydrogen as an energy source for hydrogen production.
Ru.

水素生成に関する研究はこれまでにも莫大な数が存在し
、これらＯ中Ｋｔｉ熱化学ナイクルを用−九本のｌｌ接
分解Ｏ例として、例えばＦａ−０１ｊ％ナイタｙ（Ｒ，
Ｈ，Ｗｅａｔｏｒｆ　Ｊｒ、、　Ｒ，１，Ｈｅｉａｅｍ
ａｎｐ８ｃｌａｓｃｅ、　１８０．５１１　（１９７４
）参照〕、あるいは光半導体を用ＩＡ九光電池系による
水の直接分解０例として例えｔｆ　Ｔ　ｉ　０２−Ｐ　
を光電池を用％ｆｈ、ｂ方法〔ム、Ｆｕｊｉｓｈｉｍ＆
に−Ｈａｎｄｓ、Ｂｍ１１．Ｏｋ＊ｉｍ、８ｏｃｅＪａ
ｐ、、　４４．１１４８（１９７１）参照〕などが知ら
れてｉる。There have been a huge number of studies on hydrogen production, and for example, Fa-01j%Ny(R,
H, Weatorf Jr., R,1, Heiaem
anp8clasce, 180.511 (1974
)], or use an optical semiconductor as an example of direct decomposition of water by a photovoltaic cell system.
The photocell for %fh, b method [mu, Fujishim &
- Hands, Bm11. Ok*im, 8occeJa
p., 44.1148 (1971)] are known.

しかしながら、前者Ｏ系にシいては省エネルギーという
点、又、熱再生、熱回収という操作の煩雑性が常に問題
として提起されている。更に、光半導体を用い丸糸は光
として紫外領域を用いる必要がある、光の透過性が劣る
など太陽光利用とｉう藺かも社少なからず問題を含む系
といえる。従うて光エネルギー（特に太陽光）の利用に
よゐ水素生成ということからすれば可視光領域の光を用
−九本素製造方法の開発が歯面の課題でめ）、可視光を
利用し九本の光分解に関してはこれといつえ良一方法は
見出されて−ないのが現状である。However, in the case of the former O system, energy saving and the complexity of operations such as heat regeneration and heat recovery have always been raised as problems. Furthermore, it can be said that circular threads using optical semiconductors have a number of problems, such as the need to use ultraviolet light as the light source and poor light transmittance. Therefore, when it comes to hydrogen production by using light energy (particularly sunlight), it is necessary to develop a method for producing nine elements using light in the visible light range. As for the photolysis of nine fibers, no similar method has yet been found.

このような可視光による水の分解を試みようとした例と
してａ　１　）　Ｊ−Ｍ−Ｌａｂｎらの方法（Ｊ。An example of attempting to decompose water using visible light is the method of a1) J-M-Labn et al. (J.

Ｍ−Ｌｅｋｎｅ　　Ｊ、　Ｐ、　　８　ａｕｖａｇｅｐ
　Ｎｏｕｖ、Ｊ、　Ｏｋ＠ａｓ、ｓ　　Ｌ４４９（１９
７７）参照〕、２　）　Ｇ、ＭｃＬｅｎｄｏｎらの方法
（Ｇ−ＭｃＬ＠ｎｄｏｎｅ　Ｄ−Ｓ−Ｍｉｌｌｅｒ、　
Ｊ−０，８゜０ｈａｍ−０ｏａｕｎ、ｓ　５３５　（１
９８０）参照）、５）Ｍ’Ｇｒｉｔｘｅｌらの方法（Ｋ
、Ｋａｌｙａｎａｓｕｄａｒ６ｎ、　Ｍ。M-Lekne J, P, 8 auvagep
Nouv, J. Ok@as, s L449 (19
77)], 2) G. McLendon et al.'s method (G-McL@ndone D-S-Miller,
J-0,8゜0ham-0oaun,s 535 (1
980)), 5) M'Gritxel et al.'s method (K
, Kalyanasudar6n, M.

Ｇｒｉｔｘｅｌ＊Ａｎｇｅｗ、Ｏｈｅｍ、Ｉｎｔ、Ｅｄ
、Ｂｎｇｌ、。Gritxel*Angew, Ohem, Int, Ed
,Bngl,.

１８．７０１（１９７９）参照〕、４　）　Ｈ，Ｋａｇ
ａｉらの方法〔ルＭｏｒａｄｐｏｕｒｅ　＆　Ａｍｏｕ
ｙａｌ＊　Ｐ、　Ｋｅｌ　１　ｅｖｅＨ，Ｋａｇａｎ、
、　Ｎｏｕｖ、　Ｊ、　Ｏｈｅｍ、ｓ　２ｓ　５４７　
（１９７８）参照〕更に５　）　１．０ｋｕｒａらの方
法（１，０ｋｕｒａＮ、　Ｋｉｎ−Ｔｈｕａｎ＊　Ｊ、
Ｍｏ１−０ａｔ−、！、　！１１　（１９７９）参照〕
等が知られている。これらのいずれもが電子供与体とし
ては水塊外に酸化されヤす−、電子を放出しやす一有機
物を使用し、不可逆的な酸化体となるなどの欠点を持っ
ている。更に、水素生成時Ｋａ不不一−触媒ある白金コ
ロイドなどを使用しておシ、光の透過率も悪い。又、水
からの水素生成の際は溶液ＯｐＨは極めて酸性が強く、
ある種の基質は分解す、る可能性もあるなどの欠点があ
る。18.701 (1979)], 4) H, Kag.
Ai et al.'s method [Moradpoure & Amou
yal* P, Kel 1 eveH, Kagan,
, Nouv, J., Ohem, s 2s 547
(1978)] Furthermore, 5) 1.0kura et al.'s method (1.0kuraN, Kin-Thuan* J,
Mo1-0at-,! , ! 11 (1979)]
etc. are known. All of these have drawbacks such as using an organic substance as an electron donor that is likely to be oxidized outside the water body and release electrons, resulting in irreversible oxidation. Furthermore, when a platinum colloid or the like is used as a catalyst for hydrogen generation, the light transmittance is poor. Also, when hydrogen is produced from water, the solution OpH is extremely acidic;
There are disadvantages such as the possibility that some substrates will degrade.

本発明者等社従来法Ｏ欠点を克服すべく検討した結果、
・有機溶媒あるｉは中性の水を用ｉることによ〉基質の
分解をさまたげ、照射光を効果的に利用できる水素製造
法を見出し本発明を完成しえ。As a result of the inventors' study to overcome the drawbacks of the conventional method,
・By using neutral water as an organic solvent, we have discovered a hydrogen production method that prevents the decomposition of the substrate and makes effective use of irradiated light, thereby completing the present invention.

又、本発明は電子供与体であるチオールはそれ自身がプ
曹トン源でもあ）、有効な水素生成基質といえる。Furthermore, in the present invention, thiol, which is an electron donor (it is also a carbonate source), can be said to be an effective hydrogen production substrate.

本発明は一般式 （式中、ＲＦｉアル中ル基又はアリール基である。）で
表わされるチオール化合物よシ水素を製造すｂものであ
る。チオール化合物としては、チオフェノール、０−メ
ト争クチオフエノール、べ／タフロ―チオフェノール、
β−ナフタレンチオールの如きアリールチオール、エタ
ンチオール、プロパンチオールの如きアル中ルテオール
などを用いることができる。The present invention is directed to the production of hydrogen from a thiol compound represented by the general formula (wherein RFi is an alkyl group or an aryl group). Examples of thiol compounds include thiophenol, 0-methoxythiophenol, be/taflothiophenol,
Arylthiols such as β-naphthalenethiol, luteol in alcohol such as ethanethiol and propanethiol, and the like can be used.

本発明は■ジウム錯体の存在下に行うことが必須の要件
である。四ジクム錯体紘本発明にお−て光触媒として作
用するものであ為。本発明に使用できる田ジウム錯体と
してはり０μノルポルナジエンロシウム（１）二量体、
クロロカルボニルビス（トリフェニルホスフィン）ロジ
ウム（１）％ナト２中ス（トリ７工二ル本スフィン）ロ
ジウム（１）ヒドリド、りｐロビス（シクロオクテン）
ロジウム０）、クロロトリス（トリフェニルホスフィン
）ａジクム（■入ジー声−クロロテトフカルボニルニロ
ジウム４ｐ）等を例示することができる。ロジウム錯体
の使用量はＤＪ）２〜２ｍＭ　使用できるが、光の透過
率等を考慮し、０−１〜０−４ｍＭ０範囲が好まし一〇
本発明Ｆｉｊ！に可視光照射下に行うことが必須の要件
である。本発明で―う可視光は６８０〜８００ａｍ（）
波長域の光を言うものである。本発明においてこれらの
波長域の光を中上ノンＩ）ｙプあるいはタングステン−
ハロゲン２７グ等によって得たものを用いてもよいが、
当然太陽光でありて差支えない。It is essential for the present invention to be carried out in the presence of a dium complex. The tetradium complex acts as a photocatalyst in the present invention. Examples of the metal complexes that can be used in the present invention include 0μ norpornadienerosium (1) dimer;
Chlorocarbonylbis(triphenylphosphine)Rhodium(1)%Nato2S(tris(tri-7-dimethylphosphine))Rhodium(1)hydride, cyclobis(cyclooctene)
Examples include rhodium 0), chlorotris(triphenylphosphine)a dicum (■-in-glow-chlorotetophcarbonylnirodium 4p), and the like. The amount of rhodium complex to be used can be DJ) 2 to 2mM, but in consideration of light transmittance etc., it is preferably in the range of 0-1 to 0-4mM0. It is essential that the test be carried out under visible light irradiation. In the present invention, visible light is 680 to 800 am ()
It refers to light in a wavelength range. In the present invention, light in these wavelength ranges is converted to Nakagami non-I) y-propylene or tungsten.
You may also use those obtained by halogen 27g, etc.
Naturally, it can be sunlight.

本発明は前記したロジウム錯体にルテニウム錯体を共存
させると水素の生成効率が向上するので好ましい。使用
できるルテニウム錯体としては、ジクロロトリス（ビピ
リジル）ルテニウム・６水和物、ジブ−モトリス（ビピ
リジル）ルテニウム・６水和物等を例示することができ
る。ルテニウム錯体の使用量はロジウム錯体に対して通
常はぼ当セル量を用いる。In the present invention, it is preferable to make a ruthenium complex coexist with the above-described rhodium complex, since this improves hydrogen production efficiency. Examples of the ruthenium complex that can be used include dichlorotris(bipyridyl)ruthenium hexahydrate, dibu-motris(bipyridyl)ruthenium hexahydrate, and the like. The amount of the ruthenium complex to be used is usually the equivalent cell amount to the rhodium complex.

本発明はアミン類の共存下に行うことが水素の生成効率
が向上する点で好ましい。アミンとしては、トリエタノ
ールアミン（ＴＥＡ）、）ジエチルアミン、トリアリル
アミン、ピリジン等の第三級アミン、ジエチルアミン、
ビロール等の第二級アミンを使用することができるが、
効率よく水素を得叫 るためには第三級ア（ンの使用が好ましい。アミンの使
用量はロジウム錯体に対して１〜２０倍モル用−ること
ができる。反応を効率よく行うには、２〜５倍モル用−
ることが好ましい。The present invention is preferably carried out in the coexistence of amines because hydrogen production efficiency is improved. Examples of amines include triethanolamine (TEA), tertiary amines such as diethylamine, triallylamine, and pyridine, diethylamine,
Although secondary amines such as virol can be used,
In order to efficiently obtain hydrogen, it is preferable to use a tertiary amine.The amount of amine used can be 1 to 20 times the molar amount of the rhodium complex.In order to carry out the reaction efficiently, , for 2 to 5 times molar
It is preferable that

本発明を実施する場合にはチオール自身を溶媒として使
用すること龜可能であるが、錯体Ｏ溶解性等を考慮し、
アセトニトリル−水、ア竜ト二トリルー炭酸ジメチル、
アセトニトリル−炭酸エチレンなどの混合溶媒系を用い
ることができる。更に、エタノールあるいはベンゾニト
リへアセトニトリル等のニトリル系溶媒も使用可能であ
る。When carrying out the present invention, it is possible to use the thiol itself as a solvent, but considering the solubility of the complex O,
Acetonitrile-water, arthrotonitrile-dimethyl carbonate,
Mixed solvent systems such as acetonitrile-ethylene carbonate can be used. Furthermore, nitrile solvents such as ethanol or benzonitrile-acetonitrile can also be used.

反応扛０〜６０℃で進行するが加熱、冷却等の手段を用
−る必要がない点で室温で行うことが好ましい。Although the reaction proceeds at a temperature of 0 to 60°C, it is preferable to carry out the reaction at room temperature since there is no need to use means such as heating or cooling.

以下実施例を示し詳述する。Examples will be shown and explained in detail below.

実施例１〜４ チオフェノ−Ｎ溶液を含むアセトニトリル溶液を１０　
　ｍｍＨｇ程度の高真空ラインを用い凍結−説気一溶解
を３回くシ返し、ツイン上の別なコνりに接続した、錯
体−トリエタノールアミンを含む＆−ｊム中ヤッグ付反
応容器に真空置換した。Examples 1-4 Acetonitrile solution containing thiopheno-N solution
Using a high vacuum line of about mmHg, repeat the freezing-inflation-dissolution process three times, and place the complex in a reaction vessel containing triethanolamine and a jug, which is connected to another link on the twin. Vacuum replacement was performed.

反応容器Ｅｌｌ液を置換し、筐体窒素で凍結脱気後、６
５０Ｗのタングステンハロゲンラ／プを備見えプロジェ
クタ−で光照射した。光＃１４０８ｍｍ以下をガクスフ
イルターを用いて線断し丸、一定時間光照射後、系内を
アルゴンガスて雪圧にもどじ、その一定量を採取しガス
クロマトグラフ１−で生成水素を定性定量した０反応条
件及びその結果を表１に示した。尚、力２ムクロ！トゲ
２）１−の条件は以下の通シである。Replace the Ell liquid in the reaction vessel, freeze and degas the case with nitrogen, and then
Light was irradiated with a 50W tungsten halogen lamp using a visible projector. Light #1408mm or less is cut into a circle using a gas filter. After irradiation with light for a certain period of time, the system is returned to snow pressure with argon gas, and a certain amount of it is collected and the hydrogen produced is qualitatively and quantitatively determined using a gas chromatograph 1-. The reaction conditions and results are shown in Table 1. In addition, power 2 Mukuro! Thorn 2) The conditions for 1- are as follows.

力２ム　　：モレ命−７−シーブ　５Ａ１ｍ力２ム温度
二室温、　ディテクター温［：１００℃中ヤリアーガス
：アルゴン 表　　　　１ ！ （溶媒ニアセトニトリル５ａＪ） 実施例５〜８ 溶媒を変えた以外は実施例１と同様に操作を行い、水素
生成を確認定量した。但し炭酸エチレンは固体であるＯ
で反応容器中に秤量し九。反応条件及びそＯ結果を表２
に示した。Force 2m: Molecule life - 7-sieve 5A1m Force 2m Temperature 2 Room temperature, Detector temperature [: 100℃, Yaria gas: Argon Table 1! (Solvent Niacetonitrile 5aJ) Examples 5 to 8 The same operation as in Example 1 was performed except that the solvent was changed, and hydrogen production was confirmed and quantified. However, ethylene carbonate is a solid O
Weigh into the reaction vessel at 9. Table 2 shows the reaction conditions and results.
It was shown to.

実施例９〜１１ トリアリルホス７（ンを反応容器中に秤量し九以外は実
施例１と同様に行りた。反応条件及びその結果を表６に
示しえ。Examples 9 to 11 The same procedure as in Example 1 was carried out except that 7 (7) triallylphos was weighed into the reaction vessel. The reaction conditions and results are shown in Table 6.

表　　　５ （ｊｌ［ニアセトニトリル５ａｊ） 実施例１２〜１５ ジクロロトリス（ビピリジ、４／）ルテニウムを反応容
器中に秤量して加え、各種アミンをトリエタノールアミ
ンに変えた以外は実施例１と同様に行りた。反応条件及
びその結果を表４に示した。Table 5 (jl[niacetonitrile 5aj) Examples 12-15 Same as Example 1 except that dichlorotris(bipyridi, 4/)ruthenium was weighed and added into the reaction vessel and various amines were changed to triethanolamine. I went. The reaction conditions and results are shown in Table 4.

〜〉ぐ−一 手　　続　　補　　正　　書（自発） 昭和５８年３月３θ日 特許庁長官　　若杉和夫殿 １、事件の表示 昭和５７年特許願第３５２０４　号 ２゜発明の名称 水素の製造方法 ３、補正をする者 事件との関係　　　　特許出願人 トウキヨウトチ　ヨ　ダクカスミ　セキ住所　東京都千
代田区霞が関−丁目３番１号明細書の「発明の詳細な説
明」の欄 ５、補正の内容 （１）本願明細書第１２頁２行の「アリル」を「アリー
ル」に訂正する。～〉gu-1 Procedural amendment (voluntary) March 3, 1980 Director-General of the Patent Office Kazuo Wakasugi 1. Indication of the case Patent application No. 35204 of 1983 2. Name of the invention Process for producing hydrogen 3. Amendment Relationship with the case of a person who makes a patent application Address: 3-1 Kasumigaseki-chome, Chiyoda-ku, Tokyo Column 5 of "Detailed Description of the Invention" of the specification, Contents of the amendment (1) Specification of the present application Correct "allyl" in line 2 of page 12 to "aryl".

以上that's all

Claims (2)

【特許請求の範囲】[Claims] （１）　　一般式 で表わされるチオール化合物とｐジクム錯体との混合物
に可視光を照射させることからなる、水素の製造方法（
式中、Ｒａアルキル基又社了り一に基である。）。(1) A method for producing hydrogen, which comprises irradiating a mixture of a thiol compound represented by the general formula and a p-dicum complex with visible light (
In the formula, Ra is an alkyl group or a group. ). （２）ルテニウム錯体Ｏ共存下に行うことからなＬ特許
請求の範囲第（１）項に記載の方法。 φ）　アミン類の共存下に行うことからなる、特許請求
の範囲第（１）又は０項に記載の方法。(2) The method according to claim (1), which is carried out in the coexistence of a ruthenium complex O. φ) The method according to claim 1 or 0, which is carried out in the presence of amines.
JP57035204A 1982-03-08 1982-03-08 Process for preparing hydrogen Granted JPS58156503A (en)

Priority Applications (1)

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JP57035204A JPS58156503A (en) 1982-03-08 1982-03-08 Process for preparing hydrogen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57035204A JPS58156503A (en) 1982-03-08 1982-03-08 Process for preparing hydrogen

Publications (2)

Publication Number Publication Date
JPS58156503A true JPS58156503A (en) 1983-09-17
JPS612602B2 JPS612602B2 (en) 1986-01-27

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Country Link
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1692076A2 (en) * 2003-11-26 2006-08-23 Asemblon, Inc. Method and device for hydrogen storage and delivery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1692076A2 (en) * 2003-11-26 2006-08-23 Asemblon, Inc. Method and device for hydrogen storage and delivery
EP1692076A4 (en) * 2003-11-26 2008-03-05 Asemblon Inc Method and device for hydrogen storage and delivery
US8459032B2 (en) 2003-11-26 2013-06-11 Asemblon, Inc. Method and device for hydrogen storage and delivery

Also Published As

Publication number Publication date
JPS612602B2 (en) 1986-01-27

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