JPS6257563B2 - - Google Patents
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- Publication number
- JPS6257563B2 JPS6257563B2 JP58246321A JP24632183A JPS6257563B2 JP S6257563 B2 JPS6257563 B2 JP S6257563B2 JP 58246321 A JP58246321 A JP 58246321A JP 24632183 A JP24632183 A JP 24632183A JP S6257563 B2 JPS6257563 B2 JP S6257563B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen gas
- hydrogen
- gas
- silicon
- sample
- 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
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 47
- 150000002894 organic compounds Chemical class 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 239000007789 gas Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 16
- 239000010453 quartz Substances 0.000 description 14
- 239000011863 silicon-based powder Substances 0.000 description 14
- 238000000746 purification Methods 0.000 description 12
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000003708 ampul Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 235000012000 cholesterol Nutrition 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
〔発明の技術分野〕
本発明は、有機化合物の組成式決定のための水
素の定量や不純物を含む水素ガスの高純度化に利
用される水素ガス分離法に関する。
〔発明の技術的背景とその問題点〕
有機化合物中の水素定量法としては、従来、(1)
試料をO2と共に燃焼してH2Oとして定量する、
(2)高エネルギー粒子線を照射して反射粒子線のエ
ネルギー分布から水素を定量する、などの方法が
あつた。
しかしながら、従来の方法はいずれも分析操作
が面倒である、精度が悪い、非常に特殊な装置を
必要とする、などの欠点があつた。特に微量試料
の水素定量は困難であつた。
一方、気相成長による薄膜形成装置等において
は、高純度水素ガスを導入することが多い。これ
に供給される水素ガスの純化法としては、従来、
(1)アルミナ等の吸着剤により不純物を吸着させる
方法、(2)水素ガスをパラジウム板を通過させるこ
とにより純化する方法、などがあつた。
しかしながらこれらの方法による純化装置は、
物理的吸着あるいは拡散現象を利用するものであ
つて真空装置内に純化装置を設置することが困難
である。そのために別途導入配管を必要とし、こ
の配管内壁からの不純物ガス発生が問題となる。
〔発明の目的〕
本発明は、従来法と全く異なる原理に基づき、
極微量の有機化合物試料についても簡単かつ精度
よく水素の定量分析を可能とし、また不純物を含
む水素ガスを簡便かつ安価な装置で純化すること
を可能とした水素ガス分離法を提供することを目
的とする。
〔発明の概要〕
本発明は、Ｈの他にＣ，Ｎ，Ｏのうち少くとも
一種の元素を含む試料を、真空中又は不活性ガス
中で高温加熱されたシリコンの表面に導き、Ｃ，
Ｎ，Ｏ等を固体のシリコン化合物として固定化し
て水素ガスのみを分離することを特徴としてい
る。
例えば一般式ＣoＨnＯpＮqで表わされる有機化
合物ガスの場合、次のような反応式でシリコンと
反応して分解し、水素ガスを発生する。
（Si）s＋（ＣoＨnＯpＮq）g→（SiC）s（SiO2）s＋
（Si3N4）s＋（H2）g↑
上の反応式で、添字ｓは固体、ｇは気体を示
す。常温で気体である有機化合物に限らず、常温
で液体又は固体である有機化合物も、高温で分解
しガス体化することにより上記反応をおこさせる
ことができる。そして発生した水素ガスを圧力計
で読取るか、ガスクロマトグラフイや質量分析計
により分析することにより、水素の定量分析が可
能となる。
同様の原理で、Ｃ，Ｎ，Ｏ等を不純物として含
む水素ガスをシリコンと反応させることにより、
不純物元素をシリコン化合物の形で固化して水素
ガスを純化することができる。
〔発明の効果〕
本発明によれば、簡便かつ安価な装置で従来困
難であつた有機化合物の水素の定量分析が可能と
なつた。特に１mg以下という微量試料についての
定量が精度よくできるという点で優れている。
また本発明を水素ガスの純化に利用すれば、高
純度水素ガスの供給を必要とする真空装置に一体
的に連結した状態で水素ガス純化装置を構成する
ことができ、不純物ガス発生源となる無用なガス
導入配管が必要なくなる。
〔発明の実施例〕
本発明を有機化合物の水素定量に適用した実施
例につき説明する。第１図は有機化合物ガスの反
応分解装置である。図中、１１は石英管であり、
内部に清浄な金属シリコン粉末１２を入れ、これ
を真空排気後、試料ガスインレツト１３から試料
ガスを導入し、ヒータ１４により高温加熱する。
１５１〜１５５はバルブである。
試料ガスとしてエチルアルコールを用いた場合
に加熱した石英管１１内のガス成分を質量分析計
で追跡した結果を第２図ａ〜ｄに示す。ａは加熱
前、ｂは1000℃加熱、ｃは1100℃加熱、ｄは1200
℃加熱の場合である。これらの結果から、エチル
アルコールは加熱温度が高くなるに従つて分解し
て、1200℃以上ではほぼ水素のみが検知されるこ
とがわかる。
次にコレステロール（C27H46O）の水素定量に
適用した実施例を説明する。コレステロール１mg
を金属シリコン粉末と共に石英製アンプルに入
れ、これを真空排気後封止して、1100℃の高温に
加熱した。このときの石英アンプル内の質量分析
結果を第３図と下表に示す。
[Technical Field of the Invention] The present invention relates to a hydrogen gas separation method used for quantifying hydrogen for determining the compositional formula of organic compounds and for purifying hydrogen gas containing impurities. [Technical background of the invention and its problems] Conventionally, methods for determining hydrogen in organic compounds include (1)
burning the sample with O 2 and quantifying it as H 2 O;
(2) There were methods such as irradiating a high-energy particle beam and quantifying hydrogen from the energy distribution of the reflected particle beam. However, all of the conventional methods have drawbacks such as troublesome analytical operations, poor accuracy, and the need for very special equipment. In particular, it was difficult to quantify hydrogen in trace samples. On the other hand, high purity hydrogen gas is often introduced in thin film forming apparatuses using vapor phase growth. Conventionally, methods for purifying the hydrogen gas supplied to this system include
There were two methods: (1) adsorbing impurities with an adsorbent such as alumina, and (2) purifying hydrogen gas by passing it through a palladium plate. However, purification devices using these methods
Since it uses physical adsorption or diffusion phenomena, it is difficult to install a purification device inside a vacuum device. For this purpose, a separate introduction pipe is required, and the generation of impurity gas from the inner wall of this pipe poses a problem. [Object of the invention] The present invention is based on a completely different principle from conventional methods,
The purpose of the present invention is to provide a hydrogen gas separation method that makes it possible to easily and accurately quantitatively analyze hydrogen even in extremely small amounts of organic compound samples, and to purify hydrogen gas containing impurities using simple and inexpensive equipment. shall be. [Summary of the Invention] The present invention involves introducing a sample containing at least one element among C, N, and O in addition to H onto a silicon surface heated to a high temperature in vacuum or in an inert gas, and
It is characterized by fixing N, O, etc. as solid silicon compounds and separating only hydrogen gas. For example, in the case of an organic compound gas represented by the general formula C o H n O p N q , it reacts with silicon and decomposes according to the following reaction formula to generate hydrogen gas. (Si) s + (C o H n O p N q ) g → (SiC) s (SiO 2 ) s +
(Si 3 N 4 ) s + (H 2 ) g ↑ In the above reaction formula, the subscript s represents solid and g represents gas. Not only organic compounds that are gaseous at room temperature, but also organic compounds that are liquid or solid at room temperature can be decomposed at high temperature and turned into gas to cause the above reaction. Quantitative analysis of hydrogen becomes possible by reading the generated hydrogen gas with a pressure gauge or analyzing it with gas chromatography or mass spectrometry. Using the same principle, by reacting hydrogen gas containing impurities such as C, N, and O with silicon,
Hydrogen gas can be purified by solidifying impurity elements in the form of silicon compounds. [Effects of the Invention] According to the present invention, quantitative analysis of hydrogen in organic compounds, which has been difficult in the past, has become possible with a simple and inexpensive device. In particular, it is excellent in that it allows accurate quantification of trace amounts of samples of 1 mg or less. Furthermore, if the present invention is used to purify hydrogen gas, it is possible to configure a hydrogen gas purification device in a state where it is integrally connected to a vacuum device that requires the supply of high-purity hydrogen gas, which becomes a source of impurity gas. Eliminates the need for unnecessary gas introduction piping. [Example of the Invention] An example in which the present invention is applied to hydrogen determination of an organic compound will be described. FIG. 1 shows an apparatus for reacting and decomposing organic compound gas. In the figure, 11 is a quartz tube,
A clean metal silicon powder 12 is placed inside, and after it is evacuated, a sample gas is introduced from a sample gas inlet 13 and heated to a high temperature by a heater 14.
15 1 to 15 5 are valves. Figures 2 a to d show the results of tracking gas components in the heated quartz tube 11 using a mass spectrometer when ethyl alcohol was used as the sample gas. a is before heating, b is heated to 1000℃, c is heated to 1100℃, d is 1200℃
This is the case of heating at ℃. These results show that ethyl alcohol decomposes as the heating temperature increases, and that almost only hydrogen is detected at temperatures above 1200°C. Next, an example in which the present invention is applied to hydrogen determination of cholesterol (C 27 H 46 O) will be described. Cholesterol 1mg
was placed in a quartz ampoule with metal silicon powder, which was evacuated, sealed, and heated to a high temperature of 1100°C. The results of mass spectrometry inside the quartz ampoule at this time are shown in FIG. 3 and the table below.
【表】
以上の結果から、コレステロールは気化した後
シリコンと反応して分解し、H2ガスを発生して
いることがわかる。分析したH2量は化学式から
予想される標準値とよい一致を示した。
第４図は上記実施例に用いた石英製アンプル４
１であり、４２がシリコン粉末、４３がコレステ
ロールである。
以上において、十分な分解反応をおこさせ、し
かも精度よく水素定量を行うためには、次のよう
な条件が必要であつた。
(1) 加熱温度は1100℃以上であり、かつSiC，
SiO2，Si3N4等の反応生成物が分解しない範囲
であること、即ち1100℃〜2000℃に設定するこ
と。
(2) 金属シリコンは表面が清浄であること。反応
性を高めるため粉末にすることが必要であつ
た。
(3) 真空度10-6Torr以上高真空下で行うこと。
高純度不活性ガス中でも可能である。
なお、分析すべき有機化合物は、Ｃ，Ｈ，Ｎ，
Ｏの他に金属を含むいわゆる有機金属化合物であ
つても同様に水素定量が可能である。
固体試料の分解反応装置として第５図に示すよ
うな構成を用いることもできる。図において、５
１が石英管であり、先端部が細くなつていてここ
に試料５２を入れるようになつている。即ち石英
管５１を先ず除湿した後試料５２を入れ、その上
に細孔を設けた石英ガラス板５３を介して清浄な
シリコン粉末５４を入れる。そしてこの石英管５
１をパツキンを介して分析管と接続する。５５１
は水素定量のための標準ガス導入管側バルブ、５
５２は排気系バルブ、５５３は分析計又は圧力計
につながるバルブである。石英管５１を上述のよ
うに分析管に接続した後、バルブ５５２のみを開
けた状態で真空排気し、続いて吸着水除去のため
金属シリコン粉末５４のみをヒータ５６により
100℃程度に加熱する。しかる後、シリコン粉末
５４を1100℃以上に加熱し、バルブ５５２を閉じ
て試料５２をヒータ５７により徐々に加熱すれ
ば、試料は気化してシリコン粉末５４と反応して
H2ガスを発生し、これが分析管に蓄積する。十
分に反応させた後、全系を冷却して質量分析計又
はガスクロマトグラフイにより分析するか、ある
いは圧力計により圧力を読取ることにより、発生
した水素量を求めることができる。
次に本発明を水素ガス純化に適用した実施例を
第６図により説明する。図は、本発明の方法によ
る水素ガス純化装置６１を、高純度水素ガスを必
要とする薄膜形成装置６２に一体的に連結した状
態を示している。ステンレス配管６３より導かれ
た水素ガスはバリアブルリークバルブ６４を通し
て純化装置６１に導かれる。純化装置６１は、直
径50mmの石英ガラス管６５により形成されてい
て、内部は直径１〜５mmの高純度シリコン粉末６
６で満たされている。その外部にはヒータ６７が
巻かれている。純化装置６１に導入された水素ガ
スは1100℃以上に高温加熱されたシリコン粉末６
６と十分反応して、Ｃ，Ｎ，Ｏ等の不純物がシリ
コン化合物として固定化され、純化された水素ガ
スが薄膜形成装置６２に供給される。
この実施例によれば、物理的吸着等を利用する
従来の水素ガス純化法と異なり、真空装置と水素
ガス純化装置を一体化して簡便に高純度水素ガス
の真空装置への供給が可能となる。
シリコン粉末６６の大きさは、反応面積を大き
くするためには小さい方がよいが、十分なガス流
量を得るためには大きい方がよい。これら双方を
考慮すると、実用的には直径１〜５mmとするのが
適当である。[Table] From the above results, it can be seen that cholesterol reacts with silicon and decomposes after being vaporized, generating H 2 gas. The analyzed amount of H2 showed good agreement with the standard value expected from the chemical formula. Figure 4 shows the quartz ampoule 4 used in the above example.
1, 42 is silicon powder, and 43 is cholesterol. In the above, the following conditions were necessary to cause a sufficient decomposition reaction and to accurately quantify hydrogen. (1) The heating temperature is 1100℃ or higher, and SiC,
The temperature should be within a range in which reaction products such as SiO 2 and Si 3 N 4 do not decompose, that is, the temperature should be set at 1100°C to 2000°C. (2) The surface of metal silicon must be clean. It was necessary to powder it to increase reactivity. (3) Perform under high vacuum with a degree of vacuum of 10 -6 Torr or higher.
It is possible even in high purity inert gas. The organic compounds to be analyzed include C, H, N,
Hydrogen can be similarly determined even in so-called organometallic compounds containing metals in addition to O. A configuration as shown in FIG. 5 can also be used as a solid sample decomposition reaction apparatus. In the figure, 5
1 is a quartz tube with a tapered tip into which a sample 52 can be placed. That is, a quartz tube 51 is first dehumidified, then a sample 52 is placed therein, and a clean silicon powder 54 is placed thereon through a quartz glass plate 53 provided with pores. And this quartz tube 5
1 is connected to the analysis tube via a gasket. 55 1
is the standard gas inlet pipe side valve for hydrogen quantitative determination, 5
52 is an exhaust system valve, and 553 is a valve connected to an analyzer or a pressure gauge. After connecting the quartz tube 51 to the analysis tube as described above, the vacuum is evacuated with only the valve 552 open, and then only the metal silicon powder 54 is heated with the heater 56 to remove the adsorbed water.
Heat to around 100℃. Thereafter, the silicon powder 54 is heated to 1100°C or higher, the valve 552 is closed, and the sample 52 is gradually heated by the heater 57, so that the sample vaporizes and reacts with the silicon powder 54.
Generates H2 gas, which accumulates in the analysis tube. After sufficient reaction, the amount of hydrogen generated can be determined by cooling the entire system and analyzing it with a mass spectrometer or gas chromatography, or by reading the pressure with a pressure gauge. Next, an embodiment in which the present invention is applied to hydrogen gas purification will be described with reference to FIG. The figure shows a state in which a hydrogen gas purification device 61 according to the method of the present invention is integrally connected to a thin film forming device 62 that requires high purity hydrogen gas. Hydrogen gas led from the stainless steel pipe 63 is led to the purification device 61 through a variable leak valve 64. The purification device 61 is formed of a quartz glass tube 65 with a diameter of 50 mm, and the inside contains high-purity silicon powder 6 with a diameter of 1 to 5 mm.
It is filled with 6. A heater 67 is wound around the outside. The hydrogen gas introduced into the purification device 61 is silicon powder 6 heated to a high temperature of 1100°C or higher.
6, impurities such as C, N, and O are fixed as silicon compounds, and the purified hydrogen gas is supplied to the thin film forming device 62. According to this embodiment, unlike conventional hydrogen gas purification methods that utilize physical adsorption, etc., it is possible to easily supply high-purity hydrogen gas to the vacuum device by integrating the vacuum device and the hydrogen gas purification device. . The size of the silicon powder 66 is preferably small in order to increase the reaction area, but is preferably large in order to obtain a sufficient gas flow rate. Considering both of these factors, it is practically appropriate to set the diameter to 1 to 5 mm.
第１図は本発明を有機化合物ガスの水素定量に
適用した実施例の反応分解装置を示す図、第２図
ａ〜ｄは試料の反応分解による水素ガス発生の分
析結果を示す図、第３図は固体有機化合物の水素
定量に適用した実施例の水素ガス発生の分析結果
を示す図、第４図は同実施例に用いた石英製アン
プルを示す図、第５図は他の実施例の反応分解装
置を示す図、第６図は本発明を水素ガス純化に適
用した実施例の装置を示す図である。
１１……石英管、１２……シリコン粉末、１３
……試料ガスインレツト、１４……ヒータ、４１
……石英製アンプル、４２……シリコン粉末、４
３……コレステロール（試料）、５１……石英
管、５２……試料、５３……細孔付き石英ガラス
板、５４……シリコン粉末、５６，５７……ヒー
タ、６１……純化装置、６２……薄膜形成装置、
６５……石英管、６６……シリコン粉末、６７…
…ヒータ。
FIG. 1 is a diagram showing a reaction decomposition apparatus of an embodiment in which the present invention is applied to hydrogen determination of organic compound gas, FIGS. 2 a to d are diagrams showing analysis results of hydrogen gas generation by reactive decomposition of a sample, and FIG. The figure shows the analysis results of hydrogen gas generation in an example applied to the determination of hydrogen in solid organic compounds, Figure 4 shows the quartz ampoule used in the same example, and Figure 5 shows the results of another example. FIG. 6 is a diagram showing a reaction decomposition device, and FIG. 6 is a diagram showing an example device in which the present invention is applied to hydrogen gas purification. 11...Quartz tube, 12...Silicon powder, 13
... Sample gas inlet, 14 ... Heater, 41
... Quartz ampoule, 42 ... Silicon powder, 4
3... Cholesterol (sample), 51... Quartz tube, 52... Sample, 53... Quartz glass plate with pores, 54... Silicon powder, 56, 57... Heater, 61... Purification device, 62... ...thin film forming device,
65...Quartz tube, 66...Silicon powder, 67...
…heater.
Claims (1)
元素を含む有機化合物またはその有機化合物と水
素ガスを、真空中または不活性ガス中で高温加熱
されたシリコンの表面に導いて、Ｈ以外の元素を
シリコンと反応させて固化することにより、水素
ガスのみを分離抽出することを特徴とする水素ガ
ス分離法。 ２ 前記シリコンの加熱温度は1100℃〜2000℃に
設定される特許請求の範囲第１項記載の水素ガス
分離法。[Claims] 1. An organic compound containing at least one element among C, N, and O in addition to H, or the organic compound and hydrogen gas are heated to a high temperature in vacuum or in an inert gas on the surface of silicon. A hydrogen gas separation method characterized by separating and extracting only hydrogen gas by reacting and solidifying elements other than H with silicon. 2. The hydrogen gas separation method according to claim 1, wherein the heating temperature of the silicon is set at 1100°C to 2000°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58246321A JPS60141603A (en) | 1983-12-27 | 1983-12-27 | Separation of gaseous hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58246321A JPS60141603A (en) | 1983-12-27 | 1983-12-27 | Separation of gaseous hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60141603A JPS60141603A (en) | 1985-07-26 |
| JPS6257563B2 true JPS6257563B2 (en) | 1987-12-01 |
Family
ID=17146813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58246321A Granted JPS60141603A (en) | 1983-12-27 | 1983-12-27 | Separation of gaseous hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60141603A (en) |
-
1983
- 1983-12-27 JP JP58246321A patent/JPS60141603A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60141603A (en) | 1985-07-26 |
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