JPH05115753A - Method and apparatus for removing hydrogen in gas - Google Patents
Method and apparatus for removing hydrogen in gasInfo
- Publication number
- JPH05115753A JPH05115753A JP3310023A JP31002391A JPH05115753A JP H05115753 A JPH05115753 A JP H05115753A JP 3310023 A JP3310023 A JP 3310023A JP 31002391 A JP31002391 A JP 31002391A JP H05115753 A JPH05115753 A JP H05115753A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- hydrogen
- membrane
- water
- dissolved oxygen
- 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
- 239000001257 hydrogen Substances 0.000 title claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 44
- 239000007789 gas Substances 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012528 membrane Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000011261 inert gas Substances 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005273 aeration Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ガス中の水素の除去方
法に係り、特に膜を用いるガス中の水素の除去方法及び
除去装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing hydrogen in gas, and more particularly to a method and apparatus for removing hydrogen in gas using a membrane.
【０００２】[0002]
【従来の技術】ソーダ工業等、電気分解を用いる場合に
は、陰極側に水素が発生し、水素を含むガスとなる。ま
た、半導体工業では、水素アニール等の処理工程に伴っ
て、水素を含む排ガスが発生する。従来、水素を含むガ
スは、爆発限界未満になるように窒素等の不活性ガスで
希釈するとか、パラジウム等の触媒を用い、加熱状態で
気相中の酸素と反応燃焼させる触媒燃焼等の方法で処理
されていた。2. Description of the Related Art When electrolysis is used as in the soda industry, hydrogen is generated on the cathode side and becomes a gas containing hydrogen. Further, in the semiconductor industry, exhaust gas containing hydrogen is generated along with a treatment process such as hydrogen annealing. Conventionally, a gas containing hydrogen is diluted with an inert gas such as nitrogen so as to be less than the explosion limit, or a method such as catalytic combustion in which a catalyst such as palladium is used to react and burn with oxygen in a gas phase in a heated state. Had been processed in.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記従来の方
法には、以下のような難点があった。希釈法では、希釈
に大量の不活性ガスが必要であること、希釈されただけ
であって、除去されていないため、混合・分散等の状態
によっては、配管等で部分的に高濃度の水素が滞留する
可能性がある等の問題点があった。また、気相中の酸素
との触媒燃焼による方法では、反応効率が温度の低下、
触媒の濡れ等によって低下するために、水素ガスの流量
及び濃度の変動に対して追従が困難という問題点があ
る。例えば供給水素量が低下した場合には、燃焼熱の供
給量が少なくなって触媒層の温度が低下するため、その
後水素量が増加した場合に反応不足となって水素が漏洩
することがあった。そこで、本発明は、上記問題点を解
決し、簡単な装置で、またガスの流量、濃度等の変化に
も対応が容易で、しかも安全で迅速にガス中の水素を除
去する方法及び装置を提供することを課題とする。However, the above-mentioned conventional method has the following drawbacks. In the dilution method, a large amount of inert gas is required for dilution, and it is only diluted but not removed. However, there is a problem in that Further, in the method by catalytic combustion with oxygen in the gas phase, the reaction efficiency decreases in temperature,
There is a problem in that it is difficult to follow changes in the flow rate and concentration of hydrogen gas because it decreases due to wetting of the catalyst and the like. For example, when the amount of hydrogen supply decreases, the amount of combustion heat supply decreases and the temperature of the catalyst layer decreases. Therefore, when the amount of hydrogen increases, the reaction may become insufficient and hydrogen may leak. . Therefore, the present invention provides a method and apparatus for solving the above-mentioned problems and for removing hydrogen in gas with a simple device, capable of easily responding to changes in gas flow rate, concentration, etc., and safe and prompt. The challenge is to provide.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
に、本発明では、水素を含むガス中から水素を除去する
方法において、水素を含むガスをパラジウムを担持した
膜の接ガス側に供給し、溶存酸素を含む水を該膜の接液
側に通水することを特徴とするガス中の水素の除去方法
としたものである。また、本発明では、水素を含むガス
中から水素を除去する装置において、パラジウムを担持
した膜を設け、該膜の接ガス側に水素を含むガスを供給
する手段と、接液側に溶存酸素を含む水を通水する手段
とを設けたことを特徴とするガス中の水素の除去装置と
したものである。In order to solve the above-mentioned problems, in the present invention, in a method of removing hydrogen from a gas containing hydrogen, a gas containing hydrogen is supplied to the gas-contacting side of a membrane supporting palladium. Then, water containing dissolved oxygen is passed to the liquid contact side of the membrane to remove hydrogen in the gas. Further, in the present invention, in an apparatus for removing hydrogen from a gas containing hydrogen, a membrane supporting palladium is provided, a means for supplying a gas containing hydrogen to the gas-contacting side of the membrane, and dissolved oxygen on the liquid-contacting side. And a means for passing water containing water.
【０００５】ここで、パラジウムを担持した膜として
は、水は透過せず水素は透過する膜の表面及び／又は内
部にパラジウムを担持した膜であれば良く、パラジウム
を触媒樹脂への担持方法等に準じて担持した気体透過膜
を用いることが出来る。また、水素を透過する膜の表面
にパラジウム層を気孔なく形成し、実質的に水が透過し
ない状態にした膜であっても良く、セラミック膜にパラ
ジウムメッキをした膜を用いることもできる。溶存酸素
を含む水は、一過性でも供給することができるが、通水
後の水に例えば空気等の酸素を含む気体を注入・曝気
し、溶存酸素濃度を増加させて循環使用することもでき
る。溶存酸素濃度としては飽和に近い状態が好ましい
が、４ｐｐｍ以上あれば水素の除去が十分行える。Here, the membrane supporting palladium may be a membrane supporting palladium on the surface and / or inside of a membrane which is impermeable to water and permeable to hydrogen. A gas permeable membrane supported according to the above can be used. Further, it may be a film in which a palladium layer is formed on the surface of a hydrogen permeable film without pores so that water is substantially impermeable, and a ceramic film plated with palladium may be used. Water containing dissolved oxygen can be supplied transiently, but it is also possible to inject and aerate a gas containing oxygen such as air into the water after passing water to increase the dissolved oxygen concentration and circulate it. it can. The dissolved oxygen concentration is preferably close to saturation, but if it is 4 ppm or more, hydrogen can be sufficiently removed.
【０００６】[0006]
【作用】膜の一方に供給された水素が、膜の表面及び／
又は内部に担持したパラジウムに移行し、表面上で水中
の溶存酸素と反応して水になることで、ガス中の水素が
効率よく除去される。この反応は常温で起こるため、加
熱の必要がない。また溶存酸素量を若干過剰に維持する
ことで、処理ガス中の水素濃度及び量の変動の影響を受
けず、安定して水素を処理することが出来る。[Function] Hydrogen supplied to one side of the membrane is
Alternatively, the hydrogen in the gas is efficiently removed by transferring to the palladium supported inside and reacting with the dissolved oxygen in the water on the surface to become water. This reaction does not require heating because it occurs at room temperature. Further, by maintaining the dissolved oxygen amount to be slightly excessive, it is possible to process hydrogen stably without being affected by fluctuations in the hydrogen concentration and amount in the process gas.
【０００７】[0007]
【実施例】以下、本発明の実施例を示すが、本発明は以
下の実施例に限定されるものではない。 実施例１ 図１は、本発明の実施態様の一例を示す概略模式図であ
る。貯水槽１からポンプ２を介して、溶存酸素濃度を増
加させた水をパラジウム担持膜モジュール３の接液側６
に通水し、モジュール３を通過した水は貯水槽１へ循環
させる。このパラジウム担持膜モジュールは、膜面積６
ｍ2 の気体透過膜モジュールの接液部内にパラジウムを
担持したモジュール４本を並列にして用いた。貯水槽１
では、空気曝気ライン５を介して酸素を含む気体を供給
し、水中の溶存酸素濃度を増加させている。このパラジ
ウム担持モジュール３に水素濃度６０％、流量１リット
ル／min のガスをガス注入口４から供給し、飽和に近い
溶存酸素濃度の水を流量５ｍ3 ／ｈで通水することで、
ガス中の水素濃度は１％以下となった。EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to the following examples. Example 1 FIG. 1 is a schematic diagram showing an example of an embodiment of the present invention. Water whose dissolved oxygen concentration has been increased from the water storage tank 1 via the pump 2 is brought into contact with the palladium supporting membrane module 3 on the liquid contact side 6
The water which has passed through the module 3 and has passed through the module 3 is circulated to the water tank 1. This palladium-supported membrane module has a membrane area of 6
Four modules supporting palladium in the liquid contact part of the m 2 gas permeable membrane module were used in parallel. Water tank 1
In, a gas containing oxygen is supplied through the air aeration line 5 to increase the dissolved oxygen concentration in water. By supplying a gas having a hydrogen concentration of 60% and a flow rate of 1 liter / min to the palladium-supporting module 3 from the gas inlet 4, and by flowing water having a dissolved oxygen concentration close to saturation at a flow rate of 5 m 3 / h,
The hydrogen concentration in the gas became 1% or less.
【０００８】比較例１ 実施例と同様のガスを希釈によって処理した。水素ガス
濃度１％にするためには、約６０リットル／min （３．
６ｍ3 ／ｈ）の窒素ガスが必要であった。Comparative Example 1 The same gas as in Example was treated by dilution. About 60 l / min (3.
6 m 3 / h) of nitrogen gas was required.
【０００９】比較例２ 実施例と同様のガスを触媒燃焼によって処理した。処理
後のガス中の水素濃度は１％以下であるが、パラジウム
系触媒層の加熱（８０℃以上）が必要であり、水素の除
去処理が安定して行える状態になるまでに若干の時間が
必要であった。また処理を安定して行うためにガス中の
湿度を低減する必要があり、前処理として除湿を行う必
要がある。Comparative Example 2 The same gas as in Example was treated by catalytic combustion. The hydrogen concentration in the gas after the treatment is 1% or less, but it is necessary to heat the palladium-based catalyst layer (80 ° C. or higher), and it takes some time until the hydrogen removal treatment becomes stable. Was needed. Further, it is necessary to reduce the humidity in the gas for stable treatment, and it is necessary to perform dehumidification as a pretreatment.
【００１０】[0010]
【発明の効果】本発明によれば、排ガス中の水素を簡単
な装置で、かつ安全に除去することが出来、多量の不活
性ガスを消費することもない。According to the present invention, hydrogen in exhaust gas can be safely removed with a simple device, and a large amount of inert gas is not consumed.
【図１】本発明の実施例を示す概略模式図である。FIG. 1 is a schematic diagram showing an embodiment of the present invention.
１：貯水槽、２：ポンプ、３：パラジウム担持膜モジュ
ール、４：ガス注入口、５：空気曝気ライン、６：水注
入口1: Water tank, 2: Pump, 3: Palladium carrying membrane module, 4: Gas inlet, 5: Air aeration line, 6: Water inlet
───────────────────────────────────────────────────── フロントページの続き (72)発明者 斉藤 孝行 神奈川県藤沢市本藤沢４丁目２番１号 株 式会社荏原総合研究所内 (72)発明者 中島 健 神奈川県藤沢市本藤沢４丁目２番１号 株 式会社荏原総合研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takayuki Saito 4-2-1 Motofujisawa, Fujisawa-shi, Kanagawa Inside the EBARA Research Institute, Inc. (72) Inventor Ken Nakajima 4-2-1, Fujisawa, Kanagawa No. 1 Stock company EBARA Research Institute
Claims (2)
法において、水素を含むガスをパラジウムを担持した膜
の接ガス側に供給し、溶存酸素を含む水を該膜の接液側
に通水することを特徴とするガス中の水素の除去方法。1. A method for removing hydrogen from a gas containing hydrogen, wherein a gas containing hydrogen is supplied to a gas-contacting side of a membrane supporting palladium, and water containing dissolved oxygen is passed to the liquid-contacting side of the membrane. A method for removing hydrogen in a gas, which comprises using water.
置において、パラジウムを担持した膜を設け、該膜の接
ガス側に水素を含むガスを供給する手段と、接液側に溶
存酸素を含む水を通水する手段とを設けたことを特徴と
するガス中の水素の除去装置。2. An apparatus for removing hydrogen from a gas containing hydrogen, wherein a membrane supporting palladium is provided, a means for supplying a gas containing hydrogen to the gas-contacting side of the membrane, and a means for supplying dissolved oxygen to the liquid-contacting side. A device for removing hydrogen in a gas, which is provided with means for passing water containing water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3310023A JPH0815528B2 (en) | 1991-10-30 | 1991-10-30 | Method and device for removing hydrogen in gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3310023A JPH0815528B2 (en) | 1991-10-30 | 1991-10-30 | Method and device for removing hydrogen in gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05115753A true JPH05115753A (en) | 1993-05-14 |
| JPH0815528B2 JPH0815528B2 (en) | 1996-02-21 |
Family
ID=18000231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3310023A Expired - Fee Related JPH0815528B2 (en) | 1991-10-30 | 1991-10-30 | Method and device for removing hydrogen in gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0815528B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000070655A (en) * | 1998-09-01 | 2000-03-07 | Ngk Insulators Ltd | Method and apparatus for preparing carbon monoxide with high purity |
| JP2021062316A (en) * | 2019-10-10 | 2021-04-22 | 株式会社荏原製作所 | Exhaust system and exhaust method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS551816A (en) * | 1978-06-15 | 1980-01-09 | Mitsubishi Rayon Co Ltd | Vapor-liquid contactor |
| JPS63171617A (en) * | 1987-01-09 | 1988-07-15 | Shozaburo Saito | Composite membrane excellent in permselectivity of hydrogen and its production |
-
1991
- 1991-10-30 JP JP3310023A patent/JPH0815528B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS551816A (en) * | 1978-06-15 | 1980-01-09 | Mitsubishi Rayon Co Ltd | Vapor-liquid contactor |
| JPS63171617A (en) * | 1987-01-09 | 1988-07-15 | Shozaburo Saito | Composite membrane excellent in permselectivity of hydrogen and its production |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000070655A (en) * | 1998-09-01 | 2000-03-07 | Ngk Insulators Ltd | Method and apparatus for preparing carbon monoxide with high purity |
| JP2021062316A (en) * | 2019-10-10 | 2021-04-22 | 株式会社荏原製作所 | Exhaust system and exhaust method |
| NL2026632A (en) * | 2019-10-10 | 2021-05-31 | Ebara Corp | Exhaust System and Exhaust Method |
| US11090619B2 (en) | 2019-10-10 | 2021-08-17 | Ebara Corporation | Exhaust system and exhaust method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0815528B2 (en) | 1996-02-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |