JPH08509454A - 水素流からガス状不純物を除去するための改善された方法 - Google Patents
水素流からガス状不純物を除去するための改善された方法Info
- Publication number
- JPH08509454A JPH08509454A JP6524089A JP52408994A JPH08509454A JP H08509454 A JPH08509454 A JP H08509454A JP 6524089 A JP6524089 A JP 6524089A JP 52408994 A JP52408994 A JP 52408994A JP H08509454 A JPH08509454 A JP H08509454A
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- Prior art keywords
- methane
- hydrogen
- nickel
- stream
- getter material
- Prior art date
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Classifications
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- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/304—Linear dimensions, e.g. particle shape, diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/402—Further details for adsorption processes and devices using two beds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Gas Separation By Absorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Of Gases By Adsorption (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
Claims (1)
- 【特許請求の範囲】 1.COxのようなより容易に除去可能な第1の種類の不純物および主として 窒素およびメタンからなるより除去しにくい第2の種類の不純物を包含する水素 流からガス状不純物を除去するための改善された方法であって、 A.前記流れは最初、5〜50℃でニッケルおよび/またはニッケル化合物を 包含する粒状物質からなる一つまたはそれ以上のベッドと接触状態となされる段 階にして、全ニッケル量の少なくとも1重量%(好ましくは5%)が、前記のよ り容易に除去可能な不純物が実質的に完全な仕方で除去されるまで、還元された (元素の)形式で存在する段階と、 B.前記より容易に除去可能な不純物は実質的にないが、前記より除去しにく い窒素およびメタンを依然として包含する段階Aから到来する流れはより高い温 度で非蒸発型ゲッタ材料からなる一つまたはそれ以上のベッドと接触状態となさ れる段階とから構成される方法。 2.前記流れの圧力は1〜20バールであり、前記段階Bの温度は200〜6 00℃である請求項1の方法。 3.前記水素供給流は実質的にメタンがなくそして前記段階Bの温度は300 〜350℃である請求項2の方法。 4.前記水素供給流は不純物としてメタンをも包含し そして前記段階Bの温度は400〜600℃である請求項2の方法。 5.前記ニッケルおよび/またはニッケル化合物は、100m2/gに等しいかまた はそれよりも多い(好ましくは100〜200m2/g)有効表面積を有するシリカ、キセ ロゲル、チタンシリカライトまたはシリカライトから実質的に構成されるキャリ ヤに保持されている請求項1の方法。 6.ニッケル含有ベッドは、一つまたはそれ以上の天然または合成モレキュラ ーシーブ、詳述すると天然または合成ゼオライト、シリカライトまたはチタンシ リカライトから構成される第2の収着ベッドの前にまたは(好ましくは)後にあ る請求項1の方法。 7.前記ゲッタ材料は一様かつ滑らかに研磨された内壁部を具備するハウジン グ内に包含され、前記内壁面の粗さは、中心線平均高さ(Ra)によって表現さ れ、0.50μmと等しいかそれ以下そして好ましくは0.25μmと等しいか またはそれ以下である請求項1の方法。 8.水素の空間速度は、グラム単位のゲッタ材料当たり0.5〜50cm3(標 準)/分でありそして除去しにくいメタンの量は5ppmまでである請求項4の 方法。 9.ゲッタ材料は1〜500μmそして好ましくは1〜250μmの平均粒子 寸法を有するばら粉末の形式である請求項1の方法。 10.ゲッタ材料が成形体の形式、詳述すると好ましくは0.5〜5mmの平均 寸法を有するペレットである請求項1の方法。 11.ゲッタ材料が、 A)ジルコニウム、バナジウムおよび鉄からなる合金、 B)ジルコニム、マンガンおよび鉄からなり、ジルコニウムの0.8原子数ま でがチタンにより置換されてもよい合金から選択される請求項1の方法。 12.ゲッタ材料は、三元組成図でプロットしたとき、隅部として以下に定めら れる点 (a)75%Zr−20%V−5%Fe (b)45%Zr−20%V−35%Fe (c)45%Zr−50%V−5%Fe を有する多角形内にある、重量パーセント組成を有する非蒸発型三元ゲッタ合金 である請求項11の方法。 13.ゲッタ材料は、三元組成図でプロットしたとき、隅部として以下に定めら れる点 (d)70%Zr−25%V−5%Fe (e)70%Zr−24%V−6%Fe (f)66%Zr−24%V−10%Fe (g)47%Zr−43%V−10%Fe (h)47%Zr−45%V−8%Fe (i)50%Zr−45%V−5%Fe を有する多角形内にある、重量パーセント組成を有する 非蒸発型三元ゲッタ合金である請求項12の方法。 14.Zr−V−Feゲッタ合金は下記、 i)鉄またはバナジウムがニッケル、コバルトまたはマンガンにより部分的に置 換可能である、 ii)バナジウムがニオブにより部分的に置換可能である、 iii)ジルコニウムのある部分がチタンにより置換可能である のごとく修正可能な請求項11の方法。 15.COxのようなより容易に除去可能な第1の種類の不純物および主として 窒素およびメタンからなるより除去しにくい第2の種類の不純物を包含する水素 流からガス状不純物を除去するための装置であって、 A)管路104、104’を通じて予備精製容器106、106’並びに弁1 08、108’と流体連通状態にあるガス入口部102であって、当該弁108 、108’が、保持ニッケルをベースにした粒子状物質110からなるベッドと さらに任意であるが天然または合成モレキュラーシーブ(111)からなる別の (第2の)ベッドをも包含する第1または第2の予備精製容器106、106’ を通じて不純物含有水素の通過を許容するよう交互に開かれるかまたは閉じられ るようにした前記ガス入口部と、 B)予備精製容器106、106’のいずれかからの部分精製水素流を制御し 、一方の容器が作動している間 他方の容器においてニッケルの再生を許容する管路114、114’および弁1 16、116’により予備容器106、106’がこれと流体連通状態にあると ころの最終精製容器112であって、非蒸発型ゲッタ材料118からなるベッド を包含する前記最終精製容器112とから構成される装置。 16.前記ゲッタ材料は、 A)ジルコニウム、バナジウムおよび鉄からなる合金、 B)ジルコニム、マンガンおよび鉄からなり、ジルコニウムの0.8原子数ま でがチタンにより置換可能な合金から選択される請求項15の装置。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI930850A IT1270875B (it) | 1993-04-29 | 1993-04-29 | Procedimento di purificazione dell'idrogeno e purificatore relativo |
IT93A000850 | 1993-04-29 | ||
PCT/IT1993/000052 WO1994025394A1 (en) | 1993-04-29 | 1993-05-24 | Process for the removal of gaseous impurities from a stream of hydrogen |
Publications (2)
Publication Number | Publication Date |
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JPH08509454A true JPH08509454A (ja) | 1996-10-08 |
JP2954705B2 JP2954705B2 (ja) | 1999-09-27 |
Family
ID=11365941
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6524089A Expired - Lifetime JP2954705B2 (ja) | 1993-04-29 | 1993-05-24 | 水素流からガス状不純物を除去するための改善された方法 |
Country Status (10)
Country | Link |
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US (2) | US5558844A (ja) |
EP (1) | EP0696256B1 (ja) |
JP (1) | JP2954705B2 (ja) |
KR (1) | KR0168899B1 (ja) |
CN (1) | CN1033443C (ja) |
CA (1) | CA2137792C (ja) |
DE (1) | DE69314060T2 (ja) |
IT (1) | IT1270875B (ja) |
RU (1) | RU2122518C1 (ja) |
WO (1) | WO1994025394A1 (ja) |
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ITMI20011193A1 (it) * | 2001-06-06 | 2002-12-06 | Getters Spa | Metodo per la misura mediante spettroscopia di mobilita' ionica dellaconcentrazione di acqua in argon, idrogeno, azoto e elio |
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JP5002230B2 (ja) * | 2006-10-05 | 2012-08-15 | 日本パイオニクス株式会社 | 不活性ガスの精製方法 |
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CN108342214A (zh) * | 2017-01-22 | 2018-07-31 | 何巨堂 | 富产杂质气体的加氢过程与在线第二加氢过程的氢气用法 |
CN111342346B (zh) * | 2018-12-19 | 2021-06-01 | 有研工程技术研究院有限公司 | 兼具吸放氢和杂质气体吸附功能的元件及其制备方法 |
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JP2640518B2 (ja) * | 1987-11-04 | 1997-08-13 | サエス・ゲッテルス・ソシエタ・ペル・アチオニ | 水素ガスを精製する方法と装置 |
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IT1239900B (it) * | 1990-03-30 | 1993-11-23 | Getters Spa | Metodo per determinare la fine della vita utile di un purificatore di gas e relativa apparecchiatura |
IT1248676B (it) * | 1990-06-01 | 1995-01-26 | Getters Spa | Recupero di trizio e deuterio dai loro ossidi e composti intermetallici utili a questo scopo |
JP2980425B2 (ja) * | 1990-09-14 | 1999-11-22 | 日本パイオニクス株式会社 | 希ガスの精製方法 |
IT1244156B (it) * | 1990-11-23 | 1994-07-08 | Getters Spa | Purificatore di gas avente un interruttore sensibile alla pressione per determinare il suo fine vita. |
US5154736A (en) * | 1991-03-29 | 1992-10-13 | Shell Oil Company | Process for the separation of a gas mixture |
RU2123971C1 (ru) * | 1993-04-29 | 1998-12-27 | Саес Геттерс С.П.А. | Способ удаления газообразных примесей из потока водорода и устройство для его осуществления |
-
1993
- 1993-04-29 IT ITMI930850A patent/IT1270875B/it active IP Right Grant
- 1993-05-24 RU RU95106987A patent/RU2122518C1/ru active
- 1993-05-24 JP JP6524089A patent/JP2954705B2/ja not_active Expired - Lifetime
- 1993-05-24 DE DE69314060T patent/DE69314060T2/de not_active Expired - Lifetime
- 1993-05-24 WO PCT/IT1993/000052 patent/WO1994025394A1/en active IP Right Grant
- 1993-05-24 KR KR1019940704624A patent/KR0168899B1/ko not_active IP Right Cessation
- 1993-05-24 EP EP93913468A patent/EP0696256B1/en not_active Expired - Lifetime
- 1993-05-24 CA CA002137792A patent/CA2137792C/en not_active Expired - Lifetime
- 1993-05-31 CN CN93106485A patent/CN1033443C/zh not_active Expired - Lifetime
-
1995
- 1995-02-10 US US08/386,325 patent/US5558844A/en not_active Expired - Lifetime
- 1995-06-06 US US08/471,638 patent/US5556603A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
ITMI930850A1 (it) | 1994-10-29 |
CN1094377A (zh) | 1994-11-02 |
US5556603A (en) | 1996-09-17 |
JP2954705B2 (ja) | 1999-09-27 |
KR0168899B1 (ko) | 1999-01-15 |
CA2137792C (en) | 2003-04-08 |
ITMI930850A0 (it) | 1993-04-29 |
RU95106987A (ru) | 1997-01-10 |
EP0696256B1 (en) | 1997-09-17 |
CA2137792A1 (en) | 1994-11-10 |
DE69314060D1 (de) | 1997-10-23 |
KR950702171A (ko) | 1995-06-19 |
EP0696256A1 (en) | 1996-02-14 |
WO1994025394A1 (en) | 1994-11-10 |
RU2122518C1 (ru) | 1998-11-27 |
CN1033443C (zh) | 1996-12-04 |
IT1270875B (it) | 1997-05-13 |
US5558844A (en) | 1996-09-24 |
DE69314060T2 (de) | 1998-01-15 |
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