JP4860206B2 - Method and apparatus for purifying hydrogen gas - Google Patents
Method and apparatus for purifying hydrogen gas Download PDFInfo
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- JP4860206B2 JP4860206B2 JP2005230799A JP2005230799A JP4860206B2 JP 4860206 B2 JP4860206 B2 JP 4860206B2 JP 2005230799 A JP2005230799 A JP 2005230799A JP 2005230799 A JP2005230799 A JP 2005230799A JP 4860206 B2 JP4860206 B2 JP 4860206B2
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- synthetic zeolite
- palladium catalyst
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 79
- 238000000034 method Methods 0.000 title claims description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 82
- 229910021536 Zeolite Inorganic materials 0.000 claims description 47
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 47
- 239000010457 zeolite Substances 0.000 claims description 47
- 238000000746 purification Methods 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 41
- 229910052763 palladium Inorganic materials 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 26
- 239000012535 impurity Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims 1
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910007727 Zr V Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- -1 gallium nitride compound Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 0 CCCC(C)CC(CC1(C2*3)C2(CC(C2)C(CC4)C4*4)C13C2CC4(C*)C1CCCC1)C(C)CCCCCSCC Chemical compound CCCC(C)CC(CC1(C2*3)C2(CC(C2)C(CC4)C4*4)C13C2CC4(C*)C1CCCC1)C(C)CCCCCSCC 0.000 description 1
- 229910019589 Cr—Fe Inorganic materials 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 229910007729 Zr W Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 229910003126 Zr–Ni Inorganic materials 0.000 description 1
- 229910007837 Zr—V—Ni Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Separation Of Gases By Adsorption (AREA)
Description
本発明は、水素ガスの精製方法及び精製装置に関する。さらに詳細には、水素ガス中に含まれる不純物を効率よく極めて低濃度まで除去しうる水素ガスの精製方法及び精製装置に関する。 The present invention relates to a method and apparatus for purifying hydrogen gas. More specifically, the present invention relates to a method and apparatus for purifying hydrogen gas that can efficiently remove impurities contained in hydrogen gas to a very low concentration.
水素ガスは、近年目覚ましく発展した半導体製造工業で、各種工程中のキャリアガスとして多用されている。例えば、発光ダイオードやレーザーダイオード等の素子として利用される窒化ガリウム系化合物半導体の製造工程においては、常温で液体であるトリメチルガリウム、トリメチルインジウム、またはトリメチルアルミニウムのキャリアガスとして用いられている。そして半導体の高集積化とともにガスの純度向上への要求はますます強くなっており、水素ガス中にｐｐｍレベルで含まれる窒素、酸素、一酸化炭素、二酸化炭素、水、及びメタン等の不純物を除去して１ｐｐｂ以下の超高純度に精製することが望まれている。 Hydrogen gas is widely used as a carrier gas in various processes in the semiconductor manufacturing industry which has been remarkably developed in recent years. For example, it is used as a carrier gas for trimethylgallium, trimethylindium, or trimethylaluminum that is liquid at room temperature in the manufacturing process of a gallium nitride compound semiconductor used as an element such as a light emitting diode or a laser diode. The demand for improved gas purity along with higher integration of semiconductors is becoming stronger, and impurities such as nitrogen, oxygen, carbon monoxide, carbon dioxide, water, and methane contained in hydrogen gas at the ppm level are increasing. It is desired to remove and purify to ultra-high purity of 1 ppb or less.
水素ガスの精製方法としては、例えば加熱下でのパラジウム膜またはパラジウム合金膜の水素選択透過性を利用した精製方法が知られている。また、例えば、液体窒素を冷熱源として極低温下に設定した吸着材の物理吸着性を利用した深冷吸着精製方法、ジルコニウム合金等を用いたゲッター剤による化学反応を利用した精製方法等が知られている。
しかしながら、これらの水素ガスの精製方法うち、パラジウム膜またはパラジウム合金膜を利用した精製方法は、水素ガスの選択透過性を利用しているため、不純物である水素以外の成分は全て除かれ、超高純度の水素ガスを得ることができるが、精製装置の入口側と出口側において圧力損失を生じさせる必要があるため、大流量の粗水素ガスを効率よく処理することが困難であった。また、深冷吸着精製方法は、大流量の粗水素ガスまたは粗希ガスを効率よく処理することができるが、装置が大型で複雑になるという不都合があった。また、ゲッター剤による化学反応を利用した精製方法は、ゲッター剤の再生ができないため、除去すべき不純物が多く含まれている場合は、ゲッター剤を頻繁に交換する必要があり、ランニングコストが高くなるという不都合があった。 However, among these hydrogen gas purification methods, the purification method using a palladium membrane or a palladium alloy membrane uses the selective permeability of hydrogen gas, so all components other than hydrogen, which is an impurity, are removed. Although high-purity hydrogen gas can be obtained, it is difficult to efficiently process a large flow rate of crude hydrogen gas because it is necessary to cause a pressure loss on the inlet side and the outlet side of the purifier. The cryogenic adsorption purification method can efficiently process a large flow rate of crude hydrogen gas or crude rare gas, but has the disadvantage that the apparatus is large and complicated. In addition, the purification method using a chemical reaction with a getter agent cannot regenerate the getter agent, so if there are many impurities to be removed, the getter agent must be replaced frequently, resulting in high running costs. There was an inconvenience.
従って、本発明が解決しようとする課題は、水素ガスの精製において、大型または複雑な装置を用いることなく、粗水素ガスに含まれている微量の窒素、酸素、一酸化炭素、二酸化炭素、水、メタン等の不純物を、全て１ｐｐｂ以下さらには０．１ｐｐｂ以下の超低濃度まで効率よく除去できる水素ガスの精製方法及び装置を提供することである。 Therefore, the problem to be solved by the present invention is that, in the purification of hydrogen gas, a trace amount of nitrogen, oxygen, carbon monoxide, carbon dioxide, water contained in the crude hydrogen gas is used without using a large or complicated apparatus. An object of the present invention is to provide a hydrogen gas purification method and apparatus capable of efficiently removing all impurities such as methane to ultra-low concentrations of 1 ppb or less, further 0.1 ppb or less.
本発明者らは、これらの課題を解決すべく鋭意検討した結果、粗水素ガスに不純物として含まれる酸素を水素との反応で水に変換できるパラジウム触媒は、触媒の効果を発揮できる寿命が長く容易に再生できること、パラジウム触媒と接触後の粗水素ガスに含まれる二酸化炭素及び水等を合成ゼオライトで除去し、再生ができないゲッター剤をパラジウム触媒及び合成ゼオライトの下流側に設ける構成とすることにより、ゲッター剤の寿命を延ばせることを見出した。さらに、このような構成とすることにより、大型または複雑な装置を用いることなく、粗水素ガスに含まれている窒素、酸素、一酸化炭素、二酸化炭素、水、メタンの全てを、効率よく超低濃度まで除去できることを見出し、本発明の精製方法及び精製装置に到達した。 As a result of intensive studies to solve these problems, the present inventors have found that a palladium catalyst that can convert oxygen contained in crude hydrogen gas as an impurity into water by reaction with hydrogen has a long life that can exhibit the effect of the catalyst. By making it easy to regenerate, removing carbon dioxide and water contained in the crude hydrogen gas after contact with the palladium catalyst with synthetic zeolite, and providing a getter agent that cannot be regenerated on the downstream side of the palladium catalyst and synthetic zeolite And found that the life of the getter agent can be extended. Furthermore, with such a configuration, all of nitrogen, oxygen, carbon monoxide, carbon dioxide, water, and methane contained in the crude hydrogen gas can be efficiently transduced without using a large or complicated device. The inventors have found that it can be removed to a low concentration, and arrived at the purification method and purification apparatus of the present invention.
すなわち本発明は、粗水素ガスを、０〜１００℃の温度でパラジウム触媒、０〜１００℃の温度で合成ゼオライト、及び４００〜６００℃の温度でゲッター剤とこの順に接触させて、該粗水素ガスに含まれる不純物を除去することを特徴とする水素ガスの精製方法である。
また、本発明は、上流側にパラジウム触媒、下流側に合成ゼオライトが充填された充填筒、及びゲッター剤が充填された充填筒が備えられ、粗水素ガスがこの順で流通するように該充填筒が接続されてなることを特徴とする水素ガスの精製装置でもある。
That is, the present invention comprises contacting crude hydrogen gas with a palladium catalyst at a temperature of 0 to 100 ° C., a synthetic zeolite at a temperature of 0 to 100 ° C. , and a getter agent at a temperature of 400 to 600 ° C. in this order. A method for purifying hydrogen gas, wherein impurities contained in the gas are removed.
Further, the present invention is a palladium catalyst on the upstream side, filling cylinder synthetic zeolite is filled in the downstream side, and the filling cylinder getter is filled is provided, the crude hydrogen gas the filling to flow in this order It is also a hydrogen gas refining device characterized in that cylinders are connected.
本発明の水素ガスの精製方法及び精製装置により、大型または複雑な装置を用いることなく、粗水素ガスに含まれている微量の窒素、酸素、一酸化炭素、二酸化炭素、水、メタン等の不純物を、全て１ｐｐｂ以下さらには０．１ｐｐｂ以下の超低濃度まで効率よく除去できるようになった。その結果、ランニングコストが安くなるとともに、装置のメンテナンスが容易になった。 Impurities such as nitrogen, oxygen, carbon monoxide, carbon dioxide, water, methane, etc. contained in the crude hydrogen gas without using a large or complicated device by the purification method and purification device of the hydrogen gas of the present invention Can be efficiently removed to an ultra-low concentration of 1 ppb or less and further 0.1 ppb or less. As a result, the running cost is reduced and the maintenance of the apparatus is facilitated.
本発明の水素ガスの精製方法及び精製装置は、粗水素ガスに含まれる窒素、酸素、一酸化炭素、二酸化炭素、水、メタン等の不純物を除去するための方法及び装置に適用される。
以下、本発明の水素ガスの精製方法及び精製装置を、図１〜図５を用いて説明するが、本発明がこれらに限定されるものではない。尚、図１〜図５は、本発明の水素ガスの精製装置の一例を示す構成図である。
The method and apparatus for purifying hydrogen gas according to the present invention is applied to a method and apparatus for removing impurities such as nitrogen, oxygen, carbon monoxide, carbon dioxide, water, and methane contained in crude hydrogen gas.
Hereinafter, although the purification method and purification apparatus of the hydrogen gas of this invention are demonstrated using FIGS. 1-5, this invention is not limited to these. 1-5 is a block diagram which shows an example of the refiner | purifier of the hydrogen gas of this invention.
本発明の精製方法は、粗水素ガスを、パラジウム触媒、合成ゼオライト、及びゲッター剤とこの順に接触させて、該粗水素ガスに含まれる不純物を除去する精製方法である。
また、本発明の精製方法に用いられる装置は、前記の精製方法を実施するための装置であり、図１に示すように、パラジウム触媒１が充填された充填筒、合成ゼオライト２が充填された充填筒、及びゲッター剤３が充填された充填筒が備えられ、粗水素ガスがこの順で流通するように前記充填筒が接続されてなる精製装置である。また、本発明の精製装置は、図２に示すように、パラジウム触媒１及び合成ゼオライト２が充填された充填筒、及びゲッター剤３が充填された充填筒が備えられ、粗水素ガスがこの順で流通するように前記充填筒が接続されてなる装置である。
The purification method of the present invention is a purification method in which a crude hydrogen gas is brought into contact with a palladium catalyst, a synthetic zeolite, and a getter agent in this order to remove impurities contained in the crude hydrogen gas.
Moreover, the apparatus used for the purification method of the present invention is an apparatus for carrying out the above-described purification method. As shown in FIG. 1, a packed cylinder filled with a
本発明に使用されるパラジウム触媒としては、市販のパラジウム触媒を用いることができる。また、パラジウム触媒は、通常は無機質担体に担持されているものが使用される。
また、本発明に使用される合成ゼオライトとしては、市販されている細孔径３〜１５Å相当のものがすべて使用可能である。
さらに、本発明に使用されるゲッター剤としても特に制限されることはなく、例えばＺｒ−Ｖ、Ｚｒ−Ｔｉ、Ｚｒ−Ｆｅ、Ｚｒ−Ｃｕ、Ｚｒ−Ｃｒ、Ｚｒ−Ｎｉ、Ｚｒ−Ｃｏ、Ｚｒ−Ｎｂ、Ｚｒ−Ｗ、Ｚｒ−Ｖ−Ｎｉ、Ｚｒ−Ｖ−Ｃｕ、Ｚｒ−Ｖ−Ｃｏ、Ｚｒ−Ｖ−Ｆｅ、Ｚｒ−Ｖ−Ｎｉ−Ｃｕ、Ｚｒ−Ｖ−Ｎｉ−Ｃｒ、Ｚｒ−Ｖ−Ｎｉ−Ｃｏ、Ｚｒ−Ｖ−Ｃｒ−Ｆｅ等の合金を使用することができる。これらの合金は予め水素化物とすることが好ましい。
A commercially available palladium catalyst can be used as the palladium catalyst used in the present invention. As the palladium catalyst, one supported on an inorganic carrier is usually used.
Moreover, as the synthetic zeolite used in the present invention, all commercially available ones having a pore diameter of 3 to 15 mm can be used.
Further, the getter agent used in the present invention is not particularly limited. For example, Zr-V, Zr-Ti, Zr-Fe, Zr-Cu, Zr-Cr, Zr-Ni, Zr-Co, Zr -Nb, Zr-W, Zr-V-Ni, Zr-V-Cu, Zr-V-Co, Zr-V-Fe, Zr-V-Ni-Cu, Zr-V-Ni-Cr, Zr-V Alloys such as -Ni-Co and Zr-V-Cr-Fe can be used. These alloys are preferably hydride in advance.
本発明における粗水素ガスは、不純物として通常は、窒素、酸素、一酸化炭素、二酸化炭素、水、及びメタンから選ばれる１種以上のガスを、合計で０．１〜１０００ｐｐｍ程度含む水素ガスである。
本発明のガスの精製装置は、通常はこのような粗水素ガスの導入配管４及び精製水素ガスの取出し配管５のほか、パラジウム触媒１及び合成ゼオライト２を再生するための再生ガスの導入配管６及び再生ガスの排出配管７を備えている。
The crude hydrogen gas in the present invention is usually a hydrogen gas containing about 0.1 to 1000 ppm of one or more gases selected from nitrogen, oxygen, carbon monoxide, carbon dioxide, water, and methane as impurities. is there.
The gas purification apparatus of the present invention usually has such a crude hydrogen
本発明において、粗水素ガスとパラジウム触媒の接触温度、及び、粗水素ガスと合成ゼオライトの接触温度は、通常は０〜１００℃であり、粗水素ガスとゲッター剤の接触温度は、通常は４００〜６００℃である。また、粗水素ガスと、パラジウム触媒、合成ゼオライト、ゲッター剤と接触する際のガス圧力は、通常は常圧であるが、１０ＫＰａ（絶対圧力）のような減圧あるいは１ＭＰａ（絶対圧力）のような加圧下で処理することも可能である。 In the present invention, the contact temperature between the crude hydrogen gas and the palladium catalyst, and the contact temperature between the crude hydrogen gas and the synthetic zeolite are usually 0 to 100 ° C., and the contact temperature between the crude hydrogen gas and the getter agent is usually 400. ~ 600 ° C. Further, the gas pressure when contacting the crude hydrogen gas with the palladium catalyst, the synthetic zeolite, and the getter agent is usually normal pressure, but it is a reduced pressure such as 10 KPa (absolute pressure) or 1 MPa (absolute pressure). It is also possible to process under pressure.
本発明においては、粗水素ガスがパラジウム触媒と接触することにより、粗水素ガスに不純物として含まれる酸素が水素と反応して水が生成する。また、少量であれば、粗水素ガスに含まれる一酸化炭素も吸着除去できる。また、粗水素ガスが合成ゼオライトと接触することにより、粗水素ガスに不純物として含まれる二酸化炭素、水、あるいは前記の酸素と水素の反応により生成した水が合成ゼオライトに吸着され、粗水素ガスから除去される。さらに粗水素ガスがゲッター剤と接触することにより、粗水素ガスに不純物として含まれる一酸化炭素、窒素、メタンがゲッター剤に捕捉され、粗水素ガスから除去される。前記不純物は、通常は全て１ｐｐｂ以下まで除去可能である。 In the present invention, when the crude hydrogen gas comes into contact with the palladium catalyst, oxygen contained as an impurity in the crude hydrogen gas reacts with hydrogen to produce water. In addition, if the amount is small, carbon monoxide contained in the crude hydrogen gas can also be adsorbed and removed. Further, when the crude hydrogen gas comes into contact with the synthetic zeolite, carbon dioxide contained in the crude hydrogen gas as an impurity, water, or water produced by the reaction of the oxygen and hydrogen is adsorbed on the synthetic zeolite, Removed. Further, when the crude hydrogen gas comes into contact with the getter agent, carbon monoxide, nitrogen and methane contained as impurities in the crude hydrogen gas are captured by the getter agent and removed from the crude hydrogen gas. All the impurities can usually be removed to 1 ppb or less.
本発明においては、パラジウム触媒は長時間の使用により失活し、合成ゼオライトは吸着能力の限界に達するとそれ以上不純物を吸着できなくなるので、これらを再生する必要がある。パラジウム触媒、合成ゼオライトを再生する際は、図１または図２のようなガスの精製装置の場合は、水素ガスまたは希ガスの精製処理を中止した後、例えばパラジウム触媒及び合成ゼオライトを、１００〜４００℃程度で加熱するとともに、再生ガスの導入配管６から、水素、不活性ガス等の再生ガスを、パラジウム触媒、合成ゼオライトに供給することによって行なわれる。
In the present invention, the palladium catalyst is deactivated after a long period of use, and when the synthetic zeolite reaches the limit of the adsorption capacity, impurities can no longer be adsorbed. Therefore, it is necessary to regenerate them. When regenerating the palladium catalyst and synthetic zeolite, in the case of the gas purification apparatus as shown in FIG. 1 or FIG. 2, after the purification treatment of hydrogen gas or rare gas is stopped, for example, the palladium catalyst and synthetic zeolite are Heating is performed at about 400 ° C., and a regeneration gas such as hydrogen or an inert gas is supplied from a regeneration
しかし、図３に示すように、パラジウム触媒の充填筒と合成ゼオライトの充填筒からなるラインが、並列に２ライン以上設置され、各々のラインが１筒のゲッター剤の充填筒に接続されてなる精製装置、あるいは、図４に示すように、パラジウム触媒と合成ゼオライトの充填筒が、並列に２筒以上設置され、各々の充填筒が１筒のゲッター剤の充填筒に接続されてなる精製装置を使用することにより、少なくとも１ラインまたは１筒で精製を行なうとともに、他の少なくとも１ラインまたは１筒でパラジウム触媒及び合成ゼオライトの再生を行なうことが可能となり、各々のラインまたは充填筒を適宜切替ることにより、水素ガスの精製を連続で実施できる。尚、図５に示すように、合成ゼオライトの充填筒のみが並列に２筒以上設置されてなる精製装置とすることもできる。 However, as shown in FIG. 3, two or more lines composed of a palladium catalyst filling cylinder and a synthetic zeolite filling cylinder are installed in parallel, and each line is connected to a single getter agent filling cylinder. As shown in FIG. 4, a purification apparatus or a purification apparatus in which two or more cylinders of palladium catalyst and synthetic zeolite are installed in parallel, and each cylinder is connected to one cylinder of getter agent. Can be used to purify at least one line or cylinder and regenerate the palladium catalyst and synthetic zeolite in at least one other line or cylinder. Thus, the purification of hydrogen gas can be carried out continuously. In addition, as shown in FIG. 5, it can also be set as the refinement | purification apparatus by which only the filling cylinder of a synthetic zeolite is installed in parallel 2 or more cylinders.
本発明に使用されるパラジウム触媒は、触媒作用により粗水素ガスに含まれる酸素を水素と反応させて水に変換し、下流に設置された吸着能力が大きな合成ゼオライトにより吸着除去する構成なので、ニッケル等の金属と比較して１回の再生で多量の酸素を粗水素ガスから除去することができ、再生周期を大幅に長く設定することができる。また、本発明においては、再生ができないゲッター剤をパラジウム触媒及び合成ゼオライトの下流側に設けるので、ゲッター剤の寿命を大幅に延ばすことが可能であり、水素ガスの精製を効率よく行なうことができる。 The palladium catalyst used in the present invention has a structure in which oxygen contained in the crude hydrogen gas is reacted with hydrogen by catalytic action to convert it into water, and is adsorbed and removed by a synthetic zeolite having a large adsorption capacity installed downstream. A large amount of oxygen can be removed from the crude hydrogen gas by one regeneration compared to metals such as, and the regeneration cycle can be set significantly longer. Further, in the present invention, the getter agent that cannot be regenerated is provided on the downstream side of the palladium catalyst and the synthetic zeolite, so that the life of the getter agent can be greatly extended and the purification of hydrogen gas can be performed efficiently. .
次に、本発明を実施例により具体的に説明するが、本発明がこれらにより限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by these.
（精製装置の製作）
市販のパラジウム触媒及び合成ゼオライト（細孔径５Å相当）を、内径２８．４ｍｍ、長さ１０００ｍｍのＳＵＳ３１６Ｌ製の充填筒の内部に、充填長が各々３００ｍｍ、６００ｍｍとなるように充填した。また、Ｚｒ−Ｖ（Ｚｒ７０ｗｔ％、Ｖ３０ｗｔ％）の合金からなるゲッター剤を、内径５４．９ｍｍ、長さ６００ｍｍのＳＵＳ３１６Ｌ製の充填筒の内部に、充填長が３００ｍｍとなるように充填した。前記のパラジウム触媒及び合成ゼオライトの充填筒２筒、及びゲッター剤の充填筒１筒を、図４に示すように設置して水素ガスの精製装置を製作した。
(Production of purification equipment)
A commercially available palladium catalyst and synthetic zeolite (corresponding to a pore diameter of 5 mm) were filled into a SUS316L-made filling cylinder having an inner diameter of 28.4 mm and a length of 1000 mm so that the filling lengths were 300 mm and 600 mm, respectively. Further, a getter agent made of an alloy of Zr-V (Zr 70 wt%, V 30 wt%) was filled in a filling tube made of SUS316L having an inner diameter of 54.9 mm and a length of 600 mm so that the filling length was 300 mm. The palladium catalyst and synthetic
（水素ガスの精製試験）
次に、パラジウム触媒及び合成ゼオライトの充填筒を３００℃に加熱した後、再生ガスの導入配管から水素ガスを２Ｌ／ｍｉｎの流量で４時間導入して還元処理を行ない室温に冷却した。また同様に、ゲッター剤の充填筒を５００℃に加熱した後、水素とアルゴンの混合ガス（徐々に水素濃度を上昇）を１Ｌ／ｍｉｎの流量で１０時間導入して還元処理を行ない室温に冷却した。
(Hydrogen gas purification test)
Next, after the palladium catalyst and the synthetic zeolite-filled cylinder were heated to 300 ° C., hydrogen gas was introduced from the regeneration gas introduction pipe at a flow rate of 2 L / min for 4 hours to perform a reduction treatment and cool to room temperature. Similarly, after heating the filled cylinder of the getter agent to 500 ° C., a mixed gas of hydrogen and argon (the hydrogen concentration is gradually increased) is introduced at a flow rate of 1 L / min for 10 hours to perform reduction treatment and cool to room temperature. did.
不純物として、窒素５ｐｐｍ、酸素１０ｐｐｍ、一酸化炭素１ｐｐｍ、二酸化炭素２ｐｐｍ、水３０ｐｐｍ、及びメタン０．１ｐｐｍを含む粗水素ガスを、室温、０．５ＭＰａ下、１６Ｌ／ｍｉｎの流量で、片方のパラジウム触媒及び合成ゼオライトの充填筒、及び５００℃に加熱されたゲッター剤の充填筒に導入した。この間、パラジウム触媒及び合成ゼオライトの充填筒と、ゲッター剤の充填筒の出口から排出されたガスの一部を約１０分間隔でサンプリングし、ガス検知装置（検出下限は、窒素０．１ｐｐｂ、酸素０．５ｐｐｂ、一酸化炭素０．１ｐｐｂ、二酸化炭素０．１ｐｐｂ、水１ｐｐｂ、メタン１ｐｐｂ）により前記不純物の有無を測定した。その結果、パラジウム触媒及び合成ゼオライトの充填筒の出口ガスから窒素、一酸化炭素、及びメタンが検出されたが、ゲッター剤の充填筒の出口ガスから不純物は検出されなかった。
Crude hydrogen gas containing 5 ppm nitrogen, 10 ppm oxygen, 1 ppm carbon monoxide, 2 ppm carbon dioxide, 30 ppm water, and 0.1 ppm methane as impurities at room temperature under 0.5 MPa and at a flow rate of 16 L / min. The catalyst and the synthetic zeolite were introduced into a filled cylinder and a getter agent filled cylinder heated to 500 ° C. During this time, a part of the gas discharged from the outlet of the palladium catalyst and synthetic zeolite filling tube and the getter agent filling tube was sampled at intervals of about 10 minutes, and the gas detection device (the detection lower limit was 0.1 ppb nitrogen, oxygen 0.5 ppb, carbon monoxide 0.1 ppb, carbon dioxide 0.1 ppb,
精製試験開始から４８０分後、パラジウム触媒及び合成ゼオライトの充填筒から二酸化炭素が検出された。直ちにパラジウム触媒及び合成ゼオライトの充填筒を、他の片方のパラジウム触媒及び合成ゼオライトの充填筒に切替えるとともに、使用済みのパラジウム触媒及び合成ゼオライトの充填筒を３００℃に加熱し、水素ガスを２Ｌ／ｍｉｎの流量で４時間導入して再生処理を行ない室温に冷却した。この間、ゲッター剤の充填筒の出口ガスから不純物は検出されなかった。 480 minutes after the start of the purification test, carbon dioxide was detected from the packed tube of palladium catalyst and synthetic zeolite. Immediately switch the packed cylinder of palladium catalyst and synthetic zeolite to the other filled cylinder of palladium catalyst and synthetic zeolite, heat the used palladium catalyst and synthetic zeolite filled cylinder to 300 ° C., and supply hydrogen gas at 2 L / It was introduced at a flow rate of min for 4 hours, regenerated and cooled to room temperature. During this time, no impurities were detected from the exit gas of the getter agent filling cylinder.
実施例１の精製装置の製作において、パラジウム触媒の充填筒、合成ゼオライトの充填筒、及びゲッター剤の充填筒を、図５に示すように設置したほかは実施例１と同様にして水素ガスの精製装置を製作した。
実施例１と同様にして還元処理を行なった後、実施例１と同様の粗水素ガスを、室温、０．５ＭＰａ下、１６Ｌ／ｍｉｎの流量で、１００℃に加熱されたパラジウム触媒、片方の合成ゼオライトの充填筒、及び５００℃に加熱されたゲッター剤の充填筒に導入した。この間、合成ゼオライトの充填筒と、ゲッター剤の充填筒の出口から排出されたガスの一部を約１０分間隔でサンプリングし、ガス検知装置により前記不純物の有無を測定した。その結果、合成ゼオライトの充填筒の出口ガスから窒素、一酸化炭素、及びメタンが検出されたが、ゲッター剤の充填筒の出口ガスから不純物は検出されなかった。
In the production of the purification apparatus of Example 1, hydrogen gas filling cylinders, synthetic zeolite filling cylinders, and getter agent filling cylinders were installed as shown in FIG. A purification device was manufactured.
After carrying out the reduction treatment in the same manner as in Example 1, the same crude hydrogen gas as in Example 1 was added at room temperature under 0.5 MPa at a flow rate of 16 L / min. They were introduced into a synthetic zeolite filling cylinder and a getter agent filling cylinder heated to 500 ° C. During this time, a portion of the gas discharged from the synthetic zeolite filling tube and the exit of the getter agent filling tube was sampled at intervals of about 10 minutes, and the presence or absence of the impurities was measured by a gas detector. As a result, nitrogen, carbon monoxide, and methane were detected from the exit gas of the synthetic zeolite filling cylinder, but no impurities were detected from the exit gas of the getter agent filling cylinder.
精製試験開始から５２０分後、合成ゼオライトの充填筒から二酸化炭素が検出された。直ちに合成ゼオライトの充填筒を、他の片方の合成ゼオライトの充填筒に切替えるとともに、使用済みの合成ゼオライトの充填筒を３００℃に加熱し、水素ガスを２Ｌ／ｍｉｎの流量で４時間導入して再生処理を行ない室温に冷却した。この間、ゲッター剤の充填筒の出口ガスから不純物は検出されなかった。 520 minutes after the start of the purification test, carbon dioxide was detected from the synthetic zeolite packed tube. Immediately switch the synthetic zeolite filling cylinder to the other synthetic zeolite filling cylinder, heat the used synthetic zeolite filling cylinder to 300 ° C., and introduce hydrogen gas at a flow rate of 2 L / min for 4 hours. Regeneration was performed and cooled to room temperature. During this time, no impurities were detected from the exit gas of the getter agent filling cylinder.
以上のように、本発明の水素ガスの精製方法及び精製装置は、大型または複雑な装置を用いることなく、粗水素ガスに含まれている窒素、酸素、一酸化炭素、二酸化炭素、水、メタンの全てを、１ｐｐｂ以下の超低濃度となるまで効率よく除去できることが確認された。 As described above, the method and apparatus for purifying hydrogen gas according to the present invention can include nitrogen, oxygen, carbon monoxide, carbon dioxide, water, methane contained in crude hydrogen gas without using a large or complicated apparatus. It has been confirmed that all of the above can be efficiently removed until the concentration becomes very low of 1 ppb or less.
１ パラジウム触媒
２ 合成ゼオライト
３ ゲッター剤
４ 粗水素ガスの導入配管
５ 精製水素ガスの取出し配管
６ 再生ガスの導入配管
７ 再生ガスの排出配管
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