JP4654413B2 - Hydrocarbon steam reforming catalyst - Google Patents
Hydrocarbon steam reforming catalyst Download PDFInfo
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- JP4654413B2 JP4654413B2 JP2005279436A JP2005279436A JP4654413B2 JP 4654413 B2 JP4654413 B2 JP 4654413B2 JP 2005279436 A JP2005279436 A JP 2005279436A JP 2005279436 A JP2005279436 A JP 2005279436A JP 4654413 B2 JP4654413 B2 JP 4654413B2
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- 239000003054 catalyst Substances 0.000 title claims description 38
- 229930195733 hydrocarbon Natural products 0.000 title claims description 33
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 33
- 238000000629 steam reforming Methods 0.000 title claims description 33
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 24
- 238000011282 treatment Methods 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 18
- 229910000765 intermetallic Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000010306 acid treatment Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000889 atomisation Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002715 modification method Methods 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 methane: CnHm Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000000463 material Substances 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Description
本発明は、炭化水素と水とを原料として水素を製造するための水蒸気改質用触媒に関するものである。 The present invention relates to a steam reforming catalyst for producing hydrogen using hydrocarbons and water as raw materials.
水素を燃焼すると水しか発生しないことから、地球環境の保全という観点からは、水素は理想的な燃料といえる。最近では、特に燃料電池の燃料として水素が注目されている。このような燃料としての水素の製造方法としてはこれまでに様々なものが知られている。そのうちの最も重要な方法として、メタンなどの炭化水素（CnHm）と水蒸気との反応により水素及び合成ガスを製造する方法があり、水蒸気改質反応とよばれている。その総括反応式は次の式で示され、大きな吸熱を伴う反応である。 Since only water is generated when hydrogen is burned, hydrogen is an ideal fuel from the viewpoint of conservation of the global environment. Recently, hydrogen has attracted attention as a fuel for fuel cells. Various methods for producing hydrogen as such a fuel have been known so far. Among them, the most important method is a method of producing hydrogen and synthesis gas by a reaction between a hydrocarbon such as methane (C n H m ) and steam, which is called a steam reforming reaction. The general reaction formula is shown by the following formula, and is a reaction with a large endotherm.
CnHm ＋ ｎH2O → ｎCO ＋（n+m/2）H2
従って、熱力学的には高温ほど有利であり、炭化水素の種類にもよるが、通常は700℃
以上の反応温度が必要であるとされている。このことから、炭化水素の水蒸気改質用触媒には、高い活性と共に、優れた耐熱性、高温安定性及び一定の高温強度が求められている。従来、このような炭化水素の水蒸気改質用の触媒としては、担体上に担持された遷移金属が一般的に用いられている。例えば、メタン（CH4）の水蒸気改質に対する最も高い触
媒活性を示す金属としてはRh，Ru，Ni，Ir，Pd，Pt，Reが知られている。なかでも、貴金属が最も多く使用されている。ただ、貴金属の場合には、コストが高いという問題がある。他方で、Niは比較的に安く、工業的によく使用されているが、活性が十分ではなく、耐熱性が低いという問題がある。そのため、貴金属やNiに代わる炭化水素改質用の触媒として、高活性、低コストで、耐熱性の良好な新しい触媒の開発が必要とされていた。
C n H m + nH 2 O → nCO + (n + m / 2) H 2
Therefore, thermodynamically, the higher the temperature, the more advantageous and usually 700 ° C, depending on the type of hydrocarbon.
It is said that the above reaction temperature is required. For this reason, hydrocarbon steam reforming catalysts are required to have high activity, excellent heat resistance, high-temperature stability, and constant high-temperature strength. Conventionally, a transition metal supported on a carrier is generally used as a catalyst for such steam reforming of hydrocarbons. For example, Rh, Ru, Ni, Ir, Pd, Pt, and Re are known as metals exhibiting the highest catalytic activity for steam reforming of methane (CH4). Among them, precious metals are most frequently used. However, in the case of precious metals, there is a problem that the cost is high. On the other hand, Ni is relatively cheap and often used industrially, but there is a problem that the activity is not sufficient and the heat resistance is low. Therefore, development of a new catalyst with high activity, low cost and good heat resistance has been required as a catalyst for hydrocarbon reforming in place of noble metals and Ni.
一方、金属間化合物Ni3Alは、通常の材料と異なり、降伏強度が正の温度依存性を示し
（強度の逆温度依存性と呼ばれている）、優れた高温特性、耐摩耗性を持っていることから、このような高温特性等を利用してNi3Al系金属間化合物を触媒用成形体として応用す
ることが提案されている（特許文献１）。
On the other hand, the intermetallic compound Ni 3 Al, unlike ordinary materials, has a positive temperature dependence of yield strength (called reverse temperature dependence of strength), and has excellent high-temperature characteristics and wear resistance. Therefore, it has been proposed to apply a Ni 3 Al intermetallic compound as a molded article for a catalyst using such high temperature characteristics (Patent Document 1).
また、最近、本出願の発明者らは、Ni3Al金属間化合物はメタノール改質反応に高い触
媒活性を示すことを見出してもいる（特許文献２）。
本発明は以上の通りの背景よりなされたものであって、従来の問題点を解消し、しかも、メタノール改質反応におけるNi3Al金属間化合物についての高い触媒活性として発明者
らによって得られている知見を踏まえて、高活性、低コスト、優れた耐熱性を有する、炭化水素の水蒸気改質用の新しい触媒と、これを用いた水蒸気改質方法を提供することを課題としている。
The present invention has been made based on the background as described above, solves the conventional problems, and has been obtained by the inventors as a high catalytic activity for the Ni 3 Al intermetallic compound in the methanol reforming reaction. Based on these findings, it is an object to provide a new catalyst for steam reforming of hydrocarbons having high activity, low cost, and excellent heat resistance, and a steam reforming method using the same.
本発明は、上記の課題を解決するものとして、以下のことを特徴としている。 The present invention is characterized by the following in order to solve the above problems.
１、耐熱性、活性に優れ、かつ貴金属を含まない、酸処理後、アルカリ処理する二段階処理された金属間化合物Ｎｉ３Ａｌを含有する炭化水素の水蒸気改質用触媒。
1. A catalyst for steam reforming of hydrocarbons, which is excellent in heat resistance and activity and does not contain a noble metal, and contains an intermetallic compound Ni 3 Al that has been subjected to an alkali treatment after acid treatment and then subjected to alkali treatment.
２、共存成分とともにNi3Al金属間化合物を含有し、共存成分を含めた全体の元素組成
（重量％）がNi 77-95%、Al 5-23%である炭化水素の水蒸気改質用触媒。
2. A catalyst for steam reforming of hydrocarbons containing Ni 3 Al intermetallic compound together with coexisting components, and the total elemental composition (wt%) including coexisting components is 77-95% Ni and 5-23% Al .
３、触媒表面にNiナノ粒子が存在する炭化水素の水蒸気改質用触媒。 3. Hydrocarbon steam reforming catalyst with Ni nanoparticles on the catalyst surface.
４、溶製したインゴットの切屑と機械研磨で得られた粉末もしくは回転ディスクアトマイズ法により作製された粉末形状を有している炭化水素の水蒸気改質用触媒。 4. A catalyst for steam reforming of hydrocarbons having a powder shape produced by a powder obtained by mechanical polishing and a powder obtained by slicing a molten ingot or a rotating disk atomization method.
５、金属間化合物Ｎｉ３Ａｌを酸処理後、アルカリ処理する二段階処理する炭化水素の水蒸気改質用触媒の製造方法。
5. A method for producing a hydrocarbon steam reforming catalyst, in which an intermetallic compound Ni 3 Al is acid-treated and then subjected to alkali treatment in two stages .
６、上記いずれかの触媒を用いる炭化水素の水蒸気改質方法。 6. A method for steam reforming hydrocarbon using any of the above catalysts.
７、触媒をあらかじめ水素還元処理した後に、炭化水素と水蒸気と混合ガスを前記触媒と接触させて水素を製造する炭化水素の水蒸気改質方法。 7. A hydrocarbon steam reforming method in which hydrogen is produced by bringing a hydrocarbon, steam and a mixed gas into contact with the catalyst after hydrogen reduction treatment of the catalyst in advance.
本発明によって、炭化水素の水蒸気改質反応において、広い温度範囲で高活性、優れた耐熱性を持つNi3Al金属間化合物からなる触媒が提供され、高効率、低コストの水素製造
プロセスに活用することができる。
The present invention provides a catalyst comprising a Ni 3 Al intermetallic compound having high activity and excellent heat resistance in a wide range of temperature in a hydrocarbon steam reforming reaction, which is utilized in a highly efficient and low-cost hydrogen production process. can do.
本発明においては、金属間化合物Ni3Alを主な成分とするものであるが、単独相として
の組成範囲はNi 85-88重量%、Al 12-15重量%である。このNi3Al金属間化合物を含有する
触媒では、他種のものを共存させていてもよく、例えばNiAl、Ni5Al3、Niなどが共存されていてもよい。これらの他種成分を共存する場合には、全体としての組成範囲はNi 77-95重量%、Al 5-23重量%となる。
In the present invention, the main component is the intermetallic compound Ni 3 Al, but the composition range as a single phase is 85 to 88% by weight of Ni and 12 to 15% by weight of Al. In the catalyst containing this Ni 3 Al intermetallic compound, other types may coexist, for example, NiAl, Ni 5 Al 3 , Ni, etc. may coexist. When these other components coexist, the composition range as a whole is Ni 77-95% by weight and Al 5-23% by weight.
以上のNi3Al金属間化合物を含有する触媒は、各種の形状のものとして使用してよいか
、触媒の活性、その調製方法、取扱い性等の観点からは粒状物とすることが好ましく考慮される。この場合、たとえば、回転ディスクアトマイズ法やインゴット溶製後の切削と機械的研磨等により作製することができる。
The above-mentioned catalyst containing Ni 3 Al intermetallic compound may be used in various shapes, or it is preferably considered to be a granular material from the viewpoint of the activity of the catalyst, its preparation method, handleability, etc. The In this case, for example, it can be produced by a rotating disk atomizing method, cutting after ingot melting, mechanical polishing, or the like.
また、本発明では、Ni3Alの表面形状、組成を制御することによって、触媒活性を高め
るために、あらかじめアルカリや酸で表面処理することが有効でもある。アルカリ処理は、一般的には、無機又は有機の塩基の水溶液もしくは有機溶媒の溶液を用いることができる。処理温度については、通常は、室温−100℃の範囲とすることができる。酸処理には
、無機酸または有機酸、それらの水溶液や有機溶液を用いることができる。処理温度としては、室温−50℃程度までとすることが一般的に考慮される。
In the present invention, it is also effective to perform surface treatment with an alkali or an acid in advance in order to increase the catalytic activity by controlling the surface shape and composition of Ni 3 Al. In general, the alkali treatment can use an aqueous solution of an inorganic or organic base or a solution of an organic solvent. About processing temperature, it can usually be set as the range of room temperature-100 degreeC. In the acid treatment, an inorganic acid or an organic acid, an aqueous solution or an organic solution thereof can be used. As the processing temperature, it is generally considered that the processing temperature is up to about room temperature-50 ° C.
上記のアルカリ処理の場合には、Alだけが溶出し、Niが殆んど溶出しない。たとえばNaOH水溶液を用いる場合には、その濃度は10%以上、望ましくは20-30％であり、また処理温度60-100℃、処理時間1時間以上が望ましい。酸処理の場合、AlとNiとも溶出するので、
高濃度、長時間処理すると、金属間化合物Ni3Alの損失が増えることに注意する必要があ
る。例えば、HCl水溶液の場合には、濃度20%以下、処理温度20℃付近、処理時間2時間以
下が望ましい。HNO3水溶液の場合には、濃度5%以下、処理温度20℃付近、処理時間2時間
以下が望ましい。
In the case of the above alkali treatment, only Al is eluted and Ni is hardly eluted. For example, when NaOH aqueous solution is used, the concentration is 10% or more, preferably 20-30%, and the treatment temperature is 60-100 ° C. and the treatment time is 1 hour or more. In the case of acid treatment, both Al and Ni elute,
It should be noted that the loss of the intermetallic compound Ni 3 Al increases when the treatment is performed at a high concentration for a long time. For example, in the case of an aqueous HCl solution, it is desirable that the concentration is 20% or less, the treatment temperature is around 20 ° C., and the treatment time is 2 hours or less. In the case of HNO 3 aqueous solution, it is desirable that the concentration is 5% or less, the treatment temperature is around 20 ° C., and the treatment time is 2 hours or less.
また、表面処理の効果を高めるため、酸とアルカリ処理を組み合わせ、二段階の表面処理を行うことも有効である。特に、まず、酸処理し、次いでアルカリ処理することが好適
に考慮される。酸処理により表面のAlとNiを溶出することにより、表面積を増やす。続いて、アルカリ処理により表面のAlを溶出することにより、表面積をさらに増加するとともに、表面のNi活性点を増加する。これにより触媒活性を著しく改善することが可能となる。
In order to enhance the effect of the surface treatment, it is also effective to perform a two-step surface treatment by combining an acid and an alkali treatment. In particular, it is preferable to first consider acid treatment and then alkali treatment. The surface area is increased by eluting the surface Al and Ni by acid treatment. Subsequently, by eluting the surface Al by alkali treatment, the surface area is further increased and the Ni active sites on the surface are increased. As a result, the catalytic activity can be remarkably improved.
以上のとおりの本発明の触媒は、炭化水素の水蒸気改質反応による水素の製造に用いられる。この場合の炭化水素は、メタンをはじめとする各種の炭化水素：CnHmであってよく、たとえば、メタン、エタン、プロパン、ブタン、エチレン、プロピレン等々であってよい。炭化水素と水蒸気の割合は、炭化水素の種類によっても相違するが、一般的にはモル比として、H2O：炭化水素が、50〜0.5：１の範囲とし、反応温度は、400℃〜950℃程度が考慮される。500℃〜750℃程度の比較的低い反応温度においても触媒の作用は高活性なものとなる。 The catalyst of the present invention as described above is used for production of hydrogen by a hydrocarbon steam reforming reaction. The hydrocarbon in this case may be various hydrocarbons including methane: CnHm, for example, methane, ethane, propane, butane, ethylene, propylene, and the like. Although the ratio of hydrocarbon and water vapor varies depending on the type of hydrocarbon, generally, the molar ratio is H 2 O: hydrocarbon in the range of 50 to 0.5: 1, and the reaction temperature is 400 ° C. to About 950 ° C is considered. Even at a relatively low reaction temperature of about 500 ° C to 750 ° C, the action of the catalyst becomes highly active.
反応は、バッチ式あるいは流通式のいずれでもよく、流通式の場合には、固定床、流動床等の各種の方式であってよい。 The reaction may be either a batch type or a flow type, and in the case of the flow type, various methods such as a fixed bed and a fluidized bed may be used.
なお、反応に際しては、触媒をあらかじめ水素還元処理しておくことも有効である。 In the reaction, it is also effective to subject the catalyst to a hydrogen reduction treatment in advance.
以下、本発明の例を具体的に記述する。もちろん、以下の例によって発明が限定されることはない。
＜実施例１＞
まず、回転ディスクアトマイズ法で組成86.91重量％Ni-13.09重量％AlのNi3Al粉末試料を作製した。ＢＥＴ法を用いて比表面積を測定した結果、粒子直径32μm以下の粉末の比
表面積は1.3m２/g；粒子直径32-75μmの粉末の比表面積は0.4m２/g；粒子直径75-150μｍの粉末の比表面積は0.1m２/gであった。
Examples of the present invention are specifically described below. Of course, the invention is not limited by the following examples.
<Example 1>
First, a Ni 3 Al powder sample having a composition of 86.91 wt% Ni-13.09 wt% Al was prepared by a rotating disk atomization method. As a result of measuring the specific surface area using the BET method, the specific surface area of the powder having a particle diameter of 32 μm or less is 1.3 m 2 / g; the specific surface area of the powder having a particle diameter of 32-75 μm is 0.4 m 2 / g; The specific surface area of this powder was 0.1 m 2 / g.
次に、作製したNi3Al粉末に対して以下の各種のアルカリ処理と酸処理を行った。
（１）アルカリ処理：上記粒子直径75-150μｍのNi3Al粉末３ｇを120ｇの20％NaOH水溶液に加え、93℃の温度で攪拌しながら５時間放置した。その後アルカリ水溶液をデカンテーションにより除去した。沈殿物を適量な蒸留水で洗浄し、洗液をデカンテーションにより除去した。この操作を洗液が中性になるまで繰返した。得られた沈殿生成物を脱水した。脱水後50℃で５時間乾燥して、Ni3Al触媒を調製した。ＩＣＰ発光分光分析の結果、このNaOH水溶液により、当初のNi3Al中のAl量の約2.2％（重量比）が溶出されて除去されたこ
とがわかった。一方、Niは溶出していなかった。
（２）HNO3水溶液処理：回転ディスクアトマイズ法で作製した粒子直径75-150μｍのNi3Al粉末３ｇを120ｇの２％のHNO3水溶液に加え、室温で攪拌しながら15分放置した。その後NHO3水溶液をデカンテーションにより除去した。さらに、沈殿物を適量な蒸留水で洗浄し、洗液をデカンテーションにより除去した。この操作を洗液が中性になるまで繰返した。得られた沈殿生成物を脱水した。脱水後50℃で５時間乾燥して、Ni3Al触媒を調製した。
ＩＣＰ発光分光分析の結果、このHNO3水溶液により、当初のNi3Al中のNi量の約6.6％、Al量の約7.1％(重量比)を溶出し除去されたことがわかった。
（３）酸処理とアルカリ処理との二段階表面処理：まず、Ni3Al粉末試料を上記（２）のHNO3水溶液処理により処理し、続いて、酸処理した粉末を上記（１）によってアルカリ処
理した。
Next, the following various alkali treatments and acid treatments were performed on the produced Ni 3 Al powder.
(1) Alkali treatment: 3 g of Ni 3 Al powder having a particle diameter of 75-150 μm was added to 120 g of 20% NaOH aqueous solution and left standing at 93 ° C. for 5 hours with stirring. Thereafter, the alkaline aqueous solution was removed by decantation. The precipitate was washed with an appropriate amount of distilled water, and the washing was removed by decantation. This operation was repeated until the washing liquid became neutral. The resulting precipitated product was dehydrated. After dehydration, the mixture was dried at 50 ° C. for 5 hours to prepare a Ni 3 Al catalyst. As a result of ICP emission spectroscopic analysis, it was found that about 2.2% (weight ratio) of Al in the original Ni 3 Al was eluted and removed by this NaOH aqueous solution. On the other hand, Ni was not eluted.
(2) HNO 3 aqueous solution treatment: 3 g of Ni 3 Al powder with a particle diameter of 75-150 μm prepared by the rotating disk atomization method was added to 120 g of 2% HNO 3 aqueous solution and left at room temperature for 15 minutes with stirring. Thereafter, the NHO 3 aqueous solution was removed by decantation. Further, the precipitate was washed with an appropriate amount of distilled water, and the washing solution was removed by decantation. This operation was repeated until the washing liquid became neutral. The resulting precipitated product was dehydrated. After dehydration, the mixture was dried at 50 ° C. for 5 hours to prepare a Ni 3 Al catalyst.
As a result of ICP emission spectroscopic analysis, it was found that about 6.6% of the Ni content in the original Ni 3 Al and about 7.1% (weight ratio) of the Al content were eluted and removed by this HNO 3 aqueous solution.
(3) Two-stage surface treatment of acid treatment and alkali treatment: First, a Ni 3 Al powder sample is treated by the HNO 3 aqueous solution treatment of (2) above, and then the acid-treated powder is alkalinized by (1) above. Processed.
図１はＳＥＭにより回転ディスクアトマイズ法で作製したNi3Al粉末及び上記の３種類
の表面処理（１）（２）（３）した試料の表面形態の観察結果である。酸処理及びアルカリ処理により表面組織、形態が大きく変化したことがわかる。図２は酸処理とアルカリ処理との二段階表面処理した試料の表面微細組織を詳しく観察した結果である。数10nm以下
の微細粒子が形成されていることがわかる。図３はTEM−EDSによりこれらのナノ粒子の組成は主にNiである分析結果を示す。図４は回転ディスクアトマイズ法で作製したNi3Al粉
末及び上記の３種類の表面処理（１）（２）（３）した試料のＸＲＤ分析結果である。すべての試料においては、Ni3Alのピークだけが検出された。これにより、これらの表面処
理の結果、Ni3Alの表面層のごく一部のAlとNiが溶出されるだけで、全体的にはNi3Al構造が保持されていることがわかる。
＜実施例２＞
回転ディスクアトマイズ法で作製した粉末試料（未処理試料）及び上記実施例１での（１）、（２）、（３）の方法で処理した３種類の粉末試料を触媒として、触媒反応装置（固定床流通式反応装置）で600℃１時間水素還元処理を行った後、常圧、600℃から950℃
までの各温度でメタンの水蒸気改質反応（H2O：CH4＝3.5mol：１mol）を行った。その結
果を図５で示す。水素発生速度（ml min-1 g-cat-1）は酸処理とアルカリ処理との二段階処理した試料の場合、600℃から高い水素発生速度が得られることが確認された。
＜実施例３＞
実施例１の（３）の方法で二段階処理した試料を用いて、600℃、700℃、900℃でそれ
ぞれ10時間、メタンの水蒸気改質反応を続け、Ni3Alの触媒活性の経時変化を調べた。図
６−８は測定した各生成ガスの生成速度を反応時間の関数として示した結果である。600
℃、700℃では、10時間反応しても、触媒活性の劣化が少ないことがわかった。また、900℃では、触媒活性が劣化するが、10時間反応しても、100ml min-1g-cat-1以上の水素発生速度が得られることがわかった。また、各温度で、主にH2，CO，CO2，CH4，H2Oが生成し
ていることが確認された。これにより、Ni3Alは主に以下のメタンの水蒸気改質反応、一
酸化炭素シフト反応に活性を示すことが分かる。
FIG. 1 shows the observation results of the surface morphology of Ni 3 Al powder produced by SEM with a rotating disk atomization method and the above three types of surface treatments (1), (2) and (3). It can be seen that the surface texture and morphology were greatly changed by acid treatment and alkali treatment. FIG. 2 shows the result of detailed observation of the surface microstructure of the sample subjected to the two-stage surface treatment of acid treatment and alkali treatment. It can be seen that fine particles of several tens of nm or less are formed. FIG. 3 shows an analysis result by TEM-EDS in which the composition of these nanoparticles is mainly Ni. FIG. 4 shows the XRD analysis results of the Ni 3 Al powder produced by the rotating disk atomization method and the above-mentioned three types of surface treatments (1), (2), and (3). In all samples, only the Ni 3 Al peak was detected. Thus, as a result of these surface treatments, it can be seen that only a small portion of Al and Ni in the surface layer of Ni 3 Al is eluted, and the Ni 3 Al structure is maintained as a whole.
<Example 2>
Using a powder sample (untreated sample) produced by the rotating disk atomization method and the three types of powder samples treated by the methods (1), (2) and (3) in Example 1 above as a catalyst, a catalytic reactor ( After hydrogen reduction treatment at 600 ° C for 1 hour in a fixed bed flow reactor, normal pressure, 600 ° C to 950 ° C
The steam reforming reaction of methane (H 2 O: CH 4 = 3.5 mol: 1 mol) was performed at each temperature up to. The result is shown in FIG. As for the hydrogen generation rate (ml min -1 g-cat -1 ), it was confirmed that a high hydrogen generation rate was obtained from 600 ° C. in the case of a sample subjected to two-step treatment of acid treatment and alkali treatment.
<Example 3>
Using the sample treated in two steps by the method (3) of Example 1, the steam reforming reaction of methane was continued for 10 hours at 600 ° C., 700 ° C., and 900 ° C., respectively, and the catalyst activity of Ni 3 Al was changed over time. I investigated. FIG. 6-8 shows the results of the measured production rate of each product gas as a function of reaction time. 600
At ℃ and 700 ℃, it was found that there was little deterioration in the catalytic activity even after reaction for 10 hours. Moreover, although the catalytic activity deteriorated at 900 ° C., it was found that a hydrogen generation rate of 100 ml min −1 g-cat −1 or more could be obtained even after reaction for 10 hours. In addition, it was confirmed that H 2 , CO, CO 2 , CH 4 , and H 2 O were mainly produced at each temperature. This indicates that Ni 3 Al is mainly active in the following methane steam reforming reaction and carbon monoxide shift reaction.
（１）メタンの水蒸気改質反応： CH4+ H2O → 3H2 + CO
（２）一酸化炭素シフト反応： CO + H2O → CO2 + H2
また、図９は、600℃、700℃、900℃での定温反応中のメタンの転化率の結果を示して
いる。この結果から、700℃の場合、メタン転化率が最も良好であることがわかる。
(1) Steam reforming reaction of methane: CH 4 + H 2 O → 3H 2 + CO
(2) Carbon monoxide shift reaction: CO + H 2 O → CO 2 + H 2
FIG. 9 shows the results of methane conversion during the constant temperature reaction at 600 ° C., 700 ° C., and 900 ° C. This result shows that the methane conversion is the best at 700 ° C.
Claims (7)
7. The hydrocarbon steam reforming method according to claim 6, wherein the catalyst is subjected to a hydrogen reduction treatment in advance and then contacted with a mixture of hydrocarbon and steam.
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| JP5268069B2 (en) * | 2009-03-02 | 2013-08-21 | 独立行政法人物質・材料研究機構 | Methane steam reforming catalyst |
| JP5640803B2 (en) * | 2010-03-29 | 2014-12-17 | Ｊｆｅスチール株式会社 | How to operate a blast furnace or steelworks |
| CN102782161A (en) * | 2010-03-02 | 2012-11-14 | 杰富意钢铁株式会社 | Blast furnace operation method, iron mill operation method, and method for utilizing a gas containing carbon oxides |
| JP6903324B2 (en) * | 2017-08-10 | 2021-07-14 | 国立研究開発法人物質・材料研究機構 | Hydrogen production catalyst, its production method, and hydrogen production equipment using it |
Citations (4)
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|---|---|---|---|---|
| JPS5588856A (en) * | 1978-12-27 | 1980-07-04 | Osamu Izumi | Production of nickel formed body for catalyst |
| JP2002102715A (en) * | 2000-09-29 | 2002-04-09 | Kawasaki Heavy Ind Ltd | Catalyst formed on metal surface and method for forming catalyst on metal surface |
| JP2003530207A (en) * | 2000-04-08 | 2003-10-14 | セラム リサーチ リミテッド | Raney catalyst production method by gas atomization of molten alloy |
| WO2005072865A1 (en) * | 2004-02-02 | 2005-08-11 | National Institute For Materials Science | INTERMETALLIC COMPOUND Ni3Al CATALYST FOR METHANOL REFORMING AND METHOD FOR REFORMING METHANOL USING SAME |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5588856A (en) * | 1978-12-27 | 1980-07-04 | Osamu Izumi | Production of nickel formed body for catalyst |
| JP2003530207A (en) * | 2000-04-08 | 2003-10-14 | セラム リサーチ リミテッド | Raney catalyst production method by gas atomization of molten alloy |
| JP2002102715A (en) * | 2000-09-29 | 2002-04-09 | Kawasaki Heavy Ind Ltd | Catalyst formed on metal surface and method for forming catalyst on metal surface |
| WO2005072865A1 (en) * | 2004-02-02 | 2005-08-11 | National Institute For Materials Science | INTERMETALLIC COMPOUND Ni3Al CATALYST FOR METHANOL REFORMING AND METHOD FOR REFORMING METHANOL USING SAME |
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