JP6099202B2 - Method for producing metal catalyst - Google Patents
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- 229910052751 metal Inorganic materials 0.000 title claims description 98
- 239000002184 metal Substances 0.000 title claims description 98
- 239000003054 catalyst Substances 0.000 title claims description 84
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 229910000765 intermetallic Inorganic materials 0.000 claims description 26
- 238000002386 leaching Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000002923 metal particle Substances 0.000 claims description 16
- 229910052737 gold Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910020637 Co-Cu Inorganic materials 0.000 claims description 4
- 239000011246 composite particle Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 2
- 239000010931 gold Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 18
- 229910000510 noble metal Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910017390 Au—Fe Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Description
本発明は、金属触媒の製造方法に関する。 The present invention relates to a method for producing a metal catalyst .
貴金属は、その反応性の高さから、酸化、水素化、脱水素化、ＮＯｘ分解・還元等のさまざまな反応系の触媒として用いられている。しかし、貴金属は高価であり、また資源量も少ないため、その使用量の低減が重要課題の一つとなっている。従来の貴金属を担持した触媒は、使用貴金属量あたりの表面積を最大限にするために、酸化物などの担体に貴金属粒子をナノ粒子状態で分散担持させたものが一般的である。 Noble metals are used as catalysts for various reaction systems such as oxidation, hydrogenation, dehydrogenation, NOx decomposition and reduction because of their high reactivity. However, since noble metals are expensive and have a small amount of resources, reduction of the amount used is one of the important issues. Conventional catalysts supporting noble metals are generally those in which noble metal particles are dispersed and supported on a carrier such as an oxide in order to maximize the surface area per amount of noble metal used.
このような従来の担持貴金属触媒は、含浸法、ゾルゲル法、析出沈殿法などの様々な方法により調製されている（例えば、非特許文献１参照）。その際、貴金属原料として、塩化物、硝酸塩、アミン等の無機または有機金属塩や、アセチルアセトナート等の金属錯体を用いており、金属化の過程で加熱による貴金属の前駆物質の分解や還元処理を行っている（例えば、特許文献１または２参照）。また、貴金属の塩または錯体をアルコール類などで液相還元させてカーボンに担持させる、温和な条件下での製造方法も用いられている（例えば、特許文献３参照）。また、本発明者等により、Ａｌ１００−ａ−ｂＣｕａＣｏｂ（ただし、５原子％≦ａ≦３０原子％、５原子％≦ｂ≦２５原子％）で示される組成の準結晶Ａｌ合金のインゴットを粉砕した後、リーチング処理する銅触媒の製造方法も提案されている（例えば、特許文献４参照）。 Such a conventional supported noble metal catalyst is prepared by various methods such as an impregnation method, a sol-gel method, and a precipitation method (see Non-Patent Document 1, for example). At that time, inorganic or organic metal salts such as chlorides, nitrates, amines, and metal complexes such as acetylacetonate are used as precious metal raw materials, and decomposition or reduction treatment of noble metal precursors by heating in the process of metallization. (For example, refer to Patent Document 1 or 2). Further, a production method under mild conditions in which a noble metal salt or complex is liquid-phase reduced with an alcohol or the like and supported on carbon is also used (for example, see Patent Document 3). In addition, the present inventors have made a quasicrystalline Al alloy having a composition represented by Al 100-ab Cu a Co b (where 5 atomic% ≦ a ≦ 30 atomic%, 5 atomic% ≦ b ≦ 25 atomic%). A method for producing a copper catalyst in which a leaching process is performed after pulverizing the ingot has also been proposed (see, for example, Patent Document 4).
なお、貴金属として金を担持した触媒試料は、ワールド・ゴールド・カウンシル（Ｗｏｒｌｄ Ｇｏｌｄ Ｃｏｕｎｃｉｌ；ＷＧＣ）が標準触媒試料として提供しており、比較的容易に入手することができる（例えば、非特許文献２参照）。 In addition, the catalyst sample which carry | supported gold | metal | money as a noble metal is provided as a standard catalyst sample by the World Gold Council (World Gold Council; WGC), and can be obtained comparatively easily (for example, nonpatent literature 2). reference).
しかしながら、特許文献１および２に記載の基金属触媒の製造方法では、金属化を行う際の加熱過程で、貴金属粒子の凝集が起こるため、貴金属粒子の分散性が悪く、粒子径も不均一になるという課題があった。また、特許文献３に記載の貴金属触媒の製造方法では、担体がカーボンに制限されるという課題があった。また、特許文献４に記載の銅触媒の製造方法では、高分散化したＣｕ粒子が得られるが、担体がＣｏを含むものに限定されるという課題があった。 However, in the method for producing a base metal catalyst described in Patent Documents 1 and 2, noble metal particles aggregate in the heating process during metallization, so that the dispersibility of the noble metal particles is poor and the particle diameter is not uniform. There was a problem of becoming. Further, the method for producing a noble metal catalyst described in Patent Document 3 has a problem that the support is limited to carbon. Further, in the method for producing a copper catalyst described in Patent Document 4, highly dispersed Cu particles can be obtained, but there is a problem that the support is limited to those containing Co.
本発明は、このような課題に着目してなされたもので、様々な担体に、金属粒子を均一に高分散化させることができる金属触媒の製造方法を提供することを目的とする。 The present invention has been made paying attention to such problems, and an object of the present invention is to provide a method for producing a metal catalyst capable of uniformly and highly dispersing metal particles on various supports.
上記目的を達成するために、本発明に係る金属触媒の製造方法は、Ａｌ１００−（ｘ＋ｙ）Ｍ１ ｘＭ２ ｙ（ただし、Ｍ１はＴｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｚｒ，Ｎｂ，Ｍｏ，Ｈｆ，Ｔａ，ＷおよびＲｅのうちの少なくとも１つの金属、Ｍ２はＡｕ，Ｐｔ，Ｉｒ，Ａｇ，Ｐｄ，Ｒｈ，ＲｕおよびＣｕのうちの少なくとも１つの金属、１０原子％≦ｘ≦３０原子％、０原子％＜ｙ≦１０原子％）で示される組成のＡｌ基金属間化合物（ただし、Ａｌ−Ｃｏ−Ｃｕ系化合物を除く）のインゴットを粉砕した後、アルカリ水溶液でリーチング処理することを特徴とする。 In order to achieve the above object, the method for producing a metal catalyst according to the present invention is Al 100- (x + y) M 1 x M 2 y (where M 1 is Ti, V, Cr, Mn, Fe, Co, Zr). , Nb, Mo, Hf, Ta, W and Re, M 2 is at least one metal of Au, Pt, Ir, Ag, Pd, Rh, Ru and Cu, 10 atomic% ≦ After pulverizing an ingot of an Al-based intermetallic compound having a composition represented by x ≦ 30 atomic%, 0 atomic% <y ≦ 10 atomic% (excluding an Al—Co—Cu-based compound), leaching is performed with an alkaline aqueous solution. It is characterized by processing.
また、本発明に係る金属触媒の製造方法は、Ａｌ１００−（ｘ＋ｙ）Ｍ１ ｘＭ２ ｙ（ただし、Ｍ１はＴｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｚｒ，Ｎｂ，Ｍｏ，Ｈｆ，Ｔａ，ＷおよびＲｅのうちの少なくとも１つの金属、Ｍ２はＡｕ，Ｐｔ，Ｉｒ，Ａｇ，Ｐｄ，Ｒｈ，Ｒｕ，ＮｉおよびＣｕのうちの少なくとも１つの金属、２１．５原子％≦ｘ≦２６原子％、０原子％＜ｙ≦１０原子％）で示される組成のＡｌ基金属間化合物（ただし、Ａｌ−Ｃｏ−Ｃｕ系化合物を除く）のインゴットを、液体急冷法によりフレーク状またはリボン状にした後、アルカリ水溶液でリーチング処理してもよい。 The manufacturing method of the metal catalyst according to the present invention, Al 100- (x + y) M 1 x M 2 y ( provided that, M 1 is Ti, V, Cr, Mn, Fe, Co, Zr, Nb, Mo, Hf , Ta, W and Re, M 2 is at least one metal of Au, Pt, Ir, Ag, Pd, Rh, Ru, Ni and Cu, 21.5 atomic% ≦ x ≦ An ingot of an Al-based intermetallic compound having a composition represented by 26 atomic% and 0 atomic% <y ≦ 10 atomic%) (excluding an Al—Co—Cu based compound) is flaked or ribbon-shaped by a liquid quenching method. After that, a leaching treatment with an alkaline aqueous solution may be performed.
本発明に係る金属触媒の製造方法は、Ａｌ−Ｍ１の一部を金属Ｍ２で置換したＡｌ基金属間化合物の合金を前駆物質とし、これをアルカリ水溶液でリーチング処理することにより、Ａｌを選択的に溶出させる。この工程において、金属Ｍ１が酸化物または水酸化物に変化し、金属Ｍ２はそのまま残留するため、加熱処理を必要とせずに、高分散担持金属触媒を得ることができる。加熱処理を行わないため、金属Ｍ２の粒子が凝集せず、金属Ｍ１の酸化物または水酸化物から成る担体に、均一な粒子径の金属粒子を均一に高分散化させることができる。 The method for producing a metal catalyst according to the present invention uses an Al-based intermetallic compound alloy in which a part of Al-M 1 is substituted with a metal M 2 as a precursor, and leaches it with an alkaline aqueous solution to thereby obtain Al. Elute selectively. In this step, the metal M 1 is changed to an oxide or hydroxide, the metal M 2 is left as it is, it can be without requiring heat treatment to obtain a highly dispersed supported metal catalyst. Since the heat treatment is not performed, the metal M 2 particles do not aggregate, and the metal particles having a uniform particle diameter can be uniformly and highly dispersed in the carrier made of the metal M 1 oxide or hydroxide.
このように、本発明に係る金属触媒の製造方法は、前記リーチング処理により、金属Ｍ１の酸化物粒子または水酸化物粒子に、金属Ｍ２の粒子が均一に分散した複合粒子を形成することができる。本発明に係る金属触媒の製造方法は、加熱処理を行わないため、従来の調製法と比べて簡便であり、金属粒子を様々な担体に安定して高分散化させることができる。また、金属粒子を均一に高分散化させることができるため、金属の担持効率を高めることができ、金属使用量の低減化を図ることができる。 Thus, the method for producing a metal catalyst according to the present invention forms composite particles in which metal M 2 particles are uniformly dispersed in oxide particles or hydroxide particles of metal M 1 by the leaching process. Can do. The method for producing a metal catalyst according to the present invention is simpler than conventional preparation methods because no heat treatment is performed, and metal particles can be stably dispersed in various supports. Further, since the metal particles can be uniformly and highly dispersed, the metal loading efficiency can be increased, and the amount of metal used can be reduced.
本発明に係る金属触媒の製造方法で、Ａｌ基金属間化合物は、単一相結晶合金であることが好ましく、単一相結晶合金になるよう、金属Ｍ１と金属Ｍ２の含有率ｘ，ｙがそれぞれ、１０原子％≦ｘ≦３０原子％、０原子％＜ｙ≦１０原子％となっている。Ａｌ基金属間化合物の組成は、特に、２１．５原子％≦ｘ≦２６原子％、０．５原子％＜ｙ≦４原子％であることが好ましい。この場合、組成割合ｘ，ｙがそれぞれの下限未満では、十分な触媒活性が得られなくなる傾向にある。また、ｘ，ｙがそれぞれの上限を超えると、単一な金属間化合物相を得にくくなるばかりでなく、高分散状態も得られにくくなる傾向にある。 In the method for producing a metal catalyst according to the present invention, the Al-based intermetallic compound is preferably a single-phase crystal alloy, and the contents x, M of the metal M 1 and the metal M 2 so as to become a single-phase crystal alloy. y is 10 atomic% ≦ x ≦ 30 atomic% and 0 atomic% <y ≦ 10 atomic%, respectively. The composition of the Al-based intermetallic compound is particularly preferably 21.5 atomic% ≦ x ≦ 26 atomic% and 0.5 atomic% <y ≦ 4 atomic%. In this case, when the composition ratios x and y are less than their respective lower limits, there is a tendency that sufficient catalytic activity cannot be obtained. Moreover, when x and y exceed the respective upper limits, it is difficult not only to obtain a single intermetallic compound phase but also to obtain a highly dispersed state.
本発明に係る金属触媒の製造方法は、リーチング処理の前に、Ａｌ基金属間化合物のインゴットを粉砕することにより、リーチング効率を高めることができる。また、さらに金属Ｍ２の置換組成範囲を広げ、ハンドリング性を良くするために、Ａｌ基金属間化合物のインゴットを粉砕する代わりに、液体急冷法によりフレーク状またはリボン状に形成してもよい。本発明に係る金属触媒の製造方法で、金属Ｍ１は、リーチング処理によりイオンにならず、酸化物または水酸化物になる金属であればいかなるものであってもよく、Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｚｒ，Ｎｂ，Ｍｏ，Ｈｆ，Ｔａ，ＷおよびＲｅのうちの少なくとも１つの金属から成っている。リーチング処理は、ｐＨが１２以上のアルカリ水溶液で行うことが好ましい。 The method for producing a metal catalyst according to the present invention can increase the leaching efficiency by pulverizing an ingot of an Al-based intermetallic compound before the leaching treatment. Further, further expand the replacement composition range of metal M 2, in order to improve the handling properties, instead of crushing the ingot Al-based intermetallic compound may be formed into flakes or ribbons by liquid quenching method. In the method for producing a metal catalyst according to the present invention, the metal M 1 may be any metal as long as it is a metal that does not become an ion by leaching treatment but becomes an oxide or a hydroxide, and Ti, V, Cr, It consists of at least one metal of Mn, Fe, Co, Zr, Nb, Mo, Hf, Ta, W and Re. The leaching treatment is preferably performed with an alkaline aqueous solution having a pH of 12 or more.
また、本発明に係る金属触媒の製造方法は、前記Ａｌ基金属間化合物を、５〜２０質量％濃度のＮａＯＨ水溶液でリーチング処理することにより、前記Ａｌ基金属間化合物からＡｌを溶出させることが好ましい。この場合、効率良くＡｌを溶出させることができ、金属粒子を安定して高分散化させることができる。 In the method for producing a metal catalyst according to the present invention, Al may be eluted from the Al-based intermetallic compound by leaching the Al-based intermetallic compound with an aqueous NaOH solution having a concentration of 5 to 20% by mass. preferable. In this case, Al can be efficiently eluted, and the metal particles can be stably highly dispersed.
本発明に関する金属触媒は、本発明に係る金属触媒の製造方法で製造されることを特徴とする。
本発明に関する金属触媒は、本発明に係る金属触媒の製造方法で製造されるため、金属Ｍ１の酸化物または水酸化物から成る担体に、均一な粒子径の金属粒子が均一に高分散化されている。本発明に関する金属触媒は、従来の調製法で得られる触媒と比べ、金属粒子の分散性が高く、高活性で性能が高い。なお、金属は、金属ナノ粒子状態で分散している。
Metal catalyst with respect to the present invention is characterized in that it is manufactured by the manufacturing method of the metal catalyst according to the present invention.
Metal catalyst with respect to the present invention, because it is manufactured by the manufacturing method of the metal catalyst according to the present invention, an oxide or a carrier consisting of a hydroxide, metal particles having a uniform particle size uniformly high dispersion of the metal M 1 Has been. The metal catalyst according to the present invention has high dispersibility of metal particles , high activity and high performance as compared with a catalyst obtained by a conventional preparation method. The metal is dispersed in the form of metal nanoparticles.
本発明によれば、様々な担体に、金属粒子を均一に高分散化させることができる金属触媒の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the metal catalyst which can disperse | distribute metal particles uniformly and highly to various support | carriers can be provided.
以下、図面に基づき、本発明の実施の形態について説明する。
本発明の実施の形態の金属触媒の製造方法では、まず、Ａｌ基金属間化合物のＡｌ１００−（ｘ＋ｙ）Ｍ１ ｘＭ２ ｙ（ただし、Ｍ１はＴｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｚｒ，Ｎｂ，Ｍｏ，Ｈｆ，Ｔａ，ＷおよびＲｅのうちの少なくとも１つの金属、Ｍ２はＡｕ，Ｐｔ，Ｉｒ，Ａｇ，Ｐｄ，Ｒｈ，Ｒｕ，ＮｉおよびＣｕのうちの少なくとも１つの金属、１０原子％≦ｘ≦３０原子％、０原子％＜ｙ≦１０原子％）を形成する。そのために、Ａｌと金属Ｍ１と金属Ｍ２とを、所望のＡｌ基金属間化合物の組成になるよう秤量し、その各原料を水冷した銅ハース内に入れて、アルゴン雰囲気下でアーク溶解する。そのまま銅ハース内で冷却することにより、Ａｌ基金属間化合物のインゴットを得る。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
In the method for producing a metal catalyst according to an embodiment of the present invention, first, Al 100- (x + y) M 1 x M 2 y (where M 1 is Ti, V, Cr, Mn, Fe, Co, Zr, Nb, Mo, Hf, Ta, at least one metal of W and Re, M 2 is Au, Pt, Ir, Ag, Pd, Rh, Ru, at least one metal of Ni and Cu 10 atomic% ≦ x ≦ 30 atomic%, 0 atomic% <y ≦ 10 atomic%). Therefore, Al and the metal M 1 and a metal M 2, were weighed so that the composition of the desired Al-based intermetallic compounds, the respective raw material placed in a copper hearth was cooled to arc melting in an argon atmosphere . The Al-based intermetallic compound ingot is obtained by cooling in the copper hearth as it is.
次に、得られたインゴットに対して、単ロール式液体急冷装置（例えば、株式会社真壁技研製「ＲＱＭ−Ｔ−２０」）で液体急冷法を行うことにより、フレーク状またはリボン状のＡｌ基金属間化合物を得る。このフレーク状またはリボン状のＡｌ基金属間化合物を、１０ｗｔ％のＮａＯＨ（水酸化ナノリウム）水溶液に投入して、室温で４時間攪拌してリーチング処理を行い、Ａｌ基金属間化合物からＡｌを溶出させる。このとき、ＮａＯＨ水溶液の量は、例えば、５ｇのＡｌ基金属間化合物に対して、５００ｇである。その後、吸引濾過により水溶液中から残留物を取り出し、それを洗浄して、４０℃で１２時間乾燥する。これにより、金属Ｍ１の酸化物粒子または水酸化物粒子に、金属Ｍ２のナノ粒子が均一に分散した複合粒子、すなわち本発明の実施の形態の金属触媒が得られる。 Next, the obtained ingot is subjected to a liquid quenching method using a single-roll liquid quenching apparatus (for example, “RQM-T-20” manufactured by Makabe Giken Co., Ltd.), whereby a flake-shaped or ribbon-shaped Al group is obtained. An intermetallic compound is obtained. This flaky or ribbon-like Al-based intermetallic compound is put into a 10 wt% NaOH (nanolium hydroxide) aqueous solution and stirred at room temperature for 4 hours to carry out a leaching treatment to elute Al from the Al-based intermetallic compound. Let At this time, the amount of the NaOH aqueous solution is, for example, 500 g with respect to 5 g of the Al-based intermetallic compound. Thereafter, the residue is taken out from the aqueous solution by suction filtration, washed, and dried at 40 ° C. for 12 hours. As a result, composite particles in which the metal M 2 nanoparticles are uniformly dispersed in the metal M 1 oxide particles or hydroxide particles, that is, the metal catalyst of the embodiment of the present invention are obtained.
なお、インゴットのＡｌ基金属間化合物を、液体急冷法によりフレーク状またはリボン状にする代わりに、平均一次粒子径が１００〜２００μｍ程度になるよう微粉末状に粉砕し、その粉砕物に対して、リーチング処理を行ってもよい。この場合にも、本発明の実施の形態の金属触媒が得られる。 In addition, the Al-based intermetallic compound of the ingot is pulverized into a fine powder form so that the average primary particle diameter is about 100 to 200 μm instead of flaky or ribbon-like by a liquid quenching method, Reaching processing may be performed. Also in this case, the metal catalyst of the embodiment of the present invention can be obtained.
このように、本発明の実施の形態の金属触媒の製造方法は、Ａｌ−Ｍ１の一部を金属Ｍ２で置換したＡｌ基金属間化合物の合金を前駆物質とし、これをアルカリ水溶液でリーチング処理することにより、Ａｌを選択的に溶出させる。この工程において、金属Ｍ１が酸化物または水酸化物に変化し、金属Ｍ２はそのまま残留するため、加熱処理を必要とせずに、高分散担持金属触媒を得ることができる。加熱処理を行わないため、金属Ｍ２の粒子が凝集せず、金属Ｍ１の酸化物または水酸化物から成る担体に、均一な粒子径の金属ナノ粒子を均一に高分散化させることができる。 As described above, the method for producing a metal catalyst according to the embodiment of the present invention uses an Al-based intermetallic compound alloy in which a part of Al-M 1 is substituted with metal M 2 as a precursor, and leaches this with an alkaline aqueous solution. By processing, Al is selectively eluted. In this step, the metal M 1 is changed to an oxide or hydroxide, the metal M 2 is left as it is, it can be without requiring heat treatment to obtain a highly dispersed supported metal catalyst. Since the heat treatment is not performed, the metal M 2 particles do not aggregate, and the metal nanoparticles having a uniform particle diameter can be uniformly and highly dispersed in the support made of the oxide or hydroxide of the metal M 1. .
本発明の実施の形態の金属触媒の製造方法は、加熱処理を行わないため、従来の調製法と比べて簡便であり、金属粒子を様々な担体に安定して高分散化させることができる。また、金属粒子を均一に高分散化させることができるため、金属の担持効率を高めることができ、金属使用量の低減化を図ることができる。本発明の実施の形態の金属触媒の製造方法により得られた本発明の実施の形態の金属触媒は、従来の調製法で得られる触媒と比べ、金属粒子の分散性が高く、高活性で性能が高い。 The method for producing a metal catalyst according to an embodiment of the present invention is simpler than conventional preparation methods because no heat treatment is performed, and metal particles can be stably dispersed in a variety of carriers. Further, since the metal particles can be uniformly and highly dispersed, the metal loading efficiency can be increased, and the amount of metal used can be reduced. Embodiment of the metal catalyst of the present invention obtained by the production method of the embodiment of the metal catalyst of the present invention as compared to catalysts obtained by the conventional preparation methods, high dispersibility of the metal particles, the performance at high activity Is expensive.
［状態評価および特性評価の試験試料］
本発明の実施の形態の金属触媒について、状態評価のための粉末Ｘ線回折試験、および特性評価のためのＣＯ酸化反応試験を行った。一般に、金属がナノ粒子化すると回折ピークがブロード化するため、状態評価のためにＸＲＤ法（Ｘ線回折法）を用いた。また、Ａｕ触媒は、ナノ粒子化して初めて高いＣＯ酸化活性を示すため、ナノ粒子化状態の特性評価のためにＣＯ酸化反応を行った。
[Test sample for condition evaluation and characteristic evaluation]
The metal catalyst of the embodiment of the present invention was subjected to a powder X-ray diffraction test for state evaluation and a CO oxidation reaction test for characteristic evaluation. In general, when a metal is made into nanoparticles, a diffraction peak is broadened. Therefore, an XRD method (X-ray diffraction method) was used for state evaluation. In addition, since the Au catalyst exhibits high CO oxidation activity only after being made into nanoparticles, a CO oxidation reaction was performed for evaluating the properties of the nanoparticles.
本発明の実施の形態の金属触媒の試験試料として、本発明の実施の形態の金属触媒の製造方法を用いて、表１に示す実施例１〜７を準備した。各試料とも、前駆物質のＡｌ基金属間化合物を５ｇ製造し、使用している。なお、表１中のＡｌの溶出量とは、Ａｌ基金属間化合物中のＡｌ全量に対する、リーチング処理によるＡｌの溶出量を表している。 Examples 1 to 7 shown in Table 1 were prepared as test samples for the metal catalyst according to the embodiment of the present invention using the method for producing a metal catalyst according to the embodiment of the present invention. For each sample, 5 g of an Al-based intermetallic compound as a precursor is produced and used. In addition, the elution amount of Al in Table 1 represents the elution amount of Al by leaching with respect to the total amount of Al in the Al-based intermetallic compound.
また、比較のため、表１に示す比較例１〜２も準備した。比較例１は、原料の組成以外は、本発明の実施の形態の金属触媒の製造方法と同様の方法で製造している。比較例２は、ワールド・ゴールド・カウンシルが提供している標準触媒試料Ａｕ−Ｆｅ２Ｏ３（Ｎｏ．８２Ｃ，＃０２−０５；金担持量 ４．４重量％） ５ｇに対して、水素雰囲気下で、２５０ｏＣで１時間の還元処理を行って、Ａｕ−Ｆｅ３Ｏ４の状態にしたものである。 For comparison, Comparative Examples 1 and 2 shown in Table 1 were also prepared. The comparative example 1 is manufactured by the same method as the manufacturing method of the metal catalyst of embodiment of this invention except the composition of a raw material. In Comparative Example 2, a standard catalyst sample Au-Fe 2 O 3 (No. 82C, # 02-05; gold loading amount 4.4% by weight) provided by the World Gold Council is 5 g in a hydrogen atmosphere. below, performed 1 hour of reduction treatment at 250 o C, it is obtained by the state of the Au-Fe 3 O 4.
［Ｘ線回折試験］
実施例１〜５、比較例１を用いて、リーチング処理前のＡｌ基金属間化合物、およびリーチング処理後の金属触媒について、それぞれＸ線回折試験を行った。このＸ線回折試験の結果を、図１に示す。なお、比較例２の触媒はリーチング処理を行っていないが、比較例２の触媒についてもＸ線回折試験を行い、図１（ｂ）に示している。
[X-ray diffraction test]
Using Examples 1 to 5 and Comparative Example 1, an X-ray diffraction test was performed on the Al-based intermetallic compound before the leaching treatment and the metal catalyst after the leaching treatment. The results of this X-ray diffraction test are shown in FIG. The catalyst of Comparative Example 2 was not subjected to leaching treatment, but the catalyst of Comparative Example 2 was also subjected to an X-ray diffraction test and is shown in FIG.
図１（ａ）に示すように、リーチング処理前のＡｌ基金属間化合物において、Ａｕの組成が１原子％程度までの実施例１〜３では、比較例１と同じ回折ピークパターンを示していることから、Ａｕが構造骨格中に置換されていることが確認された。また、Ａｕの組成が４原子％以上の実施例４〜５では、実施例１〜３や比較例１とは異なる回折ピークパターンを示していることから、他の相が形成されてきていることが確認された。 As shown in FIG. 1 (a), in the Al-based intermetallic compound before the leaching treatment, Examples 1 to 3 in which the composition of Au is up to about 1 atomic% show the same diffraction peak pattern as in Comparative Example 1. From this, it was confirmed that Au was substituted in the structural skeleton. Moreover, in Examples 4-5 in which the composition of Au is 4 atomic% or more, since different diffraction peak patterns are shown in Examples 1-3 and Comparative Example 1, other phases have been formed. Was confirmed.
また、図１（ｂ）に示すように、アルカリ水溶液中でリーチング処理を行うと、実施例１〜５では、比較例２と同様の回折ピークパターンを示していることから、母相が消滅してすべてＡｕおよびＦｅ３Ｏ４に変化していることが確認された。また、実施例１〜５のいずれの試料においても、Ａｕの回折ピークは極めてブロードであり、Ａｕがナノ粒子状態で高分散化していることが確認された。 Moreover, as shown in FIG.1 (b), when the leaching process is performed in alkaline aqueous solution, in Examples 1-5, since the diffraction peak pattern similar to Comparative Example 2 is shown, the parent phase disappears. It was confirmed that all changed to Au and Fe 3 O 4 . Moreover, in any sample of Examples 1-5, the diffraction peak of Au was very broad, and it was confirmed that Au was highly dispersed in a nanoparticle state.
［ＣＯ酸化反応試験］
実施例１〜７、比較例１〜２を用いて、ＣＯの酸化活性を評価する試験を行った。この試験では、触媒１００ｍｇをそれぞれ石英製反応管（内径：４ｍｍ）に充填した後、常圧固定床流通式反応装置内に設置した。次に、ＣＯ（１容量％）とＯ２（０．５容量％）とＨｅ（残部）とからなる入りガスを各触媒に接触させて、触媒に接触した後の出ガス中に含まれる成分の測定を行った。なお、入りガスの流通条件は、３０ｍｌ／ｍｉｎ，ＳＶ＝２０，０００ｈ−１とした。また、出ガス中の成分は、オンラインガスクロマトグラフィー（株式会社島津製作所製；「ＧＣ−８Ａ」、検出器：ＴＣＤ）、カラム：ＭＳ ５Ａ（ＣＯ，Ｏ２）並びにＰｏｒａｐａｋ Ｑ（ＣＯ２）により分析を行った。
[CO oxidation reaction test]
The test which evaluates the oxidation activity of CO was done using Examples 1-7 and Comparative Examples 1-2. In this test, 100 mg of the catalyst was filled in each quartz reaction tube (inner diameter: 4 mm), and then installed in an atmospheric pressure fixed bed flow type reactor. Next, the components contained in the exit gas after contacting the catalyst with an incoming gas composed of CO (1% by volume), O 2 (0.5% by volume), and He (remainder), and contacting the catalyst. Was measured. The inlet gas flow conditions were 30 ml / min, SV = 20,000 h −1 . In addition, the components in the outgas were determined by online gas chromatography (manufactured by Shimadzu Corporation; “GC-8A”, detector: TCD), column: MS 5A (CO, O 2 ), and Porapak Q (CO 2 ). Analysis was carried out.
また、ＣＯ酸化反応（ＣＯ＋１／２Ｏ２→ＣＯ２）によるＣＯ転化率を、
［ＣＯ転化率（％）］＝｛（［入りガス中のＣＯ濃度］−［出ガス中のＣＯ濃度］）
／［入りガス中のＣＯ濃度］｝×１００
により求めた。なお、この試験は触媒ごとに複数回行い、試験中の温度条件は各回ごとに、−１２℃，０℃，２０℃，５０℃，８０℃，１００℃，１２０℃，１５０℃，１８０℃，２００℃，２５０℃，３００℃，３５０℃のうちいずれかの温度に設定した。
Further, the CO conversion rate by the CO oxidation reaction (CO + 1 / 2O 2 → CO 2 )
[CO conversion rate (%)] = {([CO concentration in incoming gas] − [CO concentration in outgoing gas])
/ [CO concentration in entering gas]} × 100
Determined by This test was performed several times for each catalyst, and the temperature conditions during the test were -12 ° C, 0 ° C, 20 ° C, 50 ° C, 80 ° C, 100 ° C, 120 ° C, 150 ° C, 180 ° C, The temperature was set to any one of 200 ° C, 250 ° C, 300 ° C, and 350 ° C.
ＣＯ酸化反応試験の結果を、図２および図３に示す。図２は、金属としてＡｕを含む実施例１〜５、および比較例１〜２の結果であり、図３は、金属としてそれぞれＡｕ，Ｐｔ，Ｃｕを１原子％含む実施例３，６，７、および比較例１の結果である。 The results of the CO oxidation reaction test are shown in FIGS. FIG. 2 shows the results of Examples 1 to 5 containing Au as a metal and Comparative Examples 1 and 2, and FIG. 3 shows Examples 3, 6, and 7 containing 1 atom% of Au, Pt, and Cu as metals , respectively. And the results of Comparative Example 1.
図２に示すように、実施例１〜５のＡｕを含む触媒は、Ａｕが存在しない触媒（比較例１）に比べ、触媒活性が向上していることが確認された。また、実施例１〜５、特に実施例２〜５に示す本発明の実施の形態の金属触媒は、従来から存在する比較例２の触媒と同程度の活性を有することが確認された。実施例１〜４の結果から、Ａｕの置換量が増えるに従って触媒活性が著しく向上し、実施例３および４の触媒活性が特に高いことが確認された。ただし、実施例５に示すように、置換量が８原子％まで増えると、触媒活性が低下することも確認された。 As shown in FIG. 2, it was confirmed that the catalysts containing Au in Examples 1 to 5 had improved catalytic activity as compared with the catalyst in which no Au was present (Comparative Example 1). Moreover, it was confirmed that the metal catalyst of embodiment of this invention shown in Examples 1-5, especially Examples 2-5 has an activity comparable as the catalyst of the comparative example 2 which exists conventionally. From the results of Examples 1 to 4, it was confirmed that the catalytic activity was remarkably improved as the substitution amount of Au was increased, and the catalytic activities of Examples 3 and 4 were particularly high. However, as shown in Example 5, it was also confirmed that when the substitution amount increased to 8 atomic%, the catalytic activity decreased.
また、図３に示すように、Ａｕ以外のＰｔ，Ｃｕといった金属を含むものであっても、触媒活性が高く、担持金属触媒として有効であることが確認された。 Further, as shown in FIG. 3, it was confirmed that even a metal containing Pt or Cu other than Au has high catalytic activity and is effective as a supported metal catalyst .
図４に、実施例３の金属触媒の透過型電子顕微鏡（ＴＥＭ）写真（明視野像）を示す。図４に示すように、本発明の実施の形態の金属触媒は、ナノ粒子から構成された複合粒子であることが明らかである。また、図５に、実施例３および比較例２の触媒の細孔分布曲線を示す。この細孔分布曲線は、細孔容積（Ｖ）を細孔半径（ｒｐ）で微分した値（ｄＶ／ｄｒｐ）を、細孔半径（ｒｐ）に対してプロットした曲線である。この細孔分布曲線は、表面積測定法であるＢＥＴ法における吸着等温線から、ＢＪＨ法を用いて求めたものである。図５に示すように、実施例３の触媒は、約２ｎｍの中心細孔半径を有するポーラス構造を形成しているのに対し、比較例２の触媒は、明確なポーラス構造を有していないことが確認された。すなわち、比較例２の触媒は、ポーラスではなく、Ｆｅ３Ｏ４の粒子の上にＡｕが載っている構造を有しているのに対し、本発明の実施の形態の金属触媒はポーラスであるため、反応物質を多く溜めることができるという利点を有している。 In FIG. 4, the transmission electron microscope (TEM) photograph (bright field image) of the metal catalyst of Example 3 is shown. As shown in FIG. 4, it is clear that the metal catalyst according to the embodiment of the present invention is a composite particle composed of nanoparticles. FIG. 5 shows pore distribution curves of the catalysts of Example 3 and Comparative Example 2. The pore distribution curve, the value of pore volume (V) is differentiated by pore radius (r p) (dV / dr p), is a curve plotted against the pore radius (r p). This pore distribution curve is obtained using the BJH method from the adsorption isotherm in the BET method which is a surface area measuring method. As shown in FIG. 5, the catalyst of Example 3 forms a porous structure having a central pore radius of about 2 nm, whereas the catalyst of Comparative Example 2 does not have a clear porous structure. It was confirmed. That is, the catalyst of Comparative Example 2 is not porous but has a structure in which Au is placed on Fe 3 O 4 particles, whereas the metal catalyst of the embodiment of the present invention is porous. Therefore, there is an advantage that a large amount of reactants can be stored.
本発明によれば、ＣＯの酸化性能に優れ、十分に高度な触媒活性を有する金属触媒およびその製造方法を提供することができる。このような本発明に関する金属触媒は、特に低温でのＣＯ酸化活性に優れているため、ＣＯ酸化触媒等の用途に特に有用である。
ADVANTAGE OF THE INVENTION According to this invention, the metal catalyst which is excellent in the oxidation performance of CO, and has a sufficiently high catalyst activity, and its manufacturing method can be provided. Such a metal catalyst according to the present invention is particularly useful for applications such as a CO oxidation catalyst because it is excellent in CO oxidation activity at a low temperature.
Claims (4)
4. The Al is eluted from the Al-based intermetallic compound by leaching the Al-based intermetallic compound with an aqueous NaOH solution having a concentration of 5 to 20% by mass. 5. A method for producing a metal catalyst according to 1.
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