JP5187844B2 - CO oxidation catalyst - Google Patents
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- JP5187844B2 JP5187844B2 JP2008313902A JP2008313902A JP5187844B2 JP 5187844 B2 JP5187844 B2 JP 5187844B2 JP 2008313902 A JP2008313902 A JP 2008313902A JP 2008313902 A JP2008313902 A JP 2008313902A JP 5187844 B2 JP5187844 B2 JP 5187844B2
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- 239000003054 catalyst Substances 0.000 title claims description 21
- 238000007254 oxidation reaction Methods 0.000 title description 9
- 230000003647 oxidation Effects 0.000 title description 4
- 239000002105 nanoparticle Substances 0.000 claims description 23
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 17
- 229910000943 NiAl Inorganic materials 0.000 claims description 13
- 229910000765 intermetallic Inorganic materials 0.000 claims description 8
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、ＣＯを酸化してＣＯ２にする触媒であって、より詳しくは、２５０℃以上の温度で触媒活性を示すものに関する。 The present invention relates to a catalyst that oxidizes CO to CO 2 , and more particularly relates to a catalyst that exhibits catalytic activity at a temperature of 250 ° C. or higher.
以下の特許文献示されるように、従来ＣＯ酸化触媒は主にＰｔ，Ａｕなどの高価な貴金属や希土類等の稀少元素が使われている。
これら貴金属の使用は、ＣＯ酸化によるＣＯ２回収作業を困難とし地球温暖化防止の活動を阻害する要因の一つとなっていた。
The use of these precious metals has been one of the factors that make it difficult to recover CO 2 by CO oxidation and hinders activities to prevent global warming.
本願発明は、このような実情に鑑み、貴金属や希少金属を使用せず、一般に得やすいＮｉとＡｌを用いて、ＣＯ酸化機能を発現する触媒を提供することを特徴とする。 In view of such circumstances, the present invention is characterized by providing a catalyst that expresses a CO oxidation function using Ni and Al that are generally easily obtained without using noble metals or rare metals.
発明１の触媒は、 Ｎｉ−Ａｌ金属間化合物のナノ粒子からなることを特徴とする。 The catalyst of the invention 1 is characterized by comprising Ni-Al intermetallic compound nanoparticles.
発明２は、発明１の触媒において、その金属間化合物は、Ｎｉ３Ａｌ， ＮｉＡｌ， Ｎｉ相の少なくとも１つ以上を有することを特徴とする。 Invention 2 is characterized in that in the catalyst of Invention 1, the intermetallic compound has at least one of Ni 3 Al, NiAl, and Ni phases.
発明３は、発明１又は２の触媒において、ナノ粒子のＢＥＴ比表面積が５０m２／ｇ以上であることを特徴とすることを特徴とする。 Invention 3 is characterized in that, in the catalyst of Invention 1 or 2, the nanoparticle has a BET specific surface area of 50 m 2 / g or more.
発明４は、発明１から３のいずれかの触媒において、ＮｉＡｌ合金インゴットを真空アークプラズマ蒸着法によりナノ粒子化されたものであることを特徴とする。 Invention 4 is characterized in that, in the catalyst according to any one of Inventions 1 to 3, a NiAl alloy ingot is nanoparticulated by a vacuum arc plasma deposition method.
本発明の触媒は、貴金属や希少元素を含有しないにもかかわらず、一酸化炭素（ＣＯ）の酸化反応に対して高い触媒活性を示した。
さらに空気中でも安定なので、従来のラネーＮｉ触媒より取り扱いが簡単である。
The catalyst of the present invention showed high catalytic activity for the oxidation reaction of carbon monoxide (CO), although it contained no precious metal or rare element.
Furthermore, since it is stable in the air, it is easier to handle than conventional Raney Ni catalysts.
金属間化合物ナノ粒子の粒径の好ましい範囲は１ｎｍから１００ｎｍである。その範囲のサイズの粒子は安定的に存在することが可能で、高い比表面積を有するためである。
Ｎｉ−Ａｌの重量比の好ましい範囲は、Ｎｉは７６−９５重量％、Ａｌは５−２４重量％である。Ｎｉ−Ａｌの２元状態図により、この範囲では、Ｎｉ３ＡｌとＮｉＡｌの金属間化合物相は存在する。
この金属間化合物ナノ粒子の相構造が、Ｎｉ３Ａｌ，ＮｉＡｌ，Ｎｉ，ＮｉＯ及びＡｌ２Ｏ３相のすべてを有する必要がなく、触媒活性を有するＮｉ３Ａｌ，ＮｉＡｌ，Ｎｉの中の１つ又１つ以上の相があれば良い。
A preferable range of the particle size of the intermetallic compound nanoparticles is 1 nm to 100 nm. This is because particles having a size within that range can exist stably and have a high specific surface area.
The preferred range of the Ni-Al weight ratio is 76-95 wt% for Ni and 5-24 wt% for Al. In this range, there is an intermetallic compound phase of Ni 3 Al and NiAl according to the Ni—Al binary phase diagram.
The phase structure of the intermetallic compound nanoparticles need not have all of the Ni 3 Al, NiAl, Ni, NiO, and Al 2 O 3 phases, and is one of Ni 3 Al, NiAl, Ni having catalytic activity. There may be more than one phase.
Ｎｉ−Ａｌ金属間化合物ナノ粒子の作製
Ｎｉ（ニッケル）とＡｌ（アルミニウム）をアーク溶解炉で以下の組成の合金インゴットを作製した。
上記のＮｉＡｌ合金インゴットを用いて、真空アークプラズマ蒸着法により、表２に示すように各組成のナノ粒子試料を作製した。粉末Ｘ線回折測定によりこれらのナノ粒子試料の相の構成を確認したところ、図１に示すように、これらのナノ粒子試料は、Ｎｉ３Ａｌ，ＮｉＡｌ，Ｎｉ，ＮｉＯ及びＡｌ２Ｏ３相を主相とするものであった。
なお、図中の略称は、原材料とした合金の略称を示すものである。
Production of Ni-Al Intermetallic Compound Nanoparticles An alloy ingot having the following composition was produced using Ni (nickel) and Al (aluminum) in an arc melting furnace.
Using the above-described NiAl alloy ingot, nanoparticle samples of each composition were prepared as shown in Table 2 by vacuum arc plasma deposition. When the composition of the phases of these nanoparticle samples was confirmed by powder X-ray diffraction measurement, as shown in FIG. 1, these nanoparticle samples contained Ni 3 Al, NiAl, Ni, NiO and Al 2 O 3 phases. It was the main phase.
In addition, the abbreviation in a figure shows the abbreviation of the alloy used as a raw material.
マイクロトラック粒度分布測定装置を用いてレーザー回折・散乱法により粒子全体的粒度分布を測定した。表２のＮｏ．２のナノ粒子は１ｎｍから６００ｎｍまでの範囲で、Ｎｏ．５のナノ粒子は１ｎｍから８００ｎｍまでの範囲であることが分かった。透過電子顕微鏡（ＴＥＭ）及び走査透過電子顕微鏡（ＳＴＥＭ）により作製した表２のＮｏ．２のナノ粒子のサイズ、形状、組成を分析した。粒子サイズは主に１ｎｍから１００ｎｍまでの範囲に分布することが分かった（図２）。
窒素ガス吸着により比表面積を測定した。これらのナノ粒子試料の比表面積（ＢＥＴ法）は、５０から１１２m２／gであることが分かった（表２）。これは、従来のラネーＮｉ触媒に匹敵する大きな比表面積（５０−１００m２／g）である。
さらに、本ナノ粒子触媒はラネーＮｉより安定であるという大きなメリットがある。ラネーＮｉ触媒は空気中で強烈に酸化・燃焼するため、水などの液体中に保存する必要がある。そのため、主に液体反応にしか適用できない。これに対して、本ナノ粒子触媒は空気中でも安定で燃えることはないので、取扱いが簡単で、高温ガス反応にも応用できる。
The overall particle size distribution was measured by laser diffraction / scattering method using a microtrack particle size distribution analyzer. No. in Table 2 No. 2 nanoparticles range from 1 nm to 600 nm. 5 nanoparticles were found to range from 1 nm to 800 nm. No. 1 in Table 2 prepared by a transmission electron microscope (TEM) and a scanning transmission electron microscope (STEM). The size, shape and composition of the two nanoparticles were analyzed. It was found that the particle size was distributed mainly in the range from 1 nm to 100 nm (FIG. 2).
The specific surface area was measured by nitrogen gas adsorption. The specific surface area (BET method) of these nanoparticle samples was found to be 50 to 112 m 2 / g (Table 2). This is a large specific surface area (50-100 m 2 / g) comparable to conventional Raney Ni catalysts.
Furthermore, this nanoparticle catalyst has a great merit that it is more stable than Raney Ni. Raney Ni catalyst oxidizes and burns strongly in the air, so it must be stored in a liquid such as water. Therefore, it can be mainly applied only to liquid reactions. On the other hand, the present nanoparticle catalyst is stable even in air and does not burn, so it is easy to handle and can be applied to high temperature gas reactions.
以下のＣＯ酸化反応に対して本ナノ粒子の触媒特性を測定した。
２ＣＯ ＋ Ｏ２ → ２ＣＯ２
反応装置システム
触媒反応は固定床流通式触媒反応装置により行った。５〜２０ｍｇ程度のナノ粒子試料を内径８ｍｍの石英反応管に導入し、試料層の上下に石英ウールを１０ｍｍ厚さ程度詰めて、試料層を固定する。反応管を電気炉により加熱し、所定の温度で触媒反応を行った。温度制御は試料層に接触する熱電対により行った。反応管上部にＣＯ＋Ｏ２＋Ｈｅの混合ガスのラインに接続した。反応管下部にガスクロマトグラフィ及びガス流量計に接続し、反応物の組成と生成量を測定した。図３は反応装置システムを示す。
The catalytic properties of the nanoparticles were measured for the following CO oxidation reaction.
2CO + O 2 → 2CO 2
Reactor system The catalytic reaction was carried out by a fixed bed flow type catalytic reactor. A nanoparticle sample of about 5 to 20 mg is introduced into a quartz reaction tube having an inner diameter of 8 mm, and a sample layer is fixed by filling quartz wool with a thickness of about 10 mm above and below the sample layer. The reaction tube was heated by an electric furnace to carry out a catalytic reaction at a predetermined temperature. Temperature control was performed by a thermocouple in contact with the sample layer. The upper part of the reaction tube was connected to a mixed gas line of CO + O 2 + He. A gas chromatograph and a gas flow meter were connected to the lower part of the reaction tube, and the composition and amount of the reaction product were measured. FIG. 3 shows the reactor system.
ＣＯの酸化反応における触媒活性
組成Ｎｉ２２．４Ａｌ、Ｎｉ２５Ａｌ及びＮｉ２７Ａｌのナノ粒子試料をそれぞれに用いて、ＣＯの酸化反応を行った。ＣＯ，Ｏ２，Ｈｅの混合ガス（体積比ＣＯ：Ｏ２：Ｈｅ＝１：２：９７）を１００ ｍｌ／ｍｉｎの流量で反応管に導入して、室温から５７５℃の温度範囲でガスクロマトグラフィにより反応管出口のＣＯ， Ｏ２， ＣＯ２， Ｈｅ各ガス成分の濃度を測定した。比較のため、市販の純Ｐｔ粉末試料（フルヤ金属（株））及び回転アトマイズ法で作製したＮｉ−２５原子％Ａｌ粉末試料（高純度化学（株）作製）を用いて、同じ触媒反応を行った。Ｐｔ粉末の場合、篩で集めて粒径１５０μｍ以下の粉末０．１５ｇを反応管に導入した。アトマイズＮｉ３Ａｌ粉末の場合、篩で得られた粒径３２〜７５μｍの粉末０．４０ｇを反応管に導入した。測定した各温度でのＣＯ、ＣＯ２の濃度から、次の式でＣＯの転化率を求めた。
ＣＯの転化率（％）＝ ＣＯ２の濃度／（ＣＯの濃度＋ＣＯ２の濃度）×１０２
Catalytic activity in the oxidation reaction of CO The oxidation reaction of CO was performed using nanoparticle samples of compositions Ni22.4Al, Ni25Al and Ni27Al, respectively. A mixed gas of CO, O 2 and He (volume ratio CO: O 2 : He = 1: 2: 97) was introduced into the reaction tube at a flow rate of 100 ml / min, and gas chromatography was performed in a temperature range from room temperature to 575 ° C. Was used to measure the concentrations of CO, O 2 , CO 2 , and He gas components at the outlet of the reaction tube. For comparison, the same catalytic reaction was carried out using a commercially available pure Pt powder sample (Furuya Metal Co., Ltd.) and a Ni-25 atomic% Al powder sample (manufactured by High Purity Chemical Co., Ltd.) prepared by the rotary atomization method. It was. In the case of Pt powder, 0.15 g of powder having a particle size of 150 μm or less collected by a sieve was introduced into the reaction tube. In the case of atomized Ni 3 Al powder, 0.40 g of powder having a particle size of 32 to 75 μm obtained by sieving was introduced into the reaction tube. From the measured concentrations of CO and CO 2 at each temperature, the CO conversion rate was determined by the following equation.
CO conversion (%) = CO 2 concentration / (CO concentration + CO 2 concentration) × 10 2
表３は計算した各温度でのＣＯの転化率である。
図４はこれらのＣＯ転化率を反応温度の関数としてグラフで示したものである。Ｎｉ２２．４Ａｌ、Ｎｉ２５ＡｌとＮｉ２７Ａｌは、２５０℃から活性が出始め、温度の上昇に伴い、転化率が増加し、４００℃では約１００％のＣＯ転化率が得られた。
これらのＮｉ−Ａｌナノ粒子の触媒活性は純Ｐｔ粉末の触媒活性（図４に示す）とほぼ同じである。
一方、アトマイズで作製したＮｉ２５Ａｌは３７５℃から活性が出始め、ＣＯ転化率は温度の上昇に伴い上昇するが、５７５℃の高温でも８６％しか得られなかった。よって、本技術のナノＮｉＡｌ粒子はアトマイズ法で作製したＮｉＡｌ粉末より高い活性を持つことを示す。さらに、この結果から、貴金属元素を含まないＮｉとＡｌからなるナノ粒子触媒がＣＯ酸化反応に純Ｐｔ粉末並みの活性を示すことが分かった。
Table 3 shows the calculated CO conversion at each temperature.
FIG. 4 graphically illustrates these CO conversions as a function of reaction temperature. Ni22.4Al, Ni25Al, and Ni27Al started to show activity at 250 ° C., and the conversion increased with increasing temperature, and a CO conversion of about 100% was obtained at 400 ° C.
The catalytic activity of these Ni—Al nanoparticles is almost the same as that of pure Pt powder (shown in FIG. 4).
On the other hand, Ni25Al produced by atomization started to show activity at 375 ° C., and the CO conversion increased with increasing temperature, but only 86% was obtained even at a high temperature of 575 ° C. Therefore, it shows that the nano NiAl particle | grains of this technique have higher activity than the NiAl powder produced by the atomization method. Furthermore, from this result, it was found that a nanoparticle catalyst composed of Ni and Al not containing a noble metal element exhibits an activity similar to that of pure Pt powder in the CO oxidation reaction.
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| JP5798425B2 (en) * | 2011-09-26 | 2015-10-21 | トヨタ自動車株式会社 | Exhaust gas purification catalyst and method for producing the same |
| EP3450013A4 (en) | 2016-04-27 | 2019-10-02 | University of Science and Technology of China | Preparation method for wide-temperature catalyst used for preferential oxidation of co in a hydrogen-rich atmosphere, and product and applications |
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| JP2001220103A (en) * | 2000-02-10 | 2001-08-14 | Yusaku Takita | Hydrogen producing method by decomposition of hydrocarbon |
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