JP2017217630A - Magnesia catalyst carrier and method for producing the same - Google Patents
Magnesia catalyst carrier and method for producing the same Download PDFInfo
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Abstract
【課題】気相有機反応に用いた際に触媒上への炭素析出を抑制でき、長期間安定的に効率良く気相有機反応を実施することができる触媒担体を提供する。
【解決手段】マグネシア系触媒担体であって、酸化マグネシウム粒子の表面近傍に酸化カルシウムを含有し、該酸化カルシウムの該粒子全体に対する含有量が、Ca換算で0.005質量%〜1.5質量%である触媒担体。
【選択図】なしThe present invention provides a catalyst carrier capable of suppressing carbon deposition on a catalyst when used in a gas phase organic reaction and capable of carrying out a gas phase organic reaction stably and efficiently for a long period of time.
A magnesia-based catalyst carrier comprising calcium oxide in the vicinity of the surface of magnesium oxide particles, and the content of the calcium oxide with respect to the entire particles is 0.005% by mass to 1.5% by mass in terms of Ca. % Catalyst support.
[Selection figure] None
Description
本発明は、マグネシア(酸化マグネシウム)系触媒担体、より具体的には、カルシア(酸化カルシウム)がマグネシア粒子表面近傍に析出した形態を有する触媒担体に関する。本発明のマグネシア系触媒担体は、気相有機反応、特に、天然ガスの改質(リフォーミング)による合成ガスの製造のような触媒上に炭素の析出を生ずるおそれのある反応に使用される触媒の担体として好ましく用いることができる。 The present invention relates to a magnesia (magnesium oxide) catalyst support, and more specifically to a catalyst support having a form in which calcia (calcium oxide) is deposited in the vicinity of the surface of magnesia particles. The magnesia-based catalyst carrier of the present invention is a catalyst used for gas phase organic reactions, particularly for reactions that may cause carbon deposition on the catalyst, such as production of synthesis gas by reforming (reforming) natural gas. It can be preferably used as a carrier.
一酸化炭素と水素を主成分とする合成ガスは、ジメチルエーテル、メタノール、フィッシャー・トロプシュ油、酢酸、ジフェニルメタン・ジイソシアネート、メタクリル酸メチル等の原料として広く利用されている。このような合成ガスは、例えば、天然ガス(メタンに代表される軽質炭化水素を主成分とする)と二酸化炭素とを触媒の存在下で反応させる二酸化炭素リフォーミングや、天然ガスとスチーム(水蒸気)とを触媒の存在下で反応させるスチームリフォーミング、或いは天然ガスと二酸化炭素及びスチームを触媒の存在下で反応させる二酸化炭素/スチームリフォーミングで製造されることが多い。 Syngas mainly composed of carbon monoxide and hydrogen is widely used as a raw material for dimethyl ether, methanol, Fischer-Tropsch oil, acetic acid, diphenylmethane diisocyanate, methyl methacrylate, and the like. Such synthesis gas includes, for example, carbon dioxide reforming in which natural gas (mainly composed of light hydrocarbons represented by methane) and carbon dioxide are reacted in the presence of a catalyst, natural gas and steam (water vapor) ) In the presence of a catalyst, or carbon dioxide / steam reforming in which natural gas is reacted with carbon dioxide and steam in the presence of a catalyst.
このとき、二酸化炭素リフォーミング或いは二酸化炭素/スチームリフォーミングには、原料である軽質炭化水素と生成物である一酸化炭素との反応により触媒上に炭素が析出しやすいという問題がある。炭素が触媒上に析出すると、触媒活性が損なわれて反応効率が低下するため、長期間安定的に効率良く合成ガスを製造することが難しくなる。また、炭素の析出はリフォーミング反応器の差圧上昇や閉塞の原因にもなる。 At this time, carbon dioxide reforming or carbon dioxide / steam reforming has a problem that carbon is likely to be deposited on the catalyst by the reaction between the light hydrocarbon as the raw material and the carbon monoxide as the product. When carbon is deposited on the catalyst, the catalytic activity is impaired and the reaction efficiency is lowered. Therefore, it is difficult to stably and efficiently produce synthesis gas for a long period of time. Carbon deposition also causes an increase in the differential pressure and blockage of the reforming reactor.
触媒上に炭素が析出するという問題に対しては、例えば、アルカリ土類金属酸化物類の少なくとも1種以上の化合物と酸化アルミニウムとからなる担体上にルテニウム化合物を担持させた二酸化炭素リフォーミング触媒(特許文献1参照)や、第2族〜第4族の金属酸化物又はランタノイド金属酸化物からなる担体又はその金属酸化物を含有するアルミナの複合体からなる担体にロジウムを担持した二酸化炭素リフォーミング触媒(特許文献2参照)や、金属酸化物からなる担体にロジウム、ルテニウム、イリジウム、パラジウム及び白金の中から選ばれる少なくとも1種の触媒金属を担持させ、比表面積が25m2/g以下、該担体金属酸化物中の金属イオンの電気陰性度が13.0以下、該触媒金属の担持量が金属換算量で担体金属酸化物に対して0.0005〜0.1モル%である合成ガス製造用触媒(特許文献3参照)が知られている。
For the problem that carbon is deposited on the catalyst, for example, a carbon dioxide reforming catalyst in which a ruthenium compound is supported on a support made of aluminum oxide and at least one compound of alkaline earth metal oxides. (Refer to Patent Document 1), or a carrier made of a
一方、天然ガス(メタン)の二酸化炭素/スチームリフォーミングでは、原料ガス中における二酸化炭素やスチームとメタンとのモル比によって、原料ガスと生成する合成ガスの量比(体積比)が図1に示すように変化することから、原料ガスと生成する合成ガスの量比(体積比)が小さくなるように原料ガス中の二酸化炭素/スチームとメタンとのモル比を調整してリフォーミングを行うことが、合成効率の観点から望ましい。しかしながら、そのような原料ガス中の二酸化炭素/スチームとメタンとのモル比でリフォーミングを行うと、触媒表面上に炭素析出が非常に生じやすいという難点があった。 On the other hand, in carbon dioxide / steam reforming of natural gas (methane), the amount ratio (volume ratio) of the raw material gas to the synthetic gas produced is shown in FIG. 1 depending on the molar ratio of carbon dioxide in the raw material gas or steam and methane. As shown, the reforming is performed by adjusting the molar ratio of carbon dioxide / steam to methane in the source gas so that the volume ratio (volume ratio) of the source gas to the synthesis gas to be generated becomes small. Is desirable from the viewpoint of synthesis efficiency. However, when reforming is performed at a molar ratio of carbon dioxide / steam and methane in such a raw material gas, there is a problem that carbon deposition is very likely to occur on the catalyst surface.
上に述べたように、触媒上に炭素が析出するという問題は、効率のよい条件で気相有機反応を行わせようとする際の障害になることが多く、それは二酸化炭素リフォーミングや二酸化炭素/スチームリフォーミングに限られる問題ではない。すなわち、炭素が析出し難いような触媒担体があれば、多くの気相有機反応を効率的に行わせる可能性は飛躍的に拡大する。 As mentioned above, the problem of carbon deposition on the catalyst often becomes an obstacle when trying to carry out a gas phase organic reaction under efficient conditions, which is carbon dioxide reforming or carbon dioxide. / It is not a problem limited to steam reforming. That is, if there is a catalyst carrier that is difficult to deposit carbon, the possibility of efficiently performing many gas phase organic reactions greatly increases.
本発明は、上に述べた視点に立ち、気相有機反応、特に天然ガス(メタン)の二酸化炭素リフォーミングのような炭化水素の分解や変性を含むことにより炭素の析出を生じやすい反応において、用いる触媒上に炭素が析出しにくいような触媒担体を提供することを目的とする。 The present invention is based on the viewpoint described above, in a gas phase organic reaction, particularly in a reaction that easily causes carbon deposition by including decomposition and modification of hydrocarbon such as carbon dioxide reforming of natural gas (methane) An object of the present invention is to provide a catalyst carrier that hardly deposits carbon on the catalyst to be used.
本発明者らは、鋭意研究の結果、酸化マグネシウム粒子の表面近傍に酸化カルシウムを含有し、該酸化カルシウムの該粒子全体に対する含有量が、Ca換算で0.005質量%〜1.5質量%であるマグネシア系触媒担体を提供することにより、上記目的を達成できることを見出し、もって本発明を完成させた。 As a result of intensive studies, the inventors of the present invention contain calcium oxide in the vicinity of the surface of the magnesium oxide particle, and the content of the calcium oxide with respect to the entire particle is 0.005% by mass to 1.5% by mass in terms of Ca. It has been found that the above object can be achieved by providing a magnesia-based catalyst carrier, and thus the present invention has been completed.
前記酸化マグネシウム粒子の単位表面積あたりの酸化カルシウム含有量が、Ca換算で0.05mg−Ca/m2〜150mg−Ca/m2であることが好ましい。
The calcium oxide content per unit surface area of the magnesium oxide particles, it is preferred that 0.05mg-Ca / m 2 ~150mg- Ca /
前記酸化マグネシウム粒子の表面近傍が、該粒子の表面からの深さが該粒子の粒径の10%以内の領域であることが好ましい。 It is preferable that the vicinity of the surface of the magnesium oxide particle is a region where the depth from the surface of the particle is within 10% of the particle diameter of the particle.
前記酸化マグネシウム粒子の表面近傍が、酸化カルシウム含有層を形成していることが好ましい。 It is preferable that the vicinity of the surface of the magnesium oxide particles forms a calcium oxide-containing layer.
本発明のマグネシア系触媒担体の製造方法は、酸化カルシウムを含む原料酸化マグネシウム粒子を1000℃以上で焼成する工程を含むことにより、該原料酸化マグネシウム粒子を凝集ないし融合させて酸化マグネシウム粒子を形成するとともに、該酸化マグネシウム粒子の表面近傍に酸化カルシウムを析出させて、該酸化マグネシウム粒子の表面近傍に酸化カルシウムを含有し、該酸化カルシウムの該粒子全体に対する含有量がCa換算で0.005質量%〜1.5質量%である触媒担体を得ることを特徴とする。 The method for producing a magnesia-based catalyst carrier of the present invention includes a step of firing raw material magnesium oxide particles containing calcium oxide at 1000 ° C. or more, thereby aggregating or fusing the raw material magnesium oxide particles to form magnesium oxide particles. In addition, calcium oxide is precipitated in the vicinity of the surface of the magnesium oxide particles, calcium oxide is contained in the vicinity of the surface of the magnesium oxide particles, and the content of the calcium oxide with respect to the entire particles is 0.005% by mass in terms of Ca. It is characterized by obtaining a catalyst carrier of ˜1.5% by mass.
前記原料酸化マグネシウム粒子に対して炭素を1質量%〜5質量%の範囲内で添加した後に、焼成することが好ましい。 After adding carbon in the range of 1% by mass to 5% by mass with respect to the raw material magnesium oxide particles, firing is preferably performed.
前記触媒担体は、前記酸化マグネシウム粒子の単位表面積あたりの酸化カルシウム含有量が、Ca換算で0.05mg−Ca/m2〜150mg−Ca/m2であることが好ましい。
The catalyst support is calcium oxide content per unit surface area of the magnesium oxide particle is preferably a 0.05mg-Ca / m 2 ~150mg- Ca /
前記触媒担体は、前記酸化マグネシウム粒子の表面近傍が、該粒子の表面からの深さが該粒子の粒径の10%以内の領域であることが好ましい。 In the catalyst carrier, the vicinity of the surface of the magnesium oxide particles is preferably a region whose depth from the surface of the particles is within 10% of the particle diameter of the particles.
本発明のマグネシア系触媒担体を用いると、触媒上への炭素析出を顕著に抑制することができるので、炭素析出の惧れがある気相有機反応を長期間安定的に効率良く実施することができる。 When the magnesia-based catalyst carrier of the present invention is used, carbon deposition on the catalyst can be remarkably suppressed, so that a gas phase organic reaction that may cause carbon deposition can be stably and efficiently performed for a long period of time. it can.
本発明のマグネシア系触媒担体は、酸化マグネシウム粒子の表面近傍に酸化カルシウムを含有し、該酸化カルシウムの該粒子全体に対する含有量が、Ca換算で0.005質量%〜1.5質量%である。 The magnesia-based catalyst carrier of the present invention contains calcium oxide in the vicinity of the surface of the magnesium oxide particles, and the content of the calcium oxide with respect to the entire particles is 0.005% by mass to 1.5% by mass in terms of Ca. .
本発明のマグネシア系触媒担体を構成する酸化マグネシウム粒子の形態は特に限定されず、原料酸化マグネシウムを構成していた個々の粒子がそれぞれ単独で存在するものであってもよいし、複数個の粒子が凝集したものであってもよい。図2に、本発明の触媒担体を構成する酸化マグネシウム粒子の断面形状の例を模式的に示す。図2に示すように、酸化マグネシウム粒子の形状としては、原料酸化マグネシウムを構成していた複数個の粒子が凝集し更に互いに溶融して形成された球状(図2(a))、原料酸化マグネシウムを構成していた2つの粒子が凝集および融合して形成された、中央部51と中央部51より大きい径を有する両端部52で構成されるピーナッツ状 (図2(b))、原料酸化マグネシウムを構成していた3つの粒子が凝集および融合した形状(図2(c))等が挙げられる。なお、本発明の触媒担体はマグネシア系、すなわち酸化マグネシウムを主成分とする粒子から形成されたものである必要があり、酸化ジルコニウム(ZnO)や、アルミナ(Al2O3)等のその他の金属酸化物を主成分とするものでは、本願の効果を得ることはできない。
The form of the magnesium oxide particles constituting the magnesia-based catalyst carrier of the present invention is not particularly limited, and each particle constituting the raw material magnesium oxide may be present alone, or a plurality of particles May be agglomerated. In FIG. 2, the example of the cross-sectional shape of the magnesium oxide particle which comprises the catalyst support | carrier of this invention is shown typically. As shown in FIG. 2, the shape of the magnesium oxide particles is a spherical shape (FIG. 2A) formed by agglomerating a plurality of particles constituting the raw material magnesium oxide and melting each other, and the raw material magnesium oxide. A peanut shape formed by agglomeration and fusion of the two particles constituting the nuclei and having both
本発明の触媒担体は、酸化マグネシウム(MgO)粒子の表面近傍に酸化カルシウム(CaO)を含有するが、酸化カルシウムの存在形態はさまざまであってよい。例えば、酸化マグネシウム粒子の表面近傍の全部または一部の領域が酸化カルシウム含有層を形成していてもよい。なお、このように酸化マグネシウム粒子の表面近傍に形成された酸化カルシウム含有層は、酸化マグネシウムを含んでいてもよいし、酸化カルシウムだけからなる層が酸化マグネシウム粒子の表面を覆う形態であってもよい。また、酸化カルシウムは、酸化マグネシウム粒子の表面に局所的に偏在していてもよく、例えば、酸化マグネシウム粒子の表面の凹部に局所的に酸化カルシウムが存在していてもよい。図3に、本発明の触媒担体において、酸化マグネシウム粒子の表面に酸化カルシウムが存在する形態の例を模式的に示す。図3に示すように、触媒担体10は、酸化マグネシウム粒子11の表面全体に酸化カルシウム含有層12が形成されたもの(図3(a))や酸化マグネシウム粒子11の表面の一部に酸化カルシウム含有層13が形成されたもの(図3(b))であってもよく、また、酸化マグネシウム粒子の表面の凹部等に局所的に酸化カルシウムが存在していてもよい。
The catalyst carrier of the present invention contains calcium oxide (CaO) in the vicinity of the surface of the magnesium oxide (MgO) particles, but the presence form of calcium oxide may be various. For example, the whole or part of the region near the surface of the magnesium oxide particles may form a calcium oxide-containing layer. Note that the calcium oxide-containing layer formed in the vicinity of the surface of the magnesium oxide particles in this way may contain magnesium oxide, or the layer made of only calcium oxide may cover the surface of the magnesium oxide particles. Good. Further, calcium oxide may be locally unevenly distributed on the surface of the magnesium oxide particles. For example, calcium oxide may be locally present in the recesses on the surface of the magnesium oxide particles. FIG. 3 schematically shows an example of a form in which calcium oxide is present on the surface of magnesium oxide particles in the catalyst carrier of the present invention. As shown in FIG. 3, the
本発明の触媒担体は、このように酸化マグネシウム粒子の表面近傍に酸化カルシウムを含有する。そして、酸化マグネシウム粒子の表面近傍に存在する酸化カルシウムの当該粒子全体に対する含有量が、Ca換算で0.005質量%〜1.5質量%、特には0.3質量%〜1.4質量%である。このような構成にすることにより、二酸化炭素リフォーミングや二酸化炭素/スチームリフォーミングなどの炭素析出を伴う可能性がある気相有機反応を行う際の炭素析出を顕著に抑制することができ、長期間安定的に効率良く所望の気相有機反応を実施することができる。酸化マグネシウム粒子の表面近傍に存在する酸化カルシウムの当該粒子全体に対する含有量がCa換算で0.005質量%よりも少ない場合、触媒表面に炭素析出が起り易くなり、これが1.5質量%よりも多い場合には触媒活性が低下し、本発明の効果が得られない。 Thus, the catalyst carrier of the present invention contains calcium oxide in the vicinity of the surface of the magnesium oxide particles. And content with respect to the whole said particle | grain of the calcium oxide which exists in the surface vicinity of a magnesium oxide particle is 0.005 mass%-1.5 mass% in Ca conversion, Especially 0.3 mass%-1.4 mass% It is. By adopting such a configuration, it is possible to remarkably suppress carbon deposition during a gas phase organic reaction that may be accompanied by carbon deposition such as carbon dioxide reforming or carbon dioxide / steam reforming. A desired gas phase organic reaction can be carried out stably and efficiently over a period of time. When the content of calcium oxide present in the vicinity of the surface of the magnesium oxide particles is less than 0.005% by mass in terms of Ca, carbon deposition tends to occur on the catalyst surface, which is less than 1.5% by mass. When the amount is large, the catalytic activity is lowered and the effect of the present invention cannot be obtained.
酸化マグネシウム粒子の表面近傍に存在する酸化カルシウムの当該粒子全体に対するCa換算での含有量は、以下の方法で求められる。すなわち、酸化マグネシウム粒子に存在するCa換算の全Ca量を、試料(触媒担体)を王水で溶解しICP発光分析装置で求めればよい。このとき、酸化マグネシウム粒子の表面に存在するCaの量をEPMA(電子プローブマイクロ分析)で分析し、Caが酸化マグネシウム粒子の内部に存在せず、Caのほぼ全量が酸化マグネシウム粒子表面に存在することをEPMA分析で確認することで、上記ICP発光分析で定量したCa量を、酸化マグネシウム粒子の表面に存在する酸化カルシウムのCa換算の含有量として求めることができる。 The content of calcium oxide present in the vicinity of the surface of the magnesium oxide particles in terms of Ca with respect to the entire particles is determined by the following method. That is, the total Ca amount in terms of Ca present in the magnesium oxide particles may be obtained by dissolving the sample (catalyst support) with aqua regia and using an ICP emission spectrometer. At this time, the amount of Ca present on the surface of the magnesium oxide particles is analyzed by EPMA (electron probe microanalysis). Ca is not present inside the magnesium oxide particles, and almost all of Ca is present on the surface of the magnesium oxide particles. By confirming this by EPMA analysis, the Ca amount determined by the ICP emission analysis can be obtained as the Ca equivalent content of calcium oxide present on the surface of the magnesium oxide particles.
また、本発明の触媒担体は、酸化マグネシウム粒子の単位表面積あたりの酸化カルシウム含有量が、Ca換算で0.05mg−Ca/m2〜150mg−Ca/m2であることが好ましい。酸化マグネシウム粒子の単位表面積あたりの酸化カルシウムのCa換算含有量(mg−Ca/m2)は、酸化マグネシウム粒子1g当たりの、表面に存在する酸化カルシウムのCa換算での含有量(単位:mg)を、当該酸化マグネシウム粒子(触媒担体)の比表面積(単位:m2/g)で除すことにより求められる。
Further, the catalyst carrier of the present invention, calcium oxide content per unit surface area of the magnesium oxide particles, it is preferred that 0.05mg-Ca / m 2 ~150mg- Ca /
酸化カルシウムは、当該酸化マグネシウム粒子の表面からの深さが該粒子の粒径の10%以内の領域に存在することが好ましい。このとき「表面からの深さが該粒子の粒径の10%以内」とは、当該酸化マグネシウム粒子の重心と該重心から最も遠い表面との距離をその粒子の半径r1としたときに、触媒担体の表面から、重心に向かってr1/10の距離の位置までの領域内を意味する。 Calcium oxide is preferably present in a region where the depth from the surface of the magnesium oxide particles is within 10% of the particle size of the particles. At this time, “the depth from the surface is within 10% of the particle diameter of the particle” means that the distance between the center of gravity of the magnesium oxide particle and the surface farthest from the center of gravity is the radius r 1 of the particle, from the surface of the catalyst support, it means the region from the position of the distance r 1/10 towards the center of gravity.
本発明の触媒担体を構成する酸化マグネシウム粒子の大きさは、例えば最大径0.1〜10μmであるが、これに限られるものではない。また、酸化カルシウム含有層の厚さは例えば5〜70nmである。 The size of the magnesium oxide particles constituting the catalyst carrier of the present invention is, for example, a maximum diameter of 0.1 to 10 μm, but is not limited thereto. Moreover, the thickness of a calcium oxide content layer is 5-70 nm, for example.
本発明の触媒担体の形状は、例えば、リング状、マルチホール状、タブレット状や、ペレット状である。 The shape of the catalyst carrier of the present invention is, for example, a ring shape, a multi-hole shape, a tablet shape, or a pellet shape.
本発明のマグネシア系触媒用担体は、例えば、酸化マグネシウムを含有する原料酸化マグネシウム粒子を1000℃以上で焼成することにより、該原料酸化マグネシウム粒子を凝集させて酸化マグネシウム粒子を形成するとともに、該酸化マグネシウム粒子の表面に酸化カルシウムを析出させて製造することができる。 The magnesia-based catalyst carrier of the present invention, for example, calcinates raw magnesium oxide particles containing magnesium oxide at 1000 ° C. or more to aggregate the raw magnesium oxide particles to form magnesium oxide particles, and It can be produced by depositing calcium oxide on the surface of the magnesium particles.
すなわち、本発明の触媒担体の製造方法においては、酸化カルシウムを含有する原料酸化マグネシウム粒子を用いる。そして、この原料酸化マグネシウム粒子中に含まれる酸化カルシウム含有量は、0.005質量%〜1.5質量%、特には0.3質量%〜1.4質量%である。ここでいう「酸化カルシウムを含有する原料酸化マグネシウム粒子」とは、原料として用いる原料酸化マグネシウム粒子が酸化カルシウムを0.005質量%〜1.5質量%の範囲内で内部に例えば均一に含むものである。したがって、従来通常用いられている市販の酸化マグネシウム等の純度の高い酸化マグネシウムは酸化カルシウム含有量が少ないため、本発明において原料酸化マグネシウム粒子として用いることはできない。 That is, in the method for producing a catalyst carrier of the present invention, raw material magnesium oxide particles containing calcium oxide are used. And calcium oxide content contained in this raw material magnesium oxide particle is 0.005 mass%-1.5 mass%, especially 0.3 mass%-1.4 mass%. The “raw material magnesium oxide particles containing calcium oxide” as used herein means that the raw material magnesium oxide particles used as the raw material contain calcium oxide uniformly within the range of 0.005% by mass to 1.5% by mass, for example. . Accordingly, high-purity magnesium oxide such as commercially available magnesium oxide that has been conventionally used has a low calcium oxide content and cannot be used as raw material magnesium oxide particles in the present invention.
このような酸化カルシウムを含有する原料酸化マグネシウム粒子を、必要に応じて所望の触媒用担体の形状、例えば、リング状、マルチホール状、タブレット状、ペレット状に成形する。 The raw material magnesium oxide particles containing such calcium oxide are formed into a desired catalyst carrier shape, for example, a ring shape, a multi-hole shape, a tablet shape, or a pellet shape, if necessary.
成形する際に、炭素等の滑沢材を添加してもよい。例えば、原料酸化マグネシウム粒子に対して、炭素を1質量%〜5質量%の範囲内で添加することが好ましい。 When molding, a lubricant such as carbon may be added. For example, it is preferable to add carbon in the range of 1% by mass to 5% by mass with respect to the raw material magnesium oxide particles.
必要に応じて成形した酸化カルシウムを含有する原料酸化マグネシウム粒子を、1000℃以上で焼成して、原料酸化マグネシウム粒子を凝集させて酸化マグネシウム粒子を形成するとともに、該酸化マグネシウム粒子の表面に酸化カルシウムを析出させることにより、本発明の触媒担体を製造することができる。 The raw material magnesium oxide particles containing calcium oxide formed as necessary are fired at 1000 ° C. or higher to aggregate the raw magnesium oxide particles to form magnesium oxide particles, and the surface of the magnesium oxide particles has calcium oxide. By precipitating the catalyst, the catalyst carrier of the present invention can be produced.
原料酸化マグネシウム粒子を詳しくは後述する特定の条件で焼成すると、原料酸化マグネシウム粒子が凝集して酸化マグネシウム粒子を形成する。また、該特定の条件での焼成により原料酸化マグネシウム粒子の内部に存在する酸化カルシウムが表面に染み出す等して酸化カルシウムが酸化マグネシウム粒子の表面付近に析出し、酸化マグネシウム粒子の表面近傍に酸化カルシウム含有層を形成したり、酸化マグネシウム粒子表面の凹部等に局所的に存在するようになる。 When the raw material magnesium oxide particles are fired under specific conditions described later in detail, the raw material magnesium oxide particles are aggregated to form magnesium oxide particles. In addition, the calcium oxide present inside the raw material magnesium oxide particles exudes to the surface by firing under the specific conditions, so that the calcium oxide is precipitated near the surface of the magnesium oxide particles and oxidized near the surface of the magnesium oxide particles. A calcium-containing layer is formed, or the calcium-containing layer is locally present in the recesses on the surface of the magnesium oxide particles.
原料酸化マグネシウム粒子に含まれる酸化カルシウム量が少ない場合は、表面付近に析出する酸化カルシウム量が不十分になり、本発明の炭素析出を顕著に抑制する効果は得られない。 When the amount of calcium oxide contained in the raw material magnesium oxide particles is small, the amount of calcium oxide deposited in the vicinity of the surface becomes insufficient, and the effect of remarkably suppressing the carbon deposition of the present invention cannot be obtained.
また、焼成温度は、1000℃以上である必要がある。焼成温度が低いと、原料酸化マグネシウム粒子の内部に存在する酸化カルシウムが酸化マグネシウム粒子の表面付近に析出せず、本発明の効果が得られない。焼成温度は、1400℃以下であることが好ましい。 The firing temperature needs to be 1000 ° C. or higher. When the firing temperature is low, calcium oxide present in the raw material magnesium oxide particles does not precipitate near the surface of the magnesium oxide particles, and the effect of the present invention cannot be obtained. The firing temperature is preferably 1400 ° C. or lower.
また、本発明の触媒担体は、上記以外の方法でも製造することができる。具体的には、高純度の酸化マグネシウム(例えばCaO含有量がCa換算で0.01質量%以下で純度99.9wt%以上のMgO)を、60〜80℃にて煮沸しながら攪拌してMg(OH)2を得ると共に、同時にCa(OH)2の水溶液を滴下し攪拌することによって、Ca添加型Mg(OH)2粒子を得る。このようにして得られたCa添加型Mg(OH)2粒子は、CaOを内部にほぼ均一に含む。そして、得られたCa添加型Mg(OH)2粒子を、上記の製造方法と同様に、必要に応じて滑沢材の添加や成形をして1000℃以上好ましくは1400℃以下で焼成することにより、Ca添加型Mg(OH)2粒子を凝集させて酸化マグネシウム粒子を形成するとともに、該酸化マグネシウム粒子の表面付近に酸化カルシウムを析出させて、本発明の触媒担体を製造することができる。 The catalyst carrier of the present invention can also be produced by a method other than the above. Specifically, high-purity magnesium oxide (for example, MgO having a CaO content of 0.01 mass% or less and a purity of 99.9 wt% or more in terms of Ca) is stirred while boiling at 60 to 80 ° C., and Mg While obtaining (OH) 2 , simultaneously adding an aqueous solution of Ca (OH) 2 and stirring, Ca-added Mg (OH) 2 particles are obtained. The Ca-added Mg (OH) 2 particles thus obtained contain CaO almost uniformly inside. Then, the obtained Ca-added Mg (OH) 2 particles are calcined at 1000 ° C. or higher, preferably 1400 ° C. or lower, with a lubricant added or molded as necessary, as in the above production method. Thus, the Ca-added Mg (OH) 2 particles are aggregated to form magnesium oxide particles, and calcium oxide is precipitated near the surface of the magnesium oxide particles, whereby the catalyst carrier of the present invention can be produced.
なお、いずれの製造方法においても、基本的に酸化カルシウムを添加する操作は行わない。 In any of the production methods, basically, an operation of adding calcium oxide is not performed.
ここで、原料酸化マグネシウム粒子、Ca添加型Mg(OH)2粒子やその成形体を焼成する条件、具体的には、上記原料酸化マグネシウム粒子やCa添加型Mg(OH)2粒子の酸化カルシウム含有量や焼成温度に加えて、焼成雰囲気、焼成時間、滑沢材等の添加剤の種類及び添加量、焼成する成形体の大きさや形状等によって、原料酸化マグネシウム粒子やCa添加型Mg(OH)2粒子の凝集、酸化マグネシウム粒子の表面付近への酸化カルシウムの析出の有無や、時期及び程度が変化する。したがって、酸化マグネシウム粒子やCa添加型Mg(OH)2粒子を凝集させて酸化マグネシウム粒子を形成すると共に該酸化マグネシウム粒子の表面付近に酸化カルシウムを析出させて酸化カルシウム含有層を形成するためには、これら焼成条件のバランスを調整する必要がある。 Here, the raw material magnesium oxide particles, the Ca-added Mg (OH) 2 particles and the conditions for firing the molded body thereof, specifically, the calcium oxide content of the raw material magnesium oxide particles and Ca-added Mg (OH) 2 particles In addition to the amount and firing temperature, depending on the firing atmosphere, firing time, type and amount of additives such as lubricant, size and shape of the compact to be fired, raw material magnesium oxide particles and Ca-added Mg (OH) Agglomeration of the two particles, presence or absence of calcium oxide in the vicinity of the surface of the magnesium oxide particles, and the timing and degree change. Therefore, in order to form magnesium oxide particles by aggregating magnesium oxide particles and Ca-added Mg (OH) 2 particles and depositing calcium oxide near the surface of the magnesium oxide particles to form a calcium oxide-containing layer It is necessary to adjust the balance of these firing conditions.
本発明の触媒担体を用いて、例えば合成ガス製造触媒を製造するには、上記本発明の触媒担体に、ルテニウム(Ru)及びロジウム(Rh)の少なくとも一方の金属を担持させればよい。合成ガス製造触媒を製造するには、RuやRhを担持させればよいが、担持させる触媒金属は当該触媒を用いて実施する反応により、Ni、Ir、Os等その他の金属を適宜選択すればよく、そうして製造された触媒を用いれば当該反応において炭素析出を効果的に抑制することができる。 For example, in order to produce a synthesis gas production catalyst using the catalyst carrier of the present invention, at least one of ruthenium (Ru) and rhodium (Rh) may be supported on the catalyst carrier of the present invention. In order to produce a synthesis gas production catalyst, Ru or Rh may be supported. However, the catalyst metal to be supported may be appropriately selected from other metals such as Ni, Ir, and Os depending on the reaction carried out using the catalyst. Well, if the catalyst thus produced is used, carbon deposition can be effectively suppressed in the reaction.
触媒金属の担持量は、本発明の触媒担体に対して、通常、金属換算で200wtppm〜2000wtppmとするが、実施する反応に応じて適宜調整すればよい。触媒金属の担持量は、一般に、ICP発光分析装置で求めることが出来る。具体的には、触媒を試料を王水で溶解したのち、所定の測定波長を照射して定量することが出来る。 The amount of the catalyst metal supported is usually 200 wtppm to 2000 wtppm in terms of metal relative to the catalyst carrier of the present invention, but may be appropriately adjusted according to the reaction to be performed. The amount of catalyst metal supported can generally be determined with an ICP emission spectrometer. Specifically, the catalyst can be quantified by dissolving a sample in aqua regia and irradiating a predetermined measurement wavelength.
本発明の触媒担体の比表面積は、0.1m2/g〜1.0m2/gであることが好ましい。ここでいう「比表面積」とは、窒素ガスの吸着量からBET吸着等温式を利用して算出したBET比表面積であり、例えば、比表面積測定装置(製品名「AUTOSORB−1」、ユアサアイオニクス(株)社製)を使用し、液体窒素を用いて多点法によって測定される値である。
The specific surface area of the catalyst carrier of the present invention is preferably a 0.1m 2 /g~1.0
本発明の触媒担体に担持される触媒金属は、本発明の触媒担体の表面からの深さが当該酸化マグネシウム粒子の粒径の10%以内に存在することが好ましい。換言すると、触媒金属を担持する領域は、本発明の触媒担体が酸化カルシウムを含有する領域、すなわち酸化マグネシウム粒子の表面近傍であることが好ましい。 The catalyst metal supported on the catalyst carrier of the present invention preferably has a depth from the surface of the catalyst carrier of the present invention within 10% of the particle diameter of the magnesium oxide particles. In other words, the region supporting the catalyst metal is preferably a region where the catalyst carrier of the present invention contains calcium oxide, that is, the vicinity of the surface of the magnesium oxide particles.
本発明の触媒担体に担持される触媒金属の存在形態は特に限定されないが、酸化マグネシウム粒子の表面近傍において、酸化カルシウムに隣接して存在していることが好ましい。触媒金属が酸化マグネシウム粒子の表面の全部または一部を覆っていてもよいし、触媒金属の粒子が酸化マグネシウム粒子の表面に分散して存在していてもよい。あるいは、触媒金属は、酸化マグネシウム粒子の表面において、局所的に偏在していてもよく、例えば、酸化マグネシウム粒子の表面の凹部に存在していてもよい。また、このような層状や粒子状の触媒金属を、酸化カルシウム層の少なくとも一部が覆っていてもよいし、層状や粒子状の触媒金属と層状や粒子状の酸化カルシウムが交互に隣り合っていてもよい。 The form of the catalyst metal supported on the catalyst carrier of the present invention is not particularly limited, but is preferably present adjacent to the calcium oxide in the vicinity of the surface of the magnesium oxide particles. The catalyst metal may cover all or part of the surface of the magnesium oxide particles, or the catalyst metal particles may be dispersed on the surface of the magnesium oxide particles. Or the catalyst metal may be unevenly distributed locally on the surface of the magnesium oxide particle, for example, may exist in the recessed part of the surface of the magnesium oxide particle. Further, the layered or particulate catalyst metal may be covered by at least a part of the calcium oxide layer, or the layered or particulate catalyst metal and the layered or particulate calcium oxide are alternately adjacent to each other. May be.
本発明の触媒担体に触媒金属を担持させる方法としては、触媒金属の水溶液を本発明の触媒担体に噴霧すればよい。触媒金属の水溶液は、当該金属の硝酸塩、塩化物等の無機酸塩や、酢酸塩等の有機酸塩などを、水に溶解させることで得られる。噴霧する水溶液の量は、例えば当該触媒担体の吸水量の1.0〜1.3質量倍とすることが好ましい。なお、当該触媒担体の吸水量は、Incipient-wetness法で求めることが出来る。これは、触媒担体に純水をマイクロピペット或いはビュレットでごく少量ずつ滴下し、触媒表面が湿ってくるまでの滴下量を測定する方法である。 As a method for supporting the catalyst metal on the catalyst carrier of the present invention, an aqueous solution of the catalyst metal may be sprayed on the catalyst carrier of the present invention. An aqueous solution of a catalytic metal can be obtained by dissolving an inorganic acid salt such as nitrate or chloride of the metal or an organic acid salt such as acetate in water. The amount of the aqueous solution to be sprayed is preferably 1.0 to 1.3 times the amount of water absorbed by the catalyst carrier, for example. The water absorption amount of the catalyst carrier can be determined by the incipient-wetness method. This is a method in which pure water is dripped little by little with a micropipette or burette onto the catalyst carrier, and the amount of dripping until the catalyst surface gets wet is measured.
また、別法としては、本発明の触媒担体を水中に分散させた分散液に、担持させる金属の塩又はその水溶液を添加して混合する含浸法を採用してもよい。 Alternatively, an impregnation method in which a metal salt to be supported or an aqueous solution thereof is added to and mixed with a dispersion in which the catalyst support of the present invention is dispersed in water may be employed.
触媒金属を担持させた本発明の触媒担体を乾燥および焼成することにより、所望の触媒が得られる。乾燥や焼成の条件は特に限定されないが、例えば、乾燥温度は50〜150℃、乾燥時間は1〜3時間、焼成温度は300〜500℃、焼成時間は1〜5時間である。 A desired catalyst can be obtained by drying and calcining the catalyst carrier of the present invention on which a catalyst metal is supported. The conditions for drying and firing are not particularly limited. For example, the drying temperature is 50 to 150 ° C., the drying time is 1 to 3 hours, the firing temperature is 300 to 500 ° C., and the firing time is 1 to 5 hours.
以下に、本発明の更なる理解のために実施例を用いて説明する。以下の実施例の多くは、本発明の触媒担体を製造し、これを用いて合成ガス製造触媒を製造する場合の実施例であるが、本発明の触媒担体の用途は合成ガス製造触媒に限られず、以下に示す実施例はなんら本発明を限定するものではない。 Hereinafter, examples will be described for further understanding of the present invention. Many of the following examples are examples in the case where the catalyst carrier of the present invention is produced and a synthesis gas production catalyst is produced using the catalyst carrier, but the use of the catalyst carrier of the present invention is limited to the synthesis gas production catalyst. However, the following examples do not limit the present invention.
<実施例1>
内部に酸化カルシウム(CaO)をCa換算で0.3wt%含有する純度98.7wt%の酸化マグネシウム(MgO)の粉末(原料酸化マグネシウム粒子)に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1180℃で3h(時間)焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.10m2/gであった。
<Example 1>
A powder of 98.7 wt% magnesium oxide (MgO) containing 0.3 wt% of calcium oxide (CaO) in terms of Ca inside (raw material magnesium oxide particles), and 3.0 wt% of MgO powder as a sliding material % Carbon was mixed to form a 1/4 inch diameter cylindrical pellet. The formed pellets were calcined in air at 1180 ° C. for 3 hours (hours) to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.10 m 2 / g.
得られた触媒担体をICP発光分析(以下単に「ICP」とも記載する)で分析したところ、該触媒担体は、CaOをCa換算で0.3wt%含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子は原料酸化マグネシウム粒子よりも顕著に大きかった。したがって、原料MgO粒子が凝集してMgO粒子を形成し、且つ、原料MgO粒子が含有するCaOがMgO粒子表面に析出したと考えられる。触媒担体の断面のEPMA分析結果を図4に示す。また、得られた触媒担体のEPMA分析による各元素のmol%換算の定量結果を表1に示す。分析点P1〜P10は、図4の矢印で示した箇所である。 When the obtained catalyst support was analyzed by ICP emission analysis (hereinafter also simply referred to as “ICP”), the catalyst support contained 0.3 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. Further, the MgO particles constituting the obtained catalyst carrier were significantly larger than the raw material magnesium oxide particles. Therefore, it is considered that the raw material MgO particles aggregate to form MgO particles, and CaO contained in the raw material MgO particles is precipitated on the surface of the MgO particles. The EPMA analysis result of the cross section of the catalyst carrier is shown in FIG. In addition, Table 1 shows quantitative results in terms of mol% of each element by EPMA analysis of the obtained catalyst carrier. The analysis points P1 to P10 are points indicated by arrows in FIG.
得られた触媒担体は、図4に示されるように、球状やピーナッツ状の粒子から構成されていた。そして、各触媒担体粒子は、MgO粒子の表面の一部が、CaOを含有する層(CaO含有層)で被覆され、また、MgO粒子表面の凹部(くぼみ)にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。MgO粒子の単位表面積あたりの酸化カルシウム含有量(以下「MgO粒子表面のCaOの存在量」とも記載する)を求めたところ、Ca換算で30mg−Ca/m2であった。また、図4および表1に示すように、ピーナッツ状粒子の中央部(分析点P1及びP9)はCaをごく微量しか含まず、ほとんどのCaは両端部(分析点P2〜P8及びP10)に含まれていた。 As shown in FIG. 4, the obtained catalyst carrier was composed of spherical or peanut-like particles. Each catalyst carrier particle was partially covered with a layer containing CaO (CaO-containing layer), and CaO was present in the recesses (dents) on the surface of the MgO particles. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. When the calcium oxide content per unit surface area of the MgO particles (hereinafter also referred to as “amount of CaO present on the MgO particle surface”) was determined, it was 30 mg-Ca / m 2 in terms of Ca. Moreover, as shown in FIG. 4 and Table 1, the central part (analysis points P1 and P9) of the peanut-like particles contains a very small amount of Ca, and most of the Ca is at both ends (analysis points P2 to P8 and P10). It was included.
次に、得られた触媒担体に、0.5wt%のRuを含む硝酸ニトロシルルテニウム水溶液を、触媒担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)噴霧し、触媒担体にRuを担持させた。こうして得られたRuを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で400℃で2.0時間焼成し、触媒を得た。 Next, 0.15 cc (1.0 times the amount of water absorbed by the catalyst carrier) is sprayed onto the obtained catalyst carrier with an aqueous solution of nitrosylruthenium nitrate containing 0.5 wt% Ru against 1.0 g of the catalyst carrier. Ru was supported on the carrier. The Ru-supported catalyst support thus obtained was dried in an oven at 120 ° C. for 2.5 hours in the air, and then calcined in the electric furnace at 400 ° C. for 2.0 hours in the air to obtain a catalyst.
得られた触媒は、Ruを触媒に対し750wtppmの割合で含有するもので、そのBET比表面積は0.10m2/gであった。また、得られた触媒に対し、触媒担体と同様に、EPMA分析を行った。触媒のEPMA分析結果を図5に示す。また、得られた触媒のEPMA分析による各元素のmol%換算の定量結果を表2に示す。分析点P1〜P11は、図5の矢印で示した箇所である。 The obtained catalyst contained Ru at a ratio of 750 wtppm with respect to the catalyst, and its BET specific surface area was 0.10 m 2 / g. Further, EPMA analysis was performed on the obtained catalyst in the same manner as the catalyst carrier. The EPMA analysis result of the catalyst is shown in FIG. In addition, Table 2 shows quantitative results in terms of mol% of each element by EPMA analysis of the obtained catalyst. Analysis points P1 to P11 are points indicated by arrows in FIG.
図5に示すように、得られた触媒では、Ruは触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内の領域に存在していた。RuとCaの位置が重複するため、該Ruの近傍にCaOが存在しているといえる。なお、触媒担体中に含まれるRu及びCaOは、全てMgO粒子の表面近傍に存在していた。また、図5及び表2に示すように、ピーナッツ状粒子の中央部(分析点P3及びP10)は、Caをごく微量しか含まず、ほとんどのCaは両端部(分析点P1〜P2、P4〜P9及びP11)に含まれていた。 As shown in FIG. 5, in the obtained catalyst, Ru was present in a region close to the surface of the catalyst particles, that is, a region within 10% of the depth from the catalyst surface. Since the positions of Ru and Ca overlap, it can be said that CaO exists in the vicinity of the Ru. Note that Ru and CaO contained in the catalyst carrier were all present in the vicinity of the surface of the MgO particles. Moreover, as shown in FIG. 5 and Table 2, the central part (analysis points P3 and P10) of the peanut-like particles contains only a very small amount of Ca, and most of Ca has both end parts (analysis points P1 to P2, P4 to P4). P9 and P11).
<反応例1>
実施例1で調製した触媒50ccを反応器の触媒層に充填してメタンのCO2リフォーミング試験を実施した。なお、該反応器は、触媒層の上から原料ガスを導入し、触媒層に導入された原料ガスは下降して触媒層を通過する構成である。
<Reaction Example 1>
50 cc of the catalyst prepared in Example 1 was filled in the catalyst layer of the reactor, and a CO 2 reforming test of methane was performed. The reactor has a configuration in which a raw material gas is introduced from above the catalyst layer, and the raw material gas introduced into the catalyst layer descends and passes through the catalyst layer.
具体的には、まず、予めH2及びH2Oをモル比(H2/H2O=1/0)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理(触媒の活性化)を行った。その後、CH4:CO2:H2O(モル比)=1:2.5:1.5の原料ガスを、触媒層出口のガス圧力1471kPaG,触媒層出口のガス温度850℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, a mixed gas in which the molar ratio of H 2 and H 2 O (H 2 / H 2 O = 1/0) is preliminarily passed through the catalyst layer at 500 ° C. for 1 hour to be brought into contact with the catalyst. Thus, reduction treatment (activation of the catalyst) was performed. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 2.5: 1.5 is used, the gas pressure at the catalyst layer outlet is 1471 kPaG, the gas temperature at the catalyst layer outlet is 850 ° C., methane standard The treatment was performed under the condition of GHSV = 2500 / hour.
この結果、反応開始から5時間経過後のCH4転化率は92.5%(実験条件下でのCH4の平衡転化率=92.5%)であり、また反応開始から1500時間経過後のCH4の転化率は、92.5%であった。また、1500時間経過後に、触媒を上下方向に4等分割して抜き出ししたところ、触媒上にカーボンが析出しており、カーボン/触媒は、上部から順にそれぞれ0.20wt%(Top)、0.15wt%(Md1)、0.10wt%(Md2)、0.10wt%(Btm)であった。なお、CH4の転化率は、下記式で定義される。
CH4転化率(%)=(A−B)/A×100
A:原料ガス中のCH4モル数
B:生成物(触媒層から排出されるガス)中のCH4モル数
As a result, the CH 4 conversion after 5 hours from the start of the reaction was 92.5% (equilibrium conversion of CH 4 under the experimental conditions = 92.5%), and after 1500 hours from the start of the reaction. The conversion rate of CH 4 was 92.5%. Further, after 1500 hours, when the catalyst was extracted by dividing into four equal parts in the vertical direction, carbon was deposited on the catalyst, and the carbon / catalyst was 0.20 wt% (Top), 0. They were 15 wt% (Md1), 0.10 wt% (Md2), and 0.10 wt% (Btm). The conversion rate of CH 4 is defined by the following formula.
CH 4 conversion (%) = (A−B) / A × 100
A: raw material CH 4 moles of gas B: CH 4 moles in the product (gas discharged from the catalyst layer)
また、反応例1記載の還元処理条件で処理した触媒(原料ガス通気前の触媒)のS−TEM分析を行った。EDXにより元素マッピングした結果を図6に示す。図6において、上段の左側から順にCa、Mg、Ru、下段はTEM写真である。 Moreover, the S-TEM analysis of the catalyst (catalyst before raw material gas aeration) processed on the reduction process conditions described in Reaction Example 1 was performed. The result of element mapping by EDX is shown in FIG. In FIG. 6, Ca, Mg, Ru, and the lower stage are TEM photographs in order from the left side of the upper stage.
この結果、粒子状のRuが触媒表面に存在していることが確認された。また、図6に示すように、RuはCa近傍に存在していることが確認された。 As a result, it was confirmed that particulate Ru was present on the catalyst surface. Moreover, as shown in FIG. 6, it was confirmed that Ru exists in the Ca vicinity.
<実施例2>
内部にCaOをCa換算で0.3wt%含有する純度98.7wt%以上のMgOの粉末に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1180℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.10m2/gであった。
<Example 2>
Inside, MgO powder containing 0.3 wt% of CaO in terms of Ca and having a purity of 98.7 wt% or more is mixed with 3.0 wt% of carbon as MgO powder as a lubricant, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1180 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.10 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.3wt%含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子は原料酸化マグネシウム粒子よりも顕著に大きかった。したがって、原料MgO粒子が凝集してMgO粒子を形成し、且つ、原料MgO粒子が含有するCaOがMgO粒子表面に析出したと考えられる。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the catalyst support contained 0.3 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. Further, the MgO particles constituting the obtained catalyst carrier were significantly larger than the raw material magnesium oxide particles. Therefore, it is considered that the raw material MgO particles aggregate to form MgO particles, and CaO contained in the raw material MgO particles is precipitated on the surface of the MgO particles.
得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で30mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst carrier is in the form of particles, as in Example 1. Part of the surface of the MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of the MgO particles. It was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the amount of CaO present on the surface of the MgO particles was determined, it was 30 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、0.55wt%のRuを含む塩化ルテニウム水和物(RuCl3)水溶液を、触媒担体1.0gに対し0.17cc(触媒担体の吸水量の1.1倍)にて噴霧し、触媒担体にRuを担持させた。こうして得られたRuを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で400℃で2.0時間焼成し、触媒を得た。 Next, an aqueous ruthenium chloride hydrate (RuCl 3 ) solution containing 0.55 wt% of Ru was added to the obtained catalyst support in an amount of 0.17 cc (1.1% of the amount of water absorbed by the catalyst support). The catalyst support was loaded with Ru. The Ru-supported catalyst support thus obtained was dried in an oven at 120 ° C. for 2.5 hours in the air, and then calcined in the electric furnace at 400 ° C. for 2.0 hours in the air to obtain a catalyst.
得られた触媒は、Ruを触媒に対し900wtppmの割合で含有するもので、そのBET比表面積は0.10m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Ruは触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内の領域に存在していた。よって、該Ruの近傍にCaOが存在しているといえる。 The obtained catalyst contained Ru in a proportion of 900 wtppm with respect to the catalyst, and its BET specific surface area was 0.10 m 2 / g. Further, when the obtained catalyst was subjected to EPMA analysis in the same manner as in Example 1, Ru was present in a region close to the surface of the catalyst particles, that is, a region within 10% of the depth from the catalyst surface. Therefore, it can be said that CaO exists in the vicinity of the Ru.
<反応例2>
実施例2で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Reaction example 2>
50 cc of the catalyst prepared in Example 2 was charged into the same reactor as that used in Example 1, and a CO 2 reforming test of methane was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/3)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度850℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/3) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction process was performed by making it contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is prepared by using a gas pressure of 1960 kPaG at the outlet of the catalyst layer, a gas temperature of 850 ° C. at the outlet of the catalyst layer, and GHSV of methane reference = 2. The treatment was performed at 500 / hour.
この結果、反応開始から5時間経過後のCH4転化率は54.8%(実験条件下でのCH4の平衡転化率=54.8%)であり、また反応開始から300時間経過後のCH4の転化率は、54.8%、1100時間経過後のCH4の転化率は、53.1%であった。また1100時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は、上部から順にそれぞれ0.25wt%、0.10wt%、0.10wt%、0.04wt%であった。また、実施例1と同様に、反応例2記載の前処理条件で処理した触媒を分析したところ、粒子状のRuが触媒表面に存在していることが確認された。 As a result, the CH 4 conversion rate after 5 hours from the start of the reaction was 54.8% (equilibrium conversion rate of CH 4 under experimental conditions = 54.8%), and 300 hours after the start of the reaction. The conversion rate of CH 4 was 54.8%, and the conversion rate of CH 4 after 1100 hours was 53.1%. In addition, after 1100 hours, the amount of carbon on the catalyst extracted in four portions in the same manner as in Example 1 was 0.25 wt%, 0.10 wt%, 0.10 wt%, and 0.04 wt% in order from the top. It was. Similarly to Example 1, the catalyst treated under the pretreatment conditions described in Reaction Example 2 was analyzed, and it was confirmed that particulate Ru was present on the catalyst surface.
<実施例3>
内部にCaOをCa換算で0.3wt%含有する純度98.7wt%以上のMgOの粉末に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1180℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.10m2/gであった。
<Example 3>
Inside, MgO powder containing 0.3 wt% of CaO in terms of Ca and having a purity of 98.7 wt% or more is mixed with 3.0 wt% of carbon as MgO powder as a lubricant, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1180 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.10 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.3wt%含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子は原料酸化マグネシウム粒子よりも顕著に大きかった。したがって、原料MgO粒子が凝集してMgO粒子を形成し、且つ、原料MgO粒子が含有するCaOがMgO粒子表面に析出したと考えられる。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the catalyst support contained 0.3 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. Further, the MgO particles constituting the obtained catalyst carrier were significantly larger than the raw material magnesium oxide particles. Therefore, it is considered that the raw material MgO particles aggregate to form MgO particles, and CaO contained in the raw material MgO particles is precipitated on the surface of the MgO particles.
得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で30mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst carrier is in the form of particles, as in Example 1. Part of the surface of the MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of the MgO particles. It was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the amount of CaO present on the surface of the MgO particles was determined, it was 30 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、0.17wt%のRuを含む硝酸ルテニウム水溶液を、触媒担体1.0gに対し0.18cc(触媒担体の吸水量の1.2倍)にて噴霧し、触媒担体にRuを担持させた。こうして得られたRuを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で400℃で2.0時間焼成し、触媒を得た。 Next, an aqueous ruthenium nitrate solution containing 0.17 wt% Ru is sprayed onto the obtained catalyst carrier at 0.18 cc (1.2 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, Ru was supported on the catalyst support. The Ru-supported catalyst support thus obtained was dried in an oven at 120 ° C. for 2.5 hours in the air, and then calcined in the electric furnace at 400 ° C. for 2.0 hours in the air to obtain a catalyst.
得られた触媒は、Ruを触媒に対し300wtppmの割合で含有するもので、そのBET比表面積は0.10m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Ruは触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内の領域に存在していた。よって、該Ruの近傍にCaOが存在しているといえる。 The obtained catalyst contained Ru in a proportion of 300 wtppm with respect to the catalyst, and its BET specific surface area was 0.10 m 2 / g. Further, when the obtained catalyst was subjected to EPMA analysis in the same manner as in Example 1, Ru was present in a region close to the surface of the catalyst particles, that is, a region within 10% of the depth from the catalyst surface. Therefore, it can be said that CaO exists in the vicinity of the Ru.
<反応例3>
実施例3で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのH2O/CO2リフォーミング試験を実施した。
<Reaction Example 3>
A reactor similar to that used in Example 1 was charged with 50 cc of the catalyst prepared in Example 3, and an H 2 O / CO 2 reforming test for methane was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/6)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:3:0.3の原料ガスを、触媒層出口のガス圧力1471kPaG,触媒層出口のガス温度900℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/6) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction process was performed by making it contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 3: 0.3 is used, the gas pressure at the catalyst layer outlet is 1471 kPaG, the gas temperature at the catalyst layer outlet is 900 ° C., the methane reference GHSV = The treatment was performed at 2,500 / hour.
この結果、反応開始から5時間経過後のCH4転化率は97.0%(実験条件下でのCH4の平衡転化率=97.0%)であり、また反応開始から15,000時間経過後のCH4の転化率は、97.0%であった。また15,000時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ0.20wt%、0.05wt%、0.03wt%、0.02wt%であった。また、実施例1と同様に、反応例3記載の前処理条件で処理した触媒を分析したところ、粒子状のRuが触媒表面に存在していることが確認された。 As a result, the CH 4 conversion after 5 hours from the start of the reaction was 97.0% (equilibrium conversion of CH 4 under experimental conditions = 97.0%), and 15,000 hours had elapsed from the start of the reaction. The subsequent conversion rate of CH 4 was 97.0%. Further, after 15,000 hours had elapsed, the amount of carbon on the catalyst extracted in four portions in the same manner as in Example 1 was 0.20 wt%, 0.05 wt%, 0.03 wt%, and 0.02 wt%, respectively, in order from the top. there were. Similarly to Example 1, when the catalyst treated under the pretreatment conditions described in Reaction Example 3 was analyzed, it was confirmed that particulate Ru was present on the catalyst surface.
<実施例4>
内部にCaOをCa換算で0.3wt%含有する純度98.7wt%以上のMgOの粉末に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1150℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.12m2/gであった。
<Example 4>
Inside, MgO powder containing 0.3 wt% of CaO in terms of Ca and having a purity of 98.7 wt% or more is mixed with 3.0 wt% of carbon as MgO powder as a lubricant, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1150 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.12 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.3wt%含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子は原料酸化マグネシウム粒子よりも顕著に大きかった。したがって、原料MgO粒子が凝集してMgO粒子を形成し、且つ、原料MgO粒子が含有するCaOがMgO粒子表面に析出したと考えられる。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the catalyst support contained 0.3 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. Further, the MgO particles constituting the obtained catalyst carrier were significantly larger than the raw material magnesium oxide particles. Therefore, it is considered that the raw material MgO particles aggregate to form MgO particles, and CaO contained in the raw material MgO particles is precipitated on the surface of the MgO particles.
得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で25mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst carrier is in the form of particles, as in Example 1. Part of the surface of the MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of the MgO particles. It was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the amount of CaO present on the surface of the MgO particles was determined, it was 25 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、0.3wt%のRhを含む酢酸ロジウム(Rh(CH3COO)3)水溶液を、触媒担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)にて噴霧し、触媒担体にRhを担持させた。こうして得られたRhを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で650℃で2.0時間焼成し、触媒を得た。 Next, an aqueous solution of rhodium acetate (Rh (CH 3 COO) 3 ) containing 0.3 wt% Rh was added to the obtained catalyst carrier in an amount of 0.15 cc (1 of the water absorption amount of the catalyst carrier). (0.times.) And Rh was supported on the catalyst carrier. The catalyst carrier carrying Rh thus obtained was dried in an oven at 120 ° C. for 2.5 hours in air and then calcined in an electric furnace at 650 ° C. for 2.0 hours in air to obtain a catalyst.
得られた触媒は、Rhを触媒に対し450wtppmの割合で含有するもので、そのBET比表面積は0.12m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Rhは触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内の領域に存在していた。よって、該Rhの近傍にCaOが存在していた。 The obtained catalyst contained Rh at a ratio of 450 wtppm with respect to the catalyst, and its BET specific surface area was 0.12 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Rh was present in a region close to the surface of the catalyst particles, that is, a region within 10% of the depth from the catalyst surface. Therefore, CaO was present in the vicinity of the Rh.
<反応例4>
実施例4で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのH2O/CO2リフォーミング試験を実施した。
<Reaction Example 4>
A reactor similar to that used in Example 1 was charged with 50 cc of the catalyst prepared in Example 4, and a methane H 2 O / CO 2 reforming test was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/0)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度850℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/0) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction process was performed by making it contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is prepared by using a gas pressure of 1960 kPaG at the outlet of the catalyst layer, a gas temperature of 850 ° C. at the outlet of the catalyst layer, and GHSV of methane reference = 2. The treatment was performed at 500 / hour.
この結果、反応開始から5時間経過後のCH4転化率は54.8%(実験条件下でのCH4の平衡転化率=54.8%)であり、また反応開始から300時間経過後のCH4の転化率は、54.8%、800時間経過後のCH4の転化率は、52.3%であった。また800時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は、上部から順にそれぞれ0.15wt%、0.10wt%、0.05wt%、0.03wt%であった。また、実施例1と同様に、反応例4記載の前処理条件で処理した触媒を分析したところ、粒子状のRhが触媒表面に存在していることが確認された。 As a result, the CH 4 conversion rate after 5 hours from the start of the reaction was 54.8% (equilibrium conversion rate of CH 4 under experimental conditions = 54.8%), and 300 hours after the start of the reaction. The conversion rate of CH 4 was 54.8%, and the conversion rate of CH 4 after 800 hours was 52.3%. Further, after 800 hours, the amount of carbon on the catalyst extracted in four portions in the same manner as in Example 1 was 0.15 wt%, 0.10 wt%, 0.05 wt%, and 0.03 wt% in order from the top. It was. Similarly to Example 1, when the catalyst treated under the pretreatment conditions described in Reaction Example 4 was analyzed, it was confirmed that particulate Rh was present on the catalyst surface.
<実施例5>
内部にCaOをCa換算で0.3wt%含有する純度98.7wt%以上のMgOの粉末に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1200℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.08m2/gであった。
<Example 5>
Inside, MgO powder containing 0.3 wt% of CaO in terms of Ca and having a purity of 98.7 wt% or more is mixed with 3.0 wt% of carbon as MgO powder as a lubricant, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1200 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.08 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.3wt%含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子は原料酸化マグネシウム粒子よりも顕著に大きかった。したがって、原料MgO粒子が凝集してMgO粒子を形成し、且つ、原料MgO粒子が含有するCaOがMgO粒子表面に析出したと考えられる。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the catalyst support contained 0.3 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. Further, the MgO particles constituting the obtained catalyst carrier were significantly larger than the raw material magnesium oxide particles. Therefore, it is considered that the raw material MgO particles aggregate to form MgO particles, and CaO contained in the raw material MgO particles is precipitated on the surface of the MgO particles.
得られた触媒担体は、実施例1と同様に粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で37.5mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst support was in the same particle form as in Example 1, a part of the surface of the MgO particles was covered with a layer containing CaO, and CaO was present in the recesses on the surface of the MgO particles. . Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the amount of CaO present on the surface of the MgO particles was determined, it was 37.5 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、0.85wt%のRuを含む硝酸ニトロシルルテニウム水溶液を触媒担体1.0gに対し0.13cc(触媒担体の吸水量の1.0倍)にて噴霧し、触媒担体にRuを担持させた。こうして得られたRuを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で400℃で2.0時間焼成し、触媒を得た。 Next, an aqueous solution of nitrosylruthenium nitrate containing 0.85 wt% Ru is sprayed onto the obtained catalyst carrier at 0.13 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, Ru was supported on the catalyst support. The Ru-supported catalyst support thus obtained was dried in an oven at 120 ° C. for 2.5 hours in the air, and then calcined in the electric furnace at 400 ° C. for 2.0 hours in the air to obtain a catalyst.
得られた触媒は、Ruを触媒に対し1100wtppmの割合で含有するもので、そのBET比表面積は0.08m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Ruは触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内の領域に存在していた。よって、該Ruの近傍にCaOが存在しているといえる。 The obtained catalyst contained Ru at a rate of 1100 wtppm with respect to the catalyst, and its BET specific surface area was 0.08 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Ru was present in a region close to the surface of the catalyst particles, that is, a region within 10% of the depth from the catalyst surface. Therefore, it can be said that CaO exists in the vicinity of the Ru.
<反応例5>
実施例5で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Reaction Example 5>
50 cc of the catalyst prepared in Example 5 was charged into a reactor similar to that used in Example 1, and a CO 2 reforming test for methane was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/3)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/3) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction process was performed by making it contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is converted into a catalyst layer outlet gas pressure of 1960 kPaG, a catalyst layer outlet gas temperature of 880 ° C., methane-based GHSV = 2, The treatment was performed at 500 / hour.
この結果、反応開始から5時間経過後のCH4転化率は54.8%(実験条件下でのCH4の平衡転化率=54.8%)であり、また反応開始から300時間経過後のCH4の転化率は、54.8%、700時間経過後のCH4の転化率は、53.5%であった。また700時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は、上部から順にそれぞれ0.15wt%、0.04wt%、0.03wt%、0.01wt%であった。また、実施例1と同様に、反応例5記載の前処理条件で処理した触媒を分析したところ、粒子状のRuが触媒表面に存在していることが確認された。 As a result, the CH 4 conversion rate after 5 hours from the start of the reaction was 54.8% (equilibrium conversion rate of CH 4 under experimental conditions = 54.8%), and 300 hours after the start of the reaction. The conversion rate of CH 4 was 54.8%, and the conversion rate of CH 4 after 700 hours was 53.5%. Further, after 700 hours, the amounts of carbon on the catalyst extracted by dividing into 4 parts as in Example 1 were 0.15 wt%, 0.04 wt%, 0.03 wt%, and 0.01 wt%, respectively, from the top. It was. Further, as in Example 1, the catalyst treated under the pretreatment conditions described in Reaction Example 5 was analyzed, and it was confirmed that particulate Ru was present on the catalyst surface.
<実施例6>
内部にCaOをCa換算で0.3wt%含有する純度98.7wt%以上のMgOの粉末に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1130℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.15m2/gであった。
<Example 6>
Inside, MgO powder containing 0.3 wt% of CaO in terms of Ca and having a purity of 98.7 wt% or more is mixed with 3.0 wt% of carbon as MgO powder as a lubricant, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1130 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.15 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.3wt%含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子は原料酸化マグネシウム粒子よりも顕著に大きかった。したがって、原料MgO粒子が凝集してMgO粒子を形成し、且つ、原料MgO粒子が含有するCaOがMgO粒子表面に析出したと考えられる。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the catalyst support contained 0.3 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. Further, the MgO particles constituting the obtained catalyst carrier were significantly larger than the raw material magnesium oxide particles. Therefore, it is considered that the raw material MgO particles aggregate to form MgO particles, and CaO contained in the raw material MgO particles is precipitated on the surface of the MgO particles.
得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で20mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst carrier is in the form of particles, as in Example 1. Part of the surface of the MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of the MgO particles. It was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the amount of CaO present on the surface of the MgO particles was determined, it was 20 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、0.6wt%のRuを含む硝酸ルテニウム水溶液を、触媒担体1.0gに対し0.18cc(触媒担体の吸水量の1.2倍)にて噴霧し、触媒担体にRuを担持させた。こうして得られたRuを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で400℃で2.0時間焼成し、触媒を得た。 Next, an aqueous ruthenium nitrate solution containing 0.6 wt% Ru is sprayed on the obtained catalyst carrier at 0.18 cc (1.2 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, Ru was supported on the catalyst support. The Ru-supported catalyst support thus obtained was dried in an oven at 120 ° C. for 2.5 hours in the air, and then calcined in the electric furnace at 400 ° C. for 2.0 hours in the air to obtain a catalyst.
得られた触媒は、Ruを触媒に対し780wtppmの割合で含有するもので、そのBET比表面積は0.15m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Ruは触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内の領域に存在していた。よって、該Ruの近傍にCaOが存在していといえる。 The obtained catalyst contained Ru at a ratio of 780 wtppm with respect to the catalyst, and its BET specific surface area was 0.15 m 2 / g. Further, when the obtained catalyst was subjected to EPMA analysis in the same manner as in Example 1, Ru was present in a region close to the surface of the catalyst particles, that is, a region within 10% of the depth from the catalyst surface. Therefore, it can be said that CaO exists in the vicinity of the Ru.
<反応例6>
実施例6で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのH2O/CO2リフォーミング試験を実施した。
<Reaction example 6>
A reactor similar to that used in Example 1 was charged with 50 cc of the catalyst prepared in Example 6, and an H 2 O / CO 2 reforming test for methane was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/2)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させて、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:0.4:1の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/2) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction treatment was carried out by contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 0.4: 1 is used, the gas pressure at the catalyst layer outlet is 1960 kPaG, the gas temperature at the catalyst layer outlet is 880 ° C., the methane reference GHSV = The treatment was performed at 2,500 / hour.
この結果、反応開始から5時間経過後のCH4転化率は66.7%(実験条件下でのCH4の平衡転化率=66.7%)であり、また反応開始から13000時間経過後のCH4の転化率は、66.7%であった。また13000時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部からそれぞれ0.11wt%、0.05wt%、0.03wt%、0.01wt%であった。また、実施例1と同様に、反応例6記載の前処理条件で処理した触媒を分析したところ、粒子状のRuが触媒表面に存在していることが確認された。 As a result, the CH 4 conversion after 5 hours from the start of the reaction was 66.7% (equilibrium conversion of CH 4 under the experimental conditions = 66.7%), and after 13,000 hours from the start of the reaction. The conversion rate of CH 4 was 66.7%. Further, after 13000 hours had passed, the amount of carbon on the catalyst extracted in four portions in the same manner as in Example 1 was 0.11 wt%, 0.05 wt%, 0.03 wt%, and 0.01 wt%, respectively, from the top. Similarly to Example 1, when the catalyst treated under the pretreatment conditions described in Reaction Example 6 was analyzed, it was confirmed that particulate Ru was present on the catalyst surface.
<実施例7>
CaO含有量がCa換算で0.001wt%以下で純度99.9wt%以上のMgOの粉末を80℃にて煮沸攪拌しMg(OH)2とする際に、同時にCa(OH)2水溶液を滴下攪拌することでCa添加型Mg(OH)2粒子を得た。この添加体に滑択材として3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを更に空気中で1180℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.10m2/gであった。
<Example 7>
When an MgO powder having a CaO content of 0.001 wt% or less in terms of Ca and having a purity of 99.9 wt% or more is boiled and stirred at 80 ° C. to obtain Mg (OH) 2 , a Ca (OH) 2 aqueous solution is dropped simultaneously. By stirring, Ca-added Mg (OH) 2 particles were obtained. This additive was mixed with 3.0 wt% carbon as a sliding material to form a cylindrical pellet having a diameter of 1/4 inch. The formed pellets were further calcined in air at 1180 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.10 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.5wt%含有していた。なお、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子に表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子はCa添加型Mg(OH)2粒子よりも顕著に大きかった。したがって、Ca添加型Mg(OH)2粒子が凝集してMgO粒子を形成し、且つ、Ca添加型Mg(OH)2粒子が含有するCaOがMgO粒子表面に析出したと考えられる。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the catalyst support contained 0.5 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support, and Ca was present only in the vicinity of the surface of the MgO particles. In addition, the MgO particles constituting the obtained catalyst support were significantly larger than the Ca-added Mg (OH) 2 particles. Therefore, it is considered that Ca-added Mg (OH) 2 particles aggregate to form MgO particles, and CaO contained in the Ca-added Mg (OH) 2 particles is precipitated on the surface of the MgO particles.
得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内の領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で50mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst carrier is in the form of particles, as in Example 1. Part of the surface of the MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of the MgO particles. It was. Further, these CaOs existed in a region within 10% depth from the surface of the catalyst support. And when the amount of CaO present on the surface of the MgO particles was determined, it was 50 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、0.8wt%のRuを含む硝酸ルテニウム水溶液を、触媒担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)にて噴霧しRuを担持した触媒担体を得た。こうして得られたRuを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で400℃で2.0時間焼成し、触媒を得た。
得られた触媒は、Ruを触媒に対し1000wtppmの割合で含有するもので、BET比表面積は0.10m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Ruは触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内の領域に存在していた。よって、該Ruの近傍にCaOが存在しているといえる。
Next, an aqueous ruthenium nitrate solution containing 0.8 wt% Ru is sprayed on the obtained catalyst carrier at 0.15 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier. As a result, a catalyst carrier carrying a catalyst was obtained. The Ru-supported catalyst support thus obtained was dried in an oven at 120 ° C. for 2.5 hours in the air, and then calcined in the electric furnace at 400 ° C. for 2.0 hours in the air to obtain a catalyst.
The obtained catalyst contained Ru at a ratio of 1000 wtppm with respect to the catalyst, and the BET specific surface area was 0.10 m 2 / g. Further, when the obtained catalyst was subjected to EPMA analysis in the same manner as in Example 1, Ru was present in a region close to the surface of the catalyst particles, that is, a region within 10% of the depth from the catalyst surface. Therefore, it can be said that CaO exists in the vicinity of the Ru.
<反応例7>
実施例7で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのH2O/CO2リフォーミング試験を実施した。
<Reaction Example 7>
A reactor similar to that used in Example 1 was charged with 50 cc of the catalyst prepared in Example 7, and an H 2 O / CO 2 reforming test for methane was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/1)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:0.4:1の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/1) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction process was performed by making it contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 0.4: 1 is used, the gas pressure at the catalyst layer outlet is 1960 kPaG, the gas temperature at the catalyst layer outlet is 880 ° C., the methane reference GHSV = The treatment was performed at 2,500 / hour.
この結果、反応開始から5時間経過後のCH4転化率は66.7%(実験条件下でのCH4の平衡転化率=66.7%)であり、また反応開始から13000時間経過後のCH4の転化率は、66.7%であった。また13000時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部からそれぞれ0.15wt%、0.08wt%、0.05wt%、0.01wt%であった。また、実施例1と同様に、反応例7記載の前処理条件で処理した触媒を分析したところ、粒子状のRuが触媒表面に存在していることが確認された。 As a result, the CH 4 conversion after 5 hours from the start of the reaction was 66.7% (equilibrium conversion of CH 4 under the experimental conditions = 66.7%), and after 13,000 hours from the start of the reaction. The conversion rate of CH 4 was 66.7%. Further, after 13000 hours had elapsed, the amount of carbon on the catalyst extracted in four portions in the same manner as in Example 1 was 0.15 wt%, 0.08 wt%, 0.05 wt%, and 0.01 wt%, respectively, from the top. Similarly to Example 1, when the catalyst treated under the pretreatment conditions described in Reaction Example 7 was analyzed, it was confirmed that particulate Ru was present on the catalyst surface.
<実施例8>
CaO含有量がCa換算で0.01wt%以下で純度99.9wt%以上のMgOの粉末を100℃にて煮沸攪拌してMg(OH)2とする際に、同時にCa(OH)2水溶液を滴下攪拌することでCa添加型Mg(OH)2粒子を得た。この添加体に滑択材として3.0wt%のカーボンを混合し、直径1/4インチのペレットを形成した。形成したペレットを更に空気中で1180℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.10m2/gであった。
<Example 8>
When an MgO powder having a CaO content of 0.01 wt% or less in terms of Ca and having a purity of 99.9 wt% or more is boiled and stirred at 100 ° C. to obtain Mg (OH) 2 , the Ca (OH) 2 aqueous solution is simultaneously added. Ca-added Mg (OH) 2 particles were obtained by dropping and stirring. This additive was mixed with 3.0 wt% carbon as a sliding material to form a 1/4 inch diameter pellet. The formed pellets were further calcined in air at 1180 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.10 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で1.4wt%含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子はCa添加型Mg(OH)2粒子よりも顕著に大きかった。したがって、Ca添加型Mg(OH)2粒子が凝集してMgO粒子を形成し、且つ、Ca添加型Mg(OH)2粒子が含有するCaOがMgO粒子表面に析出したと考えられる。
得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で140mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。
The obtained catalyst support was analyzed by ICP in the same manner as in Example 1. As a result, the catalyst support contained 1.4 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. In addition, the MgO particles constituting the obtained catalyst support were significantly larger than the Ca-added Mg (OH) 2 particles. Therefore, it is considered that Ca-added Mg (OH) 2 particles aggregate to form MgO particles, and CaO contained in the Ca-added Mg (OH) 2 particles is precipitated on the surface of the MgO particles.
The obtained catalyst carrier is in the form of particles, as in Example 1. Part of the surface of the MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of the MgO particles. It was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the amount of CaO present on the surface of the MgO particles was determined, it was 140 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、0.7wt%のRuを含む硝酸ルテニウム水溶液を、触媒担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)にて噴霧し、触媒担体にRuを担持させた。こうして得られたRuを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で400℃で2.0時間焼成し、触媒を得た。 Next, an aqueous ruthenium nitrate solution containing 0.7 wt% Ru is sprayed onto the obtained catalyst carrier at 0.15 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, Ru was supported on the catalyst support. The Ru-supported catalyst support thus obtained was dried in an oven at 120 ° C. for 2.5 hours in the air, and then calcined in the electric furnace at 400 ° C. for 2.0 hours in the air to obtain a catalyst.
得られた触媒は、Ruを触媒に対し910wtppmの割合で含有するもので、BET比表面積は0.10m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、触媒粒子の表面にRuが担持されていた。そして、Ruは触媒表面から深さ10%以内の領域に存在していた。よって、該Ruの近傍にCaOが存在しているといえる。 The obtained catalyst contained Ru at a ratio of 910 wtppm with respect to the catalyst, and the BET specific surface area was 0.10 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Ru was supported on the surfaces of the catalyst particles. Ru was present in a region within 10% depth from the catalyst surface. Therefore, it can be said that CaO exists in the vicinity of the Ru.
<反応例8>
実施例8で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのH2O/CO2リフォーミング試験を実施した。
<Reaction Example 8>
A reactor similar to that used in Example 1 was charged with 50 cc of the catalyst prepared in Example 8, and a methane H 2 O / CO 2 reforming test was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/1)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:0.4:1の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/1) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction process was performed by making it contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 0.4: 1 is used, the gas pressure at the catalyst layer outlet is 1960 kPaG, the gas temperature at the catalyst layer outlet is 880 ° C., the methane reference GHSV = The treatment was performed at 2,500 / hour.
この結果、反応開始から5時間経過後のCH4転化率は66.7%(実験条件下でのCH4の平衡転化率=66.7%)であり、また反応開始から9000時間経過後のCH4の転化率は、66.7%であった。また9000時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部からそれぞれ0.21wt%、0.15wt%、0.08wt%、0.01wt%であった。また、実施例1と同様に、反応例8記載の前処理条件で処理した触媒を分析したところ、粒子状のRuが触媒表面に存在していることが確認された。 As a result, the CH 4 conversion after 5 hours from the start of the reaction was 66.7% (equilibrium conversion of CH 4 under the experimental conditions = 66.7%), and after 9000 hours from the start of the reaction. The conversion rate of CH 4 was 66.7%. Further, after 9000 hours had passed, the amount of carbon on the catalyst extracted by dividing into 4 parts in the same manner as in Example 1 was 0.21 wt%, 0.15 wt%, 0.08 wt%, and 0.01 wt%, respectively, from the top. Further, as in Example 1, the catalyst treated under the pretreatment conditions described in Reaction Example 8 was analyzed, and it was confirmed that particulate Ru was present on the catalyst surface.
<実施例9>
内部にCaOをCa換算で0.3wt%含有する純度98.7wt%以上のMgOの粉末に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1150℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.12m2/gであった。
<Example 9>
Inside, MgO powder containing 0.3 wt% of CaO in terms of Ca and having a purity of 98.7 wt% or more is mixed with 3.0 wt% of carbon as MgO powder as a lubricant, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1150 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.12 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.3wt%のCaを含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子は原料酸化マグネシウム粒子よりも顕著に大きかった。したがって、原料MgO粒子が凝集してMgO粒子を形成し、且つ、原料MgO粒子が含有するCaOがMgO粒子表面に析出したと考えられる。また、得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内の領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で25mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst support was analyzed by ICP in the same manner as in Example 1. As a result, the catalyst support contained 0.3 wt% Ca in terms of CaO. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. Further, the MgO particles constituting the obtained catalyst carrier were significantly larger than the raw material magnesium oxide particles. Therefore, it is considered that the raw material MgO particles aggregate to form MgO particles, and CaO contained in the raw material MgO particles is precipitated on the surface of the MgO particles. The obtained catalyst carrier is in the form of particles as in Example 1, a part of the surface of MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of MgO particles. Was. Further, these CaOs existed in a region within 10% depth from the surface of the catalyst support. And when the amount of CaO present on the surface of the MgO particles was determined, it was 25 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に0.81wt%のRhを含む酢酸ロジウム水溶液を、触媒担体1.0gに対し0.17cc(触媒担体の吸水量の1.1倍)にて噴霧しRhを担持した触媒担体を得た。こうして得られたRhを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で650℃で2.0時間焼成し、触媒を得た。 Next, an aqueous rhodium acetate solution containing 0.81 wt% Rh was sprayed on the obtained catalyst carrier at 0.17 cc (1.1 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, and Rh was A supported catalyst carrier was obtained. The catalyst carrier carrying Rh thus obtained was dried in an oven at 120 ° C. for 2.5 hours in air and then calcined in an electric furnace at 650 ° C. for 2.0 hours in air to obtain a catalyst.
得られた触媒は、Rhを触媒に対し1350pmの割合で含有するもので、そのBET比表面積は0.12m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Rhは触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内に存在していた。よって、該Rhの近傍にCaOが存在していると考えられる。 The obtained catalyst contained Rh at a ratio of 1350 pm with respect to the catalyst, and its BET specific surface area was 0.12 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Rh was present in a region near the surface of the catalyst particles, that is, within a depth of 10% from the catalyst surface. Therefore, it is considered that CaO exists in the vicinity of the Rh.
<反応例9>
実施例9で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのH2O/CO2リフォーミング試験を実施した。
<Reaction Example 9>
A reactor similar to that used in Example 1 was charged with 50 cc of the catalyst prepared in Example 9, and a methane H 2 O / CO 2 reforming test was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/0)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:0.4:1の原料ガスを、圧力1960kPaG,温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/0) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction process was performed by making it contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 0.4: 1 was treated under the conditions of a pressure of 1960 kPaG, a temperature of 880 ° C., and a methane standard GHSV = 2500 / hour. .
この結果、反応開始から5時間経過後のCH4転化率は66.7%(実験条件下でのCH4の平衡転化率=66.7%)であり、また反応開始から8000時間経過後のCH4の転化率は、66.7%であった。また8000時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ0.15wt%、0.07wt%、0.05wt%、0.01wt%であった。また、実施例1と同様に、反応例9記載の前処理条件で処理した触媒を分析したところ、粒子状のRhが触媒表面に存在していることが確認された。 As a result, the CH 4 conversion after 5 hours from the start of the reaction was 66.7% (equilibrium conversion of CH 4 under experimental conditions = 66.7%), and after 8000 hours from the start of the reaction. The conversion rate of CH 4 was 66.7%. Further, after 8000 hours, the amounts of carbon on the catalyst extracted by dividing into 4 parts in the same manner as in Example 1 were 0.15 wt%, 0.07 wt%, 0.05 wt%, and 0.01 wt%, respectively, from the top. . Similarly to Example 1, when the catalyst treated under the pretreatment conditions described in Reaction Example 9 was analyzed, it was confirmed that particulate Rh was present on the catalyst surface.
<実施例10>
CaO含有量がCa換算で0.001wt%以下で純度99.9wt%以上のMgOの粉末を100℃にて煮沸攪拌しMg(OH)2とする際に、同時にCa(OH)2水溶液を滴下攪拌することでCa添加型Mg(OH)2粒子を得た。この添加体に滑択材として3.0wt%のカーボンを混合し、直径1/4インチのペレットを形成した。形成したペレットを更に空気中で1180℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.10m2/gであった。
<Example 10>
When an MgO powder having a CaO content of 0.001 wt% or less in terms of Ca and having a purity of 99.9 wt% or more is boiled and stirred at 100 ° C. to make Mg (OH) 2 , a Ca (OH) 2 aqueous solution is dropped simultaneously. By stirring, Ca-added Mg (OH) 2 particles were obtained. This additive was mixed with 3.0 wt% carbon as a sliding material to form a 1/4 inch diameter pellet. The formed pellets were further calcined in air at 1180 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.10 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.01wt%含有していた。なお、EPMA分析結果から、触媒担体の内部にCaが存在せず、CaはMgO粒子表面のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子はCa添加型Mg(OH)2粒子よりも顕著に大きかった。したがって、Ca添加型Mg(OH)2粒子が凝集してMgO粒子を形成し、且つ、Ca添加型Mg(OH)2粒子が含有するCaOがMgO粒子表面に析出したと考えられる。また、得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で1mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst support was analyzed by ICP in the same manner as in Example 1. As a result, the catalyst support contained 0.01 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only on the MgO particle surface. In addition, the MgO particles constituting the obtained catalyst support were significantly larger than the Ca-added Mg (OH) 2 particles. Therefore, it is considered that Ca-added Mg (OH) 2 particles aggregate to form MgO particles, and CaO contained in the Ca-added Mg (OH) 2 particles is precipitated on the surface of the MgO particles. The obtained catalyst carrier is in the form of particles as in Example 1, a part of the surface of MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of MgO particles. Was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the amount of CaO present on the MgO particle surface was determined, it was 1 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、0.6wt%のRuを含む硝酸ルテニウム水溶液を、触媒担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)にて噴霧しRuを担持した触媒担体を得た。 Next, an aqueous ruthenium nitrate solution containing 0.6 wt% Ru is sprayed on the obtained catalyst carrier at 0.15 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier. As a result, a catalyst carrier carrying a catalyst was obtained.
次に、得られたRuを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で400℃で2.0時間焼成し、触媒を得た。 Next, the obtained catalyst support carrying Ru was dried in an oven at 120 ° C. for 2.5 hours in air, and then calcined in an electric furnace at 400 ° C. for 2.0 hours in air to obtain a catalyst.
得られた触媒は、Ruを触媒に対し780wtppmの割合で含有するもので、BET比表面積は0.10m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、触媒粒子の表面にRuが担持されていた。そして、Ruは触媒表面から深さ10%以内の領域に存在していた。よって、該Ruの近傍にCaOが存在していると考えられる。 The obtained catalyst contained Ru at a ratio of 780 wtppm with respect to the catalyst, and the BET specific surface area was 0.10 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Ru was supported on the surfaces of the catalyst particles. Ru was present in a region within 10% depth from the catalyst surface. Therefore, it is considered that CaO exists in the vicinity of the Ru.
<反応例10>
実施例10で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのH2O/CO2リフォーミング試験を実施した。
<Reaction Example 10>
A reactor similar to that used in Example 1 was charged with 50 cc of the catalyst prepared in Example 10, and an H 2 O / CO 2 reforming test for methane was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/1)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:0.4:1の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/1) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction process was performed by making it contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 0.4: 1 is used, the gas pressure at the catalyst layer outlet is 1960 kPaG, the gas temperature at the catalyst layer outlet is 880 ° C., the methane reference GHSV = The treatment was performed at 2,500 / hour.
この結果、反応開始から5時間経過後のCH4転化率は66.7%(実験条件下でのCH4の平衡転化率=66.7%)であり、また反応開始から5000時間経過後のCH4の転化率は、66.7%であった。また5000時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部からそれぞれ0.28wt%、0.17wt%、0.09wt%、0.01wt%であった。また、実施例1と同様に、反応例10記載の前処理条件で処理した触媒を分析したところ、粒子状のRuが触媒表面に存在していることが確認された。 As a result, the CH 4 conversion rate after 5 hours from the start of the reaction was 66.7% (equilibrium conversion rate of CH 4 under experimental conditions = 66.7%), and 5000 hours after the start of the reaction. The conversion rate of CH 4 was 66.7%. Further, after 5000 hours, the amount of carbon on the catalyst extracted by dividing into 4 parts in the same manner as in Example 1 was 0.28 wt%, 0.17 wt%, 0.09 wt%, and 0.01 wt% from the top, respectively. Similarly to Example 1, when the catalyst treated under the pretreatment conditions described in Reaction Example 10 was analyzed, it was confirmed that particulate Ru was present on the catalyst surface.
<実施例11>
内部にCaOをCa換算で0.3wt%含有する純度98.7wt%以上のMgOの粉末に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1100℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.20m2/gであった。
<Example 11>
Inside, MgO powder containing 0.3 wt% of CaO in terms of Ca and having a purity of 98.7 wt% or more is mixed with 3.0 wt% of carbon as MgO powder as a lubricant, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1100 ° C. for 3 hours to obtain a catalyst carrier. The resulting catalyst support had a BET specific surface area of 0.20 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.3wt%含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子は原料酸化マグネシウム粒子よりも顕著に大きかった。したがって、原料MgO粒子が凝集してMgO粒子を形成し、且つ、原料MgO粒子が含有するCaOがMgO粒子表面に析出したと考えられる。また、得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で15mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the catalyst support contained 0.3 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. Further, the MgO particles constituting the obtained catalyst carrier were significantly larger than the raw material magnesium oxide particles. Therefore, it is considered that the raw material MgO particles aggregate to form MgO particles, and CaO contained in the raw material MgO particles is precipitated on the surface of the MgO particles. The obtained catalyst carrier is in the form of particles as in Example 1, a part of the surface of MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of MgO particles. Was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the abundance of CaO on the MgO particle surface was determined, it was 15 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、8.0wt%のNiを含む硝酸ニッケル水和物水溶液を、触媒担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)にて噴霧し、触媒担体にNiを担持させた。こうして得られたNiを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で650℃で2.0時間焼成し、触媒を得た。 Next, a nickel nitrate hydrate aqueous solution containing 8.0 wt% Ni is added to the obtained catalyst carrier at 0.15 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier. It sprayed and Ni was carry | supported on the catalyst support | carrier. The catalyst carrier carrying Ni thus obtained was dried in air at 120 ° C. for 2.5 hours in the air, and then calcined in air in an electric furnace at 650 ° C. for 2.0 hours to obtain a catalyst.
得られた触媒は、Niを触媒に対し10000wtppmの割合で含有するもので、そのBET比表面積は0.20m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Niは触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内の領域にCaとNiが存在していた。 The obtained catalyst contained Ni at a rate of 10,000 wtppm with respect to the catalyst, and its BET specific surface area was 0.20 m 2 / g. Further, when the obtained catalyst was subjected to EPMA analysis in the same manner as in Example 1, Ni and Ca were present in a region close to the surface of the catalyst particles, that is, a region within 10% of the depth from the catalyst surface.
<実施例12>
内部にCaOをCa換算で0.3wt%含有する純度98.7wt%以上のMgOの粉末に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1100℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.10m2/gであった。
<Example 12>
Inside, MgO powder containing 0.3 wt% of CaO in terms of Ca and having a purity of 98.7 wt% or more is mixed with 3.0 wt% of carbon as MgO powder as a lubricant, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1100 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.10 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.3wt%含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子は原料酸化マグネシウム粒子よりも顕著に大きかった。したがって、原料MgO粒子が凝集してMgO粒子を形成し、且つ、原料MgO粒子が含有するCaOがMgO粒子表面に析出したと考えられる。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the catalyst support contained 0.3 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. Further, the MgO particles constituting the obtained catalyst carrier were significantly larger than the raw material magnesium oxide particles. Therefore, it is considered that the raw material MgO particles aggregate to form MgO particles, and CaO contained in the raw material MgO particles is precipitated on the surface of the MgO particles.
得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で15mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst carrier is in the form of particles, as in Example 1. Part of the surface of the MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of the MgO particles. It was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the abundance of CaO on the MgO particle surface was determined, it was 15 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、2.7wt%のIrを含む塩化イリジウム水溶液を、触媒担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)にて噴霧し、触媒担体にIrを担持させた。こうして得られたIrを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で650℃で2.0時間焼成し、触媒を得た。 Next, an iridium chloride aqueous solution containing 2.7 wt% of Ir is sprayed on the obtained catalyst carrier at 0.15 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, Ir was supported on the catalyst support. The catalyst carrier loaded with Ir thus obtained was dried in air at 120 ° C. for 2.5 hours in air, and then calcined in air in an electric furnace at 650 ° C. for 2.0 hours to obtain a catalyst.
得られた触媒は、Irを触媒に対し3500wtppmの割合で含有するもので、そのBET比表面積は0.20m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、CaとIrが触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内の領域に存在していた。 The obtained catalyst contained Ir at a ratio of 3500 wtppm with respect to the catalyst, and its BET specific surface area was 0.20 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Ca and Ir were present in a region close to the surface of the catalyst particles, that is, in a region within 10% of the depth from the catalyst surface.
<実施例13>
内部にCaOをCa換算で0.3wt%含有する純度98.7wt%以上のMgOの粉末に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1100℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.20m2/gであった。
<Example 13>
Inside, MgO powder containing 0.3 wt% of CaO in terms of Ca and having a purity of 98.7 wt% or more is mixed with 3.0 wt% of carbon as MgO powder as a lubricant, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1100 ° C. for 3 hours to obtain a catalyst carrier. The resulting catalyst support had a BET specific surface area of 0.20 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.3wt%含有していた。また、EPMA分析結果から、触媒担体の内部にはCaが存在せず、CaはMgO粒子の表面近傍のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子は原料酸化マグネシウム粒子よりも顕著に大きかった。したがって、原料MgO粒子が凝集してMgO粒子を形成し、且つ、原料MgO粒子が含有するCaOがMgO粒子表面に析出したと考えられる。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the catalyst support contained 0.3 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only in the vicinity of the surface of the MgO particles. Further, the MgO particles constituting the obtained catalyst carrier were significantly larger than the raw material magnesium oxide particles. Therefore, it is considered that the raw material MgO particles aggregate to form MgO particles, and CaO contained in the raw material MgO particles is precipitated on the surface of the MgO particles.
得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で15mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst carrier is in the form of particles, as in Example 1. Part of the surface of the MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of the MgO particles. It was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the abundance of CaO on the MgO particle surface was determined, it was 15 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、1.6wt%のOsを含む酸化オスミウム水溶液を、触媒担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍質量)にて噴霧し、触媒担体にOsを担持させた。こうして得られたOsを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で650℃で2.0時間焼成し、触媒を得た。 Next, an osmium oxide aqueous solution containing 1.6 wt% Os is sprayed on the obtained catalyst carrier at 0.15 cc (1.0 times the amount of water absorbed by the catalyst carrier) with respect to 1.0 g of the catalyst carrier. Then, Os was supported on the catalyst carrier. The catalyst carrier carrying Os thus obtained was dried in an oven at 120 ° C. for 2.5 hours in air and then calcined in an electric furnace at 650 ° C. for 2.0 hours in air to obtain a catalyst.
得られた触媒は、Osを触媒に対し3500wtppmの割合で含有するもので、そのBET比表面積は0.20m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、CaとOsが触媒粒子の表面に近い領域、すなわち触媒表面から深さ10%以内の領域に存在していた。 The obtained catalyst contained Os at a ratio of 3500 wtppm with respect to the catalyst, and its BET specific surface area was 0.20 m 2 / g. Further, when the obtained catalyst was subjected to EPMA analysis in the same manner as in Example 1, Ca and Os were present in a region close to the surface of the catalyst particles, that is, a region within 10% of the depth from the catalyst surface.
<比較例1>
内部にCaOをCa換算で0.3wt%含有する純度98.7wt%以上のMgOの粉末に、滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状ペレットを形成した。形成したペレットを空気中で600℃で3時間焼成し、触媒担体を得た。
<Comparative Example 1>
Inside, MgO powder containing 0.3 wt% of CaO in terms of Ca and having a purity of 98.7 wt% or more is mixed with 3.0 wt% of carbon as MgO powder as a lubricant, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 600 ° C. for 3 hours to obtain a catalyst carrier.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.3wt%含有していた。触媒担体の断面のEPMA分析結果を図7に示す。得られた触媒担体は、図7に示すように、粒子状であり、CaOはMgO粒子内部に均一に分布しており、MgO粒子表面への析出は確認されず、CaOはMgO表面に存在しなかった。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the catalyst support contained 0.3 wt% of CaO in terms of Ca. The EPMA analysis result of the cross section of the catalyst carrier is shown in FIG. As shown in FIG. 7, the obtained catalyst support is in the form of particles, CaO is uniformly distributed inside the MgO particles, precipitation on the MgO particle surface is not confirmed, and CaO exists on the MgO surface. There wasn't.
次に、得られた触媒担体に、3.9wt%のRhを含む酢酸ロジウム水溶液を、触媒担体1.0gに対し0.39cc(触媒担体の吸水量の1.1倍)にて噴霧し、Rhを担持した触媒担体を得た。こうして得られたRhを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で950℃で2.0時間焼成し、触媒を得た。 Next, an aqueous rhodium acetate solution containing 3.9 wt% Rh was sprayed onto the obtained catalyst carrier at 0.39 cc (1.1 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, A catalyst carrier carrying Rh was obtained. The catalyst carrier carrying Rh thus obtained was dried in an oven at 120 ° C. for 2.5 hours in air and then calcined in an electric furnace at 950 ° C. for 2.0 hours in air to obtain a catalyst.
得られた触媒は、Rhを触媒に対し15000pmの割合で含有するもので、そのBET比表面積は32.0m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、触媒粒子の表面にRhが担持されていた。そして、Rhは触媒表面から深さ10%以内に存在していた。そして、CaはMgO粒子内部に均一に分布しており、表面への析出は確認されず、表面にCaO含有層は存在しなかった。なお、Rh近傍にCaは存在していなかった。 The obtained catalyst contained Rh at a ratio of 15000 pm with respect to the catalyst, and its BET specific surface area was 32.0 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Rh was supported on the surfaces of the catalyst particles. Rh was present within a depth of 10% from the catalyst surface. And Ca was uniformly distributed inside the MgO particles, no precipitation on the surface was confirmed, and no CaO-containing layer was present on the surface. Ca was not present in the vicinity of Rh.
<比較反応例1>
比較例2で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 1>
The same reactor used in Example 1 was charged with 50 cc of the catalyst prepared in Comparative Example 2, and a CO 2 reforming test for methane was performed.
具体的にはまず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/3)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。反応開始から5時間経過後のCH4転化率は54.8%(実験条件下でのCH4の平衡転化率=54.8%)、30時間経過後のCH4転化率は47.3%であった。また30時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ3.2wt%、2.3wt%、2.2wt%、2.1wt%であった。また、実施例1と同様に、比較反応例2記載の前処理条件で処理した触媒を分析したところ、Rhの粒子が触媒表面に存在していることが確認された。 Specifically, first, the catalyst is brought into contact with the catalyst by circulating a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/3) in advance at 500 ° C. for 1 hour. The reduction treatment was performed. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is converted into a catalyst layer outlet gas pressure of 1960 kPaG, a catalyst layer outlet gas temperature of 880 ° C., methane-based GHSV = 2, The treatment was performed at 500 / hour. The CH 4 conversion after 5 hours from the start of the reaction was 54.8% (CH 4 equilibrium conversion under experimental conditions = 54.8%), and the CH 4 conversion after 30 hours was 47.3%. Met. Further, after 30 hours, the amount of carbon on the catalyst extracted by dividing into four parts in the same manner as in Example 1 was 3.2 wt%, 2.3 wt%, 2.2 wt%, and 2.1 wt%, respectively, from the top. . Similarly to Example 1, when the catalyst treated under the pretreatment conditions described in Comparative Reaction Example 2 was analyzed, it was confirmed that Rh particles were present on the catalyst surface.
<比較例2>
CaO含有量がCa換算で0.01wt%以下である市販のシリカアルミナ成型体を空気中で950℃で3時間焼成し、触媒担体を得た。得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体のCaO含有量はCa換算で0.01wt%以下であった。また、得られた触媒担体ではCaは表面に存在していなかった。
<Comparative example 2>
A commercially available silica alumina molded body having a CaO content of 0.01 wt% or less in terms of Ca was calcined in air at 950 ° C. for 3 hours to obtain a catalyst carrier. When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the CaO content of the catalyst support was 0.01 wt% or less in terms of Ca. In the obtained catalyst carrier, Ca was not present on the surface.
次に、得られた触媒担体に、0.48wt%のRuを含む硝酸ルテニウム水溶液を、触媒担体1.0gに対し0.58cc(触媒担体の吸水量の1.2倍)にて噴霧し、Ruを担持した触媒担体シリカアルミナを得た。こうして得られたRuを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で950℃で2.0時間焼成し、触媒を得た。 Next, an aqueous ruthenium nitrate solution containing 0.48 wt% Ru is sprayed onto the obtained catalyst carrier at 0.58 cc (1.2 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, A catalyst carrier silica alumina carrying Ru was obtained. The Ru-supported catalyst support thus obtained was dried in an oven at 120 ° C. for 2.5 hours in air, and then calcined in air in an electric furnace at 950 ° C. for 2.0 hours to obtain a catalyst.
得られた触媒は、Ruを触媒に対し850wtppmの割合で含有するもので、そのBET比表面積は24.0m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Ru近傍にCaは存在していなかった。 The obtained catalyst contained Ru at a ratio of 850 wtppm with respect to the catalyst, and its BET specific surface area was 24.0 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Ca was not present in the vicinity of Ru.
<比較反応例2>
比較例2で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 2>
The same reactor used in Example 1 was charged with 50 cc of the catalyst prepared in Comparative Example 2, and a CO 2 reforming test for methane was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/0)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。反応開始から5時間経過後のCH4転化率は35.3%(実験条件下でのCH4の平衡転化率=54.8%)、20時間経過後のCH4転化率は28.2%であった。また20時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ1.8wt%、1.3wt%、0.8wt%、0.5wt%であった。また、実施例1と同様に、比較反応例2記載の前処理条件で処理した触媒を分析したところ、Ruの粒子が触媒表面に存在していることが確認された。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/0) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction process was performed by making it contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is converted into a catalyst layer outlet gas pressure of 1960 kPaG, a catalyst layer outlet gas temperature of 880 ° C., methane-based GHSV = 2, The treatment was performed at 500 / hour. The CH 4 conversion after 5 hours from the start of the reaction was 35.3% (equilibrium conversion of CH 4 under experimental conditions = 54.8%), and the CH 4 conversion after 20 hours was 28.2%. Met. Further, after 20 hours, the amounts of carbon on the catalyst extracted by dividing into four parts in the same manner as in Example 1 were 1.8 wt%, 1.3 wt%, 0.8 wt%, and 0.5 wt%, respectively, from the top. . Similarly to Example 1, when the catalyst treated under the pretreatment conditions described in Comparative Reaction Example 2 was analyzed, it was confirmed that Ru particles were present on the catalyst surface.
<比較例3>
CaO含有量がCa換算で0.01wt%以下である市販のZnO成型体を空気中で950℃で3時間焼成し、触媒担体を得た。得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体のCaO含有量はCa換算で0.01wt%以下であった。また、得られた触媒担体ではCaは表面に存在していなかった。
<Comparative Example 3>
A commercially available ZnO molded body having a CaO content of 0.01 wt% or less in terms of Ca was calcined in air at 950 ° C. for 3 hours to obtain a catalyst carrier. When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the CaO content of the catalyst support was 0.01 wt% or less in terms of Ca. In the obtained catalyst carrier, Ca was not present on the surface.
次に、得られた触媒担体に、0.37wt%のRhを含む酢酸ロジウム水溶液を、触媒担体1.0gに対し0.37cc(触媒担体の吸水量の1.0倍)にて噴霧しRhを担持した触媒担体ZnOを得た。得られたRhを担持した触媒担体のBET比表面積は1.5m2/gであった。また、得られたRhを担持した触媒担体について、実施例1と同様にEPMA分析したところ、Caは表面に偏在していなかった。 Next, an aqueous rhodium acetate solution containing 0.37 wt% Rh is sprayed onto the obtained catalyst carrier at 0.37 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier. As a result, a catalyst carrier ZnO carrying N was obtained. The resulting catalyst carrier carrying Rh had a BET specific surface area of 1.5 m 2 / g. Further, when the obtained catalyst carrier carrying Rh was analyzed by EPMA in the same manner as in Example 1, Ca was not unevenly distributed on the surface.
次に、得られたRhを担持した触媒担体ZnOを空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で950℃で2.0時間焼成し、触媒を得た。得られた触媒は、Rhを触媒に対し900wtppmの割合で含有するもので、そのBET比表面積は1.50m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Rh近傍にCaは存在していなかった。 Next, the obtained catalyst carrier ZnO carrying Rh was dried in air at 120 ° C. for 2.5 hours in the air, and then calcined in air in an electric furnace at 950 ° C. for 2.0 hours to obtain a catalyst. . The obtained catalyst contained Rh at a ratio of 900 wtppm with respect to the catalyst, and its BET specific surface area was 1.50 m 2 / g. Further, when the obtained catalyst was subjected to EPMA analysis in the same manner as in Example 1, Ca was not present in the vicinity of Rh.
<比較反応例3>
比較例3で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 3>
The same reactor used in Example 1 was charged with 50 cc of the catalyst prepared in Comparative Example 3, and a CO 2 reforming test for methane was performed.
具体的にはまず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/2)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比=1:1:0)の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。反応開始から5時間経過後のCH4転化率は15.8%(実験条件下でのCH4の平衡転化率=54.8%)、40時間経過後のCH4転化率は10.2%であった。また40時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ5.5wt%、5.1wt%、3.2wt%、2.1wt%であった。また、実施例1と同様に、分析したところ、Rhの粒子が触媒表面に存在していることが確認された。 Specifically, first, the catalyst is brought into contact with the catalyst by circulating a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/2) in advance at 500 ° C. for 1 hour. The reduction treatment was performed. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio = 1: 1: 0) is used, the gas pressure at the catalyst layer outlet is 1960 kPaG, the gas temperature at the catalyst layer outlet is 880 ° C., the methane reference GHSV = 2, The treatment was performed at 500 / hour. The CH 4 conversion after 5 hours from the start of the reaction is 15.8% (equilibrium conversion of CH 4 under experimental conditions = 54.8%), and the CH 4 conversion after 40 hours is 10.2%. Met. In addition, after 40 hours, the amount of carbon on the catalyst extracted by dividing into four parts in the same manner as in Example 1 was 5.5 wt%, 5.1 wt%, 3.2 wt%, and 2.1 wt%, respectively, in order from the top. . Further, as in Example 1, the analysis confirmed that Rh particles were present on the catalyst surface.
<比較例4>
市販のCaO成型体を空気中で950℃で3時間焼成し、触媒担体を得た。得られた触媒担体について、実施例1と同様にICP分析した。得られた触媒担体は、担体自体の構成成分がCaOであった。
<Comparative Example 4>
A commercially available CaO molded body was calcined in air at 950 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst support was analyzed by ICP in the same manner as in Example 1. In the obtained catalyst carrier, the constituent component of the carrier itself was CaO.
次に、得られた触媒担体に、0.3wt%のRhを含む酢酸ロジウム水溶液を、触媒担体1.0gに対し0.25cc(触媒担体の吸水量の1.1倍)にて噴霧し、Rhを担持した触媒担体を得た。こうして得られたRhを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で950℃で2.0時間焼成し、触媒を得た。 Next, an aqueous rhodium acetate solution containing 0.3 wt% Rh is sprayed on the obtained catalyst carrier at 0.25 cc (1.1 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, A catalyst carrier carrying Rh was obtained. The catalyst carrier carrying Rh thus obtained was dried in an oven at 120 ° C. for 2.5 hours in air and then calcined in an electric furnace at 950 ° C. for 2.0 hours in air to obtain a catalyst.
得られた触媒は、Rhを触媒に対し780wtppmの割合で含有するもので、そのBET比表面積は8.90m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、担体CaO表面上にRhが担持されていた。 The obtained catalyst contained Rh at a ratio of 780 wtppm with respect to the catalyst, and its BET specific surface area was 8.90 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Rh was supported on the surface of the support CaO.
<比較反応例4>
比較例7で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 4>
The same reactor used in Example 1 was charged with 50 cc of the catalyst prepared in Comparative Example 7, and a CO 2 reforming test for methane was performed.
具体的には、まず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/5)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。反応開始から5時間経過後のCH4転化率は25.3%(実験条件下でのCH4の平衡転化率=54.8%)、70時間経過後のCH4転化率は18.2%であった。また70時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ17.4wt%、10.3wt%、5.1wt%、4.7wt%であった。また、実施例1と同様に、比較反応例4記載の前処理条件で処理した触媒を分析したところ、粒子状のRhが触媒表面に存在していることが確認された。 Specifically, first, the catalyst is prepared by passing a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/5) in advance through the catalyst layer at 500 ° C. for 1 hour. The reduction process was performed by making it contact. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is converted into a catalyst layer outlet gas pressure of 1960 kPaG, a catalyst layer outlet gas temperature of 880 ° C., methane-based GHSV = 2, The treatment was performed at 500 / hour. The CH 4 conversion after 5 hours from the start of the reaction was 25.3% (equilibrium conversion of CH 4 under experimental conditions = 54.8%), and the CH 4 conversion after 70 hours was 18.2%. Met. Further, after 70 hours, the amounts of carbon on the catalyst extracted by dividing into 4 parts in the same manner as in Example 1 were 17.4 wt%, 10.3 wt%, 5.1 wt%, and 4.7 wt%, respectively, from the top. . Similarly to Example 1, when the catalyst treated under the pretreatment conditions described in Comparative Reaction Example 4 was analyzed, it was confirmed that particulate Rh was present on the catalyst surface.
<比較例5>
CaO含有量がCa換算で0.01wt%以下である市販のZrO2成型体を空気中で950℃で3時間焼成し、触媒担体を得た。得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体のCaO含有量はCa換算で0.01wt%以下であった。得られた触媒担体は、担体成分自体の構成成分がCaOである。
<Comparative Example 5>
A commercially available ZrO 2 molded body having a CaO content of 0.01 wt% or less in terms of Ca was calcined in air at 950 ° C. for 3 hours to obtain a catalyst carrier. When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the CaO content of the catalyst support was 0.01 wt% or less in terms of Ca. In the obtained catalyst carrier, the constituent component of the carrier component itself is CaO.
次に、得られた触媒担体に、0.28wt%のRhを含む酢酸ロジウム水溶液を、触媒担体1.0gに対し0.22cc(触媒担体の吸水量の1.2倍質量)にて噴霧し、Rhを担持した触媒担体を得た。こうして得られたRhを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で950℃で2.0時間焼成し、触媒を得た。 Next, an aqueous rhodium acetate solution containing 0.28 wt% Rh is sprayed onto the obtained catalyst carrier at 0.22 cc (1.2 times the amount of water absorbed by the catalyst carrier) with respect to 1.0 g of the catalyst carrier. Thus, a catalyst carrier carrying Rh was obtained. The catalyst carrier carrying Rh thus obtained was dried in an oven at 120 ° C. for 2.5 hours in air and then calcined in an electric furnace at 950 ° C. for 2.0 hours in air to obtain a catalyst.
得られた触媒は、Rhを触媒に対し900wtppmの割合で含有するもので、そのBET比表面積は4.20m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、粒子状のRuが触媒表面に存在していることが確認された。 The obtained catalyst contained Rh at a rate of 900 wtppm with respect to the catalyst, and its BET specific surface area was 4.20 m 2 / g. Further, when the obtained catalyst was subjected to EPMA analysis in the same manner as in Example 1, it was confirmed that particulate Ru was present on the catalyst surface.
<比較反応例5>
比較例8で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 5>
The same reactor used in Example 1 was charged with 50 cc of the catalyst prepared in Comparative Example 8, and a CO 2 reforming test for methane was performed.
具体的にはまず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/3)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。反応開始から5時間経過後のCH4転化率は37.8%(実験条件下でのCH4の平衡転化率=54.8%)、10時間経過後のCH4転化率は30.2%であった。また10時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部からそれぞれ順に1.5wt%、2.3wt%、3.2wt%、3.2wt%であった。また、実施例1と同様に、比較反応例5記載の前処理条件で処理した分析したところ、Rhの粒子が触媒表面に存在していることが確認された。 Specifically, first, the catalyst is brought into contact with the catalyst by circulating a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/3) in advance at 500 ° C. for 1 hour. After performing the reduction treatment, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is used, the gas pressure at the catalyst layer outlet is 1960 kPaG, and the gas temperature at the catalyst layer outlet is 880. The treatment was carried out under the conditions of ℃ and GHSV based on methane = 2500 / hour. The conversion rate of CH 4 after 5 hours from the start of the reaction was 37.8% (equilibrium conversion rate of CH 4 under experimental conditions = 54.8%), and the conversion rate of CH 4 after 10 hours was 30.2%. Met. Further, after 10 hours, the amount of carbon on the catalyst extracted by dividing into 4 parts in the same manner as in Example 1 was 1.5 wt%, 2.3 wt%, 3.2 wt%, and 3.2 wt%, respectively, from the top. . Further, in the same manner as in Example 1, when the analysis was performed under the pretreatment conditions described in Comparative Reaction Example 5, it was confirmed that Rh particles were present on the catalyst surface.
<比較例6>
CaO含有量がCa換算で0.01wt%以下である市販のAl2O3成型体を空気中で950℃で3時間焼成し、触媒担体を得た。得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体のCaO含有量はCa換算で0.01wt%以下であった。また、得られた触媒担体ではCaは表面に存在していなかった。
<Comparative Example 6>
A commercially available Al 2 O 3 molded body having a CaO content of 0.01 wt% or less in terms of Ca was calcined in the air at 950 ° C. for 3 hours to obtain a catalyst carrier. When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the CaO content of the catalyst support was 0.01 wt% or less in terms of Ca. In the obtained catalyst carrier, Ca was not present on the surface.
次に、得られた触媒に、0.16wt%のRhを含む酢酸ロジウム水溶液を、触媒担体1.0gに対し0.75cc(触媒担体の吸水量の1.0倍)にて噴霧し、Rhを担持した触媒担体を得た。こうして得られたRhを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で950℃で2.0時間焼成し、触媒を得た。 Next, an aqueous rhodium acetate solution containing 0.16 wt% Rh was sprayed onto the obtained catalyst at 0.75 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, and Rh As a result, a catalyst carrier carrying a catalyst was obtained. The catalyst carrier carrying Rh thus obtained was dried in an oven at 120 ° C. for 2.5 hours in air and then calcined in an electric furnace at 950 ° C. for 2.0 hours in air to obtain a catalyst.
得られた触媒は、Rhを触媒に対し1200wtppmの割合で含有するもので、そのBET比表面積は110.0m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Rh近傍に選択的にCaは存在していなかった。 The obtained catalyst contained Rh at a ratio of 1200 wtppm with respect to the catalyst, and its BET specific surface area was 110.0 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Ca was not selectively present in the vicinity of Rh.
<比較反応例6>
比較例9で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 6>
The same reactor used in Example 1 was charged with 50 cc of the catalyst prepared in Comparative Example 9, and a CO 2 reforming test for methane was performed.
具体的にはまず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/1)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。反応開始から5時間経過後のCH4転化率は54.8%(実験条件下でのCH4の平衡転化率=54.8%)、50時間経過後のCH4転化率は51.2%であった。また50時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ16.1wt%、10.3wt%、5.2wt%、4.8wt%であった。また、実施例1と同様に、分析したところ、Ruの粒子が触媒表面に存在していることが確認された。 Specifically, first, the catalyst is brought into contact with the catalyst by circulating a gas mixture of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/1) in advance at 500 ° C. for 1 hour. The reduction treatment was performed. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is converted into a catalyst layer outlet gas pressure of 1960 kPaG, a catalyst layer outlet gas temperature of 880 ° C., methane-based GHSV = 2, The treatment was performed at 500 / hour. The CH 4 conversion after 5 hours from the start of the reaction was 54.8% (equilibrium conversion of CH 4 under experimental conditions = 54.8%), and the CH 4 conversion after 50 hours was 51.2%. Met. Further, after 50 hours, the amounts of carbon on the catalyst extracted in four portions in the same manner as in Example 1 were 16.1 wt%, 10.3 wt%, 5.2 wt%, and 4.8 wt%, respectively, from the top. . Further, as in Example 1, the analysis confirmed that Ru particles were present on the catalyst surface.
<比較例7>
CaO含有量がCa換算で0.001wt%以下である純度99.9wt%以上のMgOの粉末にMgO粉末に対して滑択材として3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1100℃で3時間焼成し、触媒担体を得た。得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体のCaO含有量はCa換算で0.001wt%以下であり、そのBET比表面積は0.2m2/gであった。また、表面へのCaOの析出は確認されず、CaOは触媒担体表面に存在しなかった。
<Comparative Example 7>
An MgO powder having a purity of 99.9 wt% or more with a CaO content of 0.001 wt% or less in terms of Ca is mixed with 3.0 wt% carbon as a lubricant with respect to the MgO powder, and the diameter is 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1100 ° C. for 3 hours to obtain a catalyst carrier. When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the CaO content of the catalyst support was 0.001 wt% or less in terms of Ca, and the BET specific surface area was 0.2 m 2 / g. Met. Moreover, precipitation of CaO on the surface was not confirmed, and CaO was not present on the catalyst support surface.
次に、得られた触媒担体に、0.73wt%のRhを含む酢酸Rh水溶液を担体1.0gに対し0.18cc(触媒担体の吸水量の1.2倍質量)にて噴霧し、Rhを担持した触媒担体を得た。こうして得られたRhを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で950℃で2.0時間焼成し、触媒を得た。 Next, an aqueous Rh acetate solution containing 0.73 wt% Rh was sprayed onto the obtained catalyst carrier at a rate of 0.18 cc (1.2 times the amount of water absorbed by the catalyst carrier) with respect to 1.0 g of the carrier. As a result, a catalyst carrier carrying a catalyst was obtained. The catalyst carrier carrying Rh thus obtained was dried in an oven at 120 ° C. for 2.5 hours in air and then calcined in an electric furnace at 950 ° C. for 2.0 hours in air to obtain a catalyst.
得られた触媒は、Rhを触媒に対し1300wtppmの割合で含有するもので、そのBET比表面積は0.20m2/gであった。また、得られた触媒を、実施例1と同様にEPMAにて分析したところ、Rh近傍にCaは存在していなかった。 The obtained catalyst contained Rh at a rate of 1300 wtppm with respect to the catalyst, and its BET specific surface area was 0.20 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Ca was not present in the vicinity of Rh.
<比較反応例7>
比較例10で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 7>
50 cc of the catalyst prepared in Comparative Example 10 was charged into the same reactor as that used in Example 1, and a CO 2 reforming test of methane was performed.
具体的にはまず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/3)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。 Specifically, first, the catalyst is brought into contact with the catalyst by circulating a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/3) in advance at 500 ° C. for 1 hour. After performing the reduction treatment, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is used, the gas pressure at the catalyst layer outlet is 1960 kPaG, and the gas temperature at the catalyst layer outlet is 880. The treatment was carried out under the conditions of ℃ and GHSV based on methane = 2500 / hour.
この結果、反応開始から5時間経過後のCH4転化率は54.8%(実験条件下でのCH4の平衡転化率=54.8%)、70時間経過後のCH4転化率は52.3%であった。また70時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ6.5wt%、3.5wt%、3.2wt%、2.4wt%であった。また、実施例1と同様に、分析したところ、Rhの粒子が触媒表面に存在していることが確認された。 As a result, the CH 4 conversion after 5 hours from the start of the reaction was 54.8% (CH 4 equilibrium conversion under experimental conditions = 54.8%), and the CH 4 conversion after 70 hours was 52 3%. Further, after 70 hours, the amounts of carbon on the catalyst extracted in four portions in the same manner as in Example 1 were 6.5 wt%, 3.5 wt%, 3.2 wt%, and 2.4 wt%, respectively, from the top. . Further, as in Example 1, the analysis confirmed that Rh particles were present on the catalyst surface.
<比較例8>
CaO含有量がCa換算で0.001wt%以下である純度99.9wt%以上のMgOの粉末に滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを空気中で1100℃で3時間焼成し、触媒担体を得た。得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体のCaO含有量はCa換算で0.001wt%以下であった。また、得られた触媒担体は、表面へのCaOの析出は確認されず、CaOは触媒担体表面に存在しなかった。
<Comparative Example 8>
Mixing MgO powder having a purity of 99.9 wt% or more with a CaO content of 0.001 wt% or less in terms of Ca as a lubricant, 3.0 wt% of carbon with respect to the MgO powder, and having a diameter of 1/4 inch. A cylindrical pellet was formed. The formed pellets were calcined in air at 1100 ° C. for 3 hours to obtain a catalyst carrier. When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the CaO content of the catalyst support was 0.001 wt% or less in terms of Ca. Moreover, precipitation of CaO on the surface of the obtained catalyst carrier was not confirmed, and CaO was not present on the surface of the catalyst carrier.
次に、得られた触媒担体に、0.87wt%のRhを含む酢酸ロジウム水溶液を担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)にて噴霧し、Rhを担持した触媒担体を得た。こうして得られたRhを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、更に、0.5wt%のPtを含む塩化白金酸水溶液を担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)にて噴霧し、Rh及びPtを担持した触媒担体を得た。得られたRh及びPtを担持した触媒担体を空気中において電気炉で950℃で2.0時間焼成し、触媒を得た。 Next, an aqueous rhodium acetate solution containing 0.87 wt% Rh is sprayed onto the obtained catalyst carrier at 0.15 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the carrier, A supported catalyst carrier was obtained. The catalyst carrier carrying Rh thus obtained was dried in an oven at 120 ° C. for 2.5 hours in the air, and then an aqueous chloroplatinic acid solution containing 0.5 wt% Pt was added to 1.0 g of the carrier. Spraying was performed at 15 cc (1.0 times the amount of water absorbed by the catalyst carrier) to obtain a catalyst carrier carrying Rh and Pt. The obtained catalyst carrier carrying Rh and Pt was calcined in air in an electric furnace at 950 ° C. for 2.0 hours to obtain a catalyst.
得られた触媒は、Rhを触媒に対し1300wtppm、Ptを触媒に対して750wtppmの割合で含有するもので、そのBET比表面積は0.20m2/gであった。また、得られた触媒を、実施例1と同様にEPMAにて分析したところ、Rh及びPt近傍にCaは存在していなかった。 The obtained catalyst contained Rh in a proportion of 1300 wtppm with respect to the catalyst and Pt in a proportion of 750 wtppm with respect to the catalyst, and its BET specific surface area was 0.20 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Ca was not present in the vicinity of Rh and Pt.
<比較反応例8>
比較例11で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 8>
50 cc of the catalyst prepared in Comparative Example 11 was charged into the same reactor as that used in Example 1, and a CO 2 reforming test of methane was performed.
具体的にはまず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/3)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った。その後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。反応開始から5時間経過後のCH4転化率は54.8%(実験条件下でのCH4の平衡転化率=54.8%)、15時間経過後のCH4転化率は54.8%であった。また15時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ1.6wt%、2.3wt%、3.2wt%、2.7wt%であった。また、実施例1と同様に、比較反応例8記載の前処理条件で処理した触媒を分析したところ、Rhの粒子が触媒表面に存在していることが確認された。 Specifically, first, the catalyst is brought into contact with the catalyst by circulating a mixed gas of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/3) in advance at 500 ° C. for 1 hour. The reduction treatment was performed. Thereafter, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is converted into a catalyst layer outlet gas pressure of 1960 kPaG, a catalyst layer outlet gas temperature of 880 ° C., methane-based GHSV = 2, The treatment was performed at 500 / hour. The CH 4 conversion after 5 hours from the start of the reaction was 54.8% (CH 4 equilibrium conversion under experimental conditions = 54.8%), and the CH 4 conversion after 15 hours was 54.8%. Met. Further, after 15 hours, the amount of carbon on the catalyst extracted in four portions in the same manner as in Example 1 was 1.6 wt%, 2.3 wt%, 3.2 wt%, and 2.7 wt% in order from the top. . Similarly to Example 1, when the catalyst treated under the pretreatment conditions described in Comparative Reaction Example 8 was analyzed, it was confirmed that Rh particles were present on the catalyst surface.
<比較例9>
CaO含有量がCa換算で0.001wt%以下で純度99.9wt%以上のMgOの粉末に滑択材としてMgO粉末に対して3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットに5.1wt%のLaを含む硝酸ランタン水溶液を噴霧しLaを担持させ、更に空気中で1100℃で3時間焼成し、触媒担体を得た。得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体のLa含有量は1.5wt%であり、CaO含有量はCa換算で0.001wt%以下であった。また、得られた触媒担体は、表面へのCaOの析出は確認されず、CaOは触媒担体表面に存在しなかった。
<Comparative Example 9>
A cylinder having a CaO content of 0.001 wt% or less and a purity of 99.9 wt% or more mixed with 3.0 wt% of carbon as Mg O powder as a lubricant, and having a 1/4 inch diameter cylinder Shaped pellets were formed. A lanthanum nitrate aqueous solution containing 5.1 wt% La was sprayed on the formed pellets to support La, and further calcined in air at 1100 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst support was analyzed by ICP in the same manner as in Example 1. As a result, the La content of the catalyst support was 1.5 wt%, and the CaO content was 0.001 wt% or less in terms of Ca. . Moreover, precipitation of CaO on the surface of the obtained catalyst carrier was not confirmed, and CaO was not present on the surface of the catalyst carrier.
次に、得られた触媒担体に、0.67wt%のRhを含む酢酸ロジウム水溶液を担体1.0gに対し0.20cc(触媒担体の吸水量の1.3倍)にて噴霧し、Rhを担持した触媒担体を得た。こうして得られたRhを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、更に、空気中において電気炉で950℃で2.0時間焼成し、触媒を得た。 Next, an aqueous rhodium acetate solution containing 0.67 wt% Rh is sprayed onto the obtained catalyst carrier at 0.20 cc (1.3 times the amount of water absorbed by the catalyst carrier) with respect to 1.0 g of the carrier. A supported catalyst carrier was obtained. The catalyst carrier carrying Rh thus obtained was dried in an oven at 120 ° C. for 2.5 hours in the air, and further calcined in an electric furnace at 950 ° C. for 2.0 hours in the air to obtain a catalyst.
得られた触媒は、Rhを触媒に対し1300wtppmの割合で含有するもので、そのBET比表面積は0.20m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、Rh近傍にCa及びLaは存在していなかった。 The obtained catalyst contained Rh at a rate of 1300 wtppm with respect to the catalyst, and its BET specific surface area was 0.20 m 2 / g. Further, when the obtained catalyst was subjected to EPMA analysis in the same manner as in Example 1, Ca and La were not present in the vicinity of Rh.
<比較反応例9>
比較例12で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 9>
The same reactor used in Example 1 was charged with 50 cc of the catalyst prepared in Comparative Example 12, and a CO 2 reforming test for methane was performed.
具体的にはまず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/0)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。反応開始から5時間経過後のCH4転化率は54.8%(実験条件下でのCH4の平衡転化率=54.8%)、50時間経過後のCH4転化率は54.8%であった。また50時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ7.2wt%、5.1wt%、2.1wt%、1.2wt%であった。また、実施例1と同様に、比較反応例9記載の前処理条件で処理した触媒を分析したところ、Rhの粒子が触媒表面に存在していることが確認された。 Specifically, first, the catalyst is brought into contact with the catalyst by circulating a gas mixture of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/0) in advance at 500 ° C. for 1 hour. After performing the reduction treatment, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is used, the gas pressure at the catalyst layer outlet is 1960 kPaG, and the gas temperature at the catalyst layer outlet is 880. The treatment was carried out under the conditions of ℃ and GHSV based on methane = 2500 / hour. The CH 4 conversion after 5 hours from the start of the reaction was 54.8% (equilibrium conversion of CH 4 under experimental conditions = 54.8%), and the CH 4 conversion after 50 hours was 54.8%. Met. Further, after 50 hours, the amounts of carbon on the catalyst extracted by dividing into 4 parts as in Example 1 were 7.2 wt%, 5.1 wt%, 2.1 wt%, and 1.2 wt%, respectively, from the top. . Similarly to Example 1, analysis of the catalyst treated under the pretreatment conditions described in Comparative Reaction Example 9 confirmed that Rh particles were present on the catalyst surface.
<比較例10>
CaO含有量がCa換算で0.001wt%以下で純度99.9wt%以上のMgOの粉末を100℃にて煮沸攪拌しMg(OH)2とする際に、同時にCa(OH)2水溶液を滴下攪拌することでCa添加型Mg(OH)2粒子を得た。この添加体に滑択材として3.0wt%のカーボンを混合し、直径1/4インチの円筒状のペレットを形成した。形成したペレットを更に空気中で1180℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.10m2/gであった。
<Comparative Example 10>
When an MgO powder having a CaO content of 0.001 wt% or less in terms of Ca and having a purity of 99.9 wt% or more is boiled and stirred at 100 ° C. to make Mg (OH) 2 , a Ca (OH) 2 aqueous solution is dropped simultaneously. By stirring, Ca-added Mg (OH) 2 particles were obtained. This additive was mixed with 3.0 wt% carbon as a sliding material to form a cylindrical pellet having a diameter of 1/4 inch. The formed pellets were further calcined in air at 1180 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.10 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体のCaO含有量は1.8wt%であった。なお、EPMA分析結果から、触媒担体の内部にCaが存在せず、CaはMgO粒子表面のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子はCa添加型Mg(OH)2粒子よりも顕著に大きかった。したがって、Ca添加型Mg(OH)2粒子が凝集してMgO粒子を形成し、且つ、Ca添加型Mg(OH)2粒子が含有するCaOがMgO粒子表面に析出したと考えられる。また、得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で180mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 When the obtained catalyst support was analyzed by ICP in the same manner as in Example 1, the CaO content of the catalyst support was 1.8 wt%. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only on the MgO particle surface. In addition, the MgO particles constituting the obtained catalyst support were significantly larger than the Ca-added Mg (OH) 2 particles. Therefore, it is considered that Ca-added Mg (OH) 2 particles aggregate to form MgO particles, and CaO contained in the Ca-added Mg (OH) 2 particles is precipitated on the surface of the MgO particles. The obtained catalyst carrier is in the form of particles as in Example 1, a part of the surface of MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of MgO particles. Was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the amount of CaO present on the surface of the MgO particles was determined, it was 180 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、0.87wt%のRhを含む酢酸ロジウム水溶液を、触媒担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)にて噴霧し、Rhを担持した触媒担体を得た。次に、得られたRhを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、更に、空気中において電気炉で950℃で2.0時間焼成し、触媒を得た。 Next, an aqueous rhodium acetate solution containing 0.87 wt% Rh is sprayed onto the obtained catalyst carrier at 0.15 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier, A catalyst carrier carrying Rh was obtained. Next, the obtained catalyst support carrying Rh was dried in an oven at 120 ° C. for 2.5 hours in the air, and further calcined in an electric furnace at 950 ° C. for 2.0 hours in the air to obtain a catalyst. It was.
得られた触媒は、Rhを触媒に対し1300wtppmの割合で含有するもので、そのBET比表面積は0.10m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、触媒粒子の表面にRhが担持されていた。そして、Rhは触媒表面から深さ10%以内の領域に存在していた。よって、該Rhの近傍にCaOが存在していると考えられる。 The obtained catalyst contained Rh at a rate of 1300 wtppm with respect to the catalyst, and its BET specific surface area was 0.10 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Rh was supported on the surfaces of the catalyst particles. Rh was present in a region within 10% of the depth from the catalyst surface. Therefore, it is considered that CaO exists in the vicinity of the Rh.
<比較反応例10>
比較例10で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 10>
50 cc of the catalyst prepared in Comparative Example 10 was charged into the same reactor as that used in Example 1, and a CO 2 reforming test of methane was performed.
具体的にはまず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/0)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。反応開始から5時間経過後のCH4転化率は53.9%(実験条件下でのCH4の平衡転化率=54.8%)、50時間経過後のCH4転化率は53.1%であった。また50時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ0.6wt%、0.4wt%、0.1wt%、0.05wt%であった。また、比較反応例記載の前処理条件で処理した触媒を分析したところ、粒子状のRhが触媒表面に存在していることが確認された。 Specifically, first, the catalyst is brought into contact with the catalyst by circulating a gas mixture of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/0) in advance at 500 ° C. for 1 hour. After performing the reduction treatment, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is used, the gas pressure at the catalyst layer outlet is 1960 kPaG, and the gas temperature at the catalyst layer outlet is 880. The treatment was carried out under the conditions of ℃ and GHSV based on methane = 2500 / hour. The CH 4 conversion after 5 hours from the start of the reaction was 53.9% (equilibrium conversion of CH 4 under experimental conditions = 54.8%), and the CH 4 conversion after 5 hours was 53.1%. Met. Further, after 50 hours, the amounts of carbon on the catalyst extracted in four portions in the same manner as in Example 1 were 0.6 wt%, 0.4 wt%, 0.1 wt%, and 0.05 wt%, respectively, from the top. . Further, when the catalyst treated under the pretreatment conditions described in the comparative reaction example was analyzed, it was confirmed that particulate Rh was present on the catalyst surface.
<比較例11>
CaO含有量がCa換算で0.001wt%以下で純度99.9wt%以上のMgOの粉末を100℃にて煮沸攪拌しMg(OH)2とする際に、同時にCa(OH)2水溶液を滴下攪拌することでCa添加型Mg(OH)2粒子を得た。この添加体に滑択材として3.0wt%のカーボンを混合し、直径1/4インチのペレットを形成した。形成したペレットを更に空気中で1060℃で3時間焼成し、触媒担体を得た。得られた触媒担体のBET比表面積は0.10m2/gであった。
<Comparative Example 11>
When an MgO powder having a CaO content of 0.001 wt% or less in terms of Ca and having a purity of 99.9 wt% or more is boiled and stirred at 100 ° C. to make Mg (OH) 2 , a Ca (OH) 2 aqueous solution is dropped simultaneously. By stirring, Ca-added Mg (OH) 2 particles were obtained. This additive was mixed with 3.0 wt% carbon as a sliding material to form a 1/4 inch diameter pellet. The formed pellets were further calcined in air at 1060 ° C. for 3 hours to obtain a catalyst carrier. The obtained catalyst carrier had a BET specific surface area of 0.10 m 2 / g.
得られた触媒担体を、実施例1と同様に、ICPで分析したところ、該触媒担体はCaOをCa換算で0.001wt%含有していた。なお、EPMA分析結果から、触媒担体の内部にCaが存在せず、CaはMgO粒子表面のみに存在していることが確認された。また、得られた触媒担体を構成するMgO粒子はCa添加型Mg(OH)2粒子よりも顕著に大きかった。したがって、Ca添加型Mg(OH)2粒子が凝集してMgO粒子を形成し、且つ、Ca添加型Mg(OH)2粒子が含有するCaOがMgO粒子表面に析出したと考えられる。また、得られた触媒担体は、実施例1と同様に、粒子状であり、MgO粒子の表面の一部が、CaOを含有する層で被覆され、また、MgO粒子表面の凹部にCaOが存在していた。また、これらCaOは触媒担体の表面から深さ10%以内である領域に存在していた。そして、MgO粒子表面のCaOの存在量を求めたところ、Ca換算で0.02mg−Ca/m2であった。また、ピーナッツ状粒子の中央部はCaをごく微量しか含まず、ほとんどのCaは両端部に含まれていた。 The obtained catalyst support was analyzed by ICP in the same manner as in Example 1. As a result, the catalyst support contained 0.001 wt% of CaO in terms of Ca. From the EPMA analysis results, it was confirmed that Ca was not present inside the catalyst support and Ca was present only on the MgO particle surface. In addition, the MgO particles constituting the obtained catalyst support were significantly larger than the Ca-added Mg (OH) 2 particles. Therefore, it is considered that Ca-added Mg (OH) 2 particles aggregate to form MgO particles, and CaO contained in the Ca-added Mg (OH) 2 particles is precipitated on the surface of the MgO particles. The obtained catalyst carrier is in the form of particles as in Example 1, a part of the surface of MgO particles is covered with a layer containing CaO, and CaO is present in the recesses on the surface of MgO particles. Was. Moreover, these CaO existed in the area | region which is within 10% of the depth from the surface of a catalyst support | carrier. And when the amount of CaO present on the surface of the MgO particles was determined, it was 0.02 mg-Ca / m 2 in terms of Ca. Moreover, the center part of peanut-like particle | grains contained only trace amount Ca, and most Ca was contained in both ends.
次に、得られた触媒担体に、0.7wt%のRuを含む硝酸ルテニウム水溶液を、触媒担体1.0gに対し0.15cc(触媒担体の吸水量の1.0倍)にて噴霧しRuを担持した触媒担体を得た。次に、得られたRuを担持した触媒担体を空気中においてオーブンで120℃で2.5時間乾燥した後、空気中において電気炉で400℃で2.0時間焼成し、触媒を得た。 Next, an aqueous ruthenium nitrate solution containing 0.7 wt% Ru is sprayed onto the obtained catalyst carrier at 0.15 cc (1.0 times the water absorption amount of the catalyst carrier) with respect to 1.0 g of the catalyst carrier. As a result, a catalyst carrier carrying a catalyst was obtained. Next, the obtained catalyst support carrying Ru was dried in an oven at 120 ° C. for 2.5 hours in air, and then calcined in an electric furnace at 400 ° C. for 2.0 hours in air to obtain a catalyst.
得られた触媒は、Ruを触媒に対し910wtppmの割合で含有するもので、BET比表面積は0.10m2/gであった。また、得られた触媒を、実施例1と同様にEPMA分析したところ、触媒粒子の表面にRuが担持されていた。そして、Ruは触媒表面から深さ10%以内も領域に存在していた。よって、該Ruの近傍にCaOが存在していると考えられる。 The obtained catalyst contained Ru at a ratio of 910 wtppm with respect to the catalyst, and the BET specific surface area was 0.10 m 2 / g. Further, when the obtained catalyst was analyzed by EPMA in the same manner as in Example 1, Ru was supported on the surfaces of the catalyst particles. And Ru existed in the region within 10% depth from the catalyst surface. Therefore, it is considered that CaO exists in the vicinity of the Ru.
<比較反応例11>
比較例11で調製した触媒50ccを実施例1で用いたものと同様の反応器に充填してメタンのCO2リフォーミング試験を実施した。
<Comparative Reaction Example 11>
50 cc of the catalyst prepared in Comparative Example 11 was charged into the same reactor as that used in Example 1, and a CO 2 reforming test of methane was performed.
具体的にはまず、触媒は、予めH2及びH2Oをモル比(H2/H2O=1/0)である混合ガスを500℃で1時間触媒層を流通させて触媒と接触させることにより、還元処理を行った後、CH4:CO2:H2O(モル比)=1:1:0の原料ガスを、触媒層出口のガス圧力1960kPaG,触媒層出口のガス温度880℃,メタン基準のGHSV=2,500/時の条件で処理した。反応開始から5時間経過後のCH4転化率は53.9%(実験条件下でのCH4の平衡転化率=54.8%)、50時間経過後のCH4転化率は53.3%であった。また50時間経過後に、実施例1と同様に4分割して抜き出しした触媒上のカーボン量は上部から順にそれぞれ0.5wt%、0.5wt%、0.1wt%、0.05wt%であった。また、比較反応例11記載の前処理条件で処理した触媒を分析したところ、粒子状のRuが触媒表面に存在していることが確認された。 Specifically, first, the catalyst is brought into contact with the catalyst by circulating a gas mixture of H 2 and H 2 O in a molar ratio (H 2 / H 2 O = 1/0) in advance at 500 ° C. for 1 hour. After performing the reduction treatment, a raw material gas of CH 4 : CO 2 : H 2 O (molar ratio) = 1: 1: 0 is used, the gas pressure at the catalyst layer outlet is 1960 kPaG, and the gas temperature at the catalyst layer outlet is 880. The treatment was carried out under the conditions of ℃ and GHSV based on methane = 2500 / hour. The CH 4 conversion after 5 hours from the start of the reaction was 53.9% (equilibrium conversion of CH 4 under experimental conditions = 54.8%), and the CH 4 conversion after 50 hours was 53.3%. Met. Further, after 50 hours, the amounts of carbon on the catalyst extracted by dividing into four parts in the same manner as in Example 1 were 0.5 wt%, 0.5 wt%, 0.1 wt%, and 0.05 wt%, respectively, from the top. . Further, when the catalyst treated under the pretreatment conditions described in Comparative Reaction Example 11 was analyzed, it was confirmed that particulate Ru was present on the catalyst surface.
実施例1〜13及び比較例1〜11の製造条件、得られた担体及び触媒の性状を表3に示し、反応例1〜10及び比較反応例1〜11の条件及び結果を表4に示す。表3及び表4に示すように、本発明の触媒担体を用いて製造した実施例1〜10の触媒を用いたCO2リフォーム反応では、カーボンの析出量が顕著に低かった(反応例1〜10参照)。そして、長時間通気しても、メタン転化率が維持されており、長期間安定的に効率良く合成ガスを製造していた。 Table 3 shows the production conditions of Examples 1 to 13 and Comparative Examples 1 to 11, properties of the obtained carriers and catalysts, and Table 4 shows the conditions and results of Reaction Examples 1 to 10 and Comparative Reaction Examples 1 to 11. . As shown in Tables 3 and 4, in the CO 2 reforming reaction using the catalysts of Examples 1 to 10 produced using the catalyst carrier of the present invention, the amount of carbon deposited was significantly low (Reaction Examples 1 to 1). 10). And even if it ventilated for a long time, the methane conversion rate was maintained and the synthesis gas was manufactured stably and efficiently for a long period of time.
一方、焼成温度が低くCaOがMgO粒子表面に析出しなかった比較例1、担体がMgOを含有しない比較例2〜6、含有するCaO量が本発明の範囲外の比較例7〜11は、カーボンの析出量が多く、短時間でカーボンが析出した(比較反応例1〜11参照)。また、比較例1及び3〜8は、CH4転化率も実施例と比べて低かった。 On the other hand, Comparative Example 1 in which the firing temperature was low and CaO did not precipitate on the surface of MgO particles, Comparative Examples 2 to 6 in which the carrier did not contain MgO, and Comparative Examples 7 to 11 in which the amount of CaO contained was outside the scope of the present invention, A large amount of carbon was deposited, and carbon was deposited in a short time (see Comparative Reaction Examples 1 to 11). In Comparative Examples 1 and 3 to 8, the CH 4 conversion was also low compared to the Examples.
なお、実施例11〜13は、本発明の触媒担体を用いてRh及びRu以外の触媒金属を担持させることにより触媒を製造した例を示すものである。これらの触媒は、CO2リフォーム反応以外の反応に用いることができ、その際にカーボンの析出を抑えることができると考えられる。 In addition, Examples 11-13 show the example which manufactured the catalyst by carrying | supporting catalyst metals other than Rh and Ru using the catalyst support | carrier of this invention. These catalysts can be used for reactions other than the CO 2 reforming reaction, and at that time, it is considered that the precipitation of carbon can be suppressed.
10 合成ガス製造触媒用担体
11 酸化マグネシウム粒子
12、13 酸化カルシウム含有層
10 Support for synthesis
Claims (9)
酸化マグネシウム粒子の表面近傍に酸化カルシウムを含有し、該酸化カルシウムの該粒子全体に対する含有量が、Ca換算で0.005質量%〜1.5質量%であることを特徴とする触媒担体。 A magnesia catalyst carrier,
A catalyst carrier comprising calcium oxide in the vicinity of the surface of magnesium oxide particles, wherein the content of the calcium oxide with respect to the entire particles is 0.005% by mass to 1.5% by mass in terms of Ca.
酸化カルシウムを含有する原料酸化マグネシウム粒子を1000℃以上で焼成する工程を含むことにより、該原料酸化マグネシウム粒子を凝集させて酸化マグネシウム粒子を形成するとともに、該酸化マグネシウム粒子の表面に酸化カルシウムを析出させて、該酸化マグネシウム粒子の表面近傍に酸化カルシウムを含有し、該酸化カルシウムの該粒子全体に対する含有量がCa換算で0.005質量%〜1.5質量%である触媒担体を得ることを特徴とする触媒担体の製造方法。 A method for producing a magnesia-based catalyst carrier, comprising:
By including firing the raw material magnesium oxide particles containing calcium oxide at 1000 ° C. or more, the raw material magnesium oxide particles are aggregated to form magnesium oxide particles, and calcium oxide is deposited on the surface of the magnesium oxide particles And obtaining a catalyst carrier that contains calcium oxide in the vicinity of the surface of the magnesium oxide particles, and that the content of the calcium oxide is 0.005% by mass to 1.5% by mass in terms of Ca. A method for producing a catalyst carrier.
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