JP4931099B2 - Catalyst for producing cycloolefin and method for producing cycloolefin - Google Patents

Catalyst for producing cycloolefin and method for producing cycloolefin Download PDF

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JP4931099B2
JP4931099B2 JP2003339268A JP2003339268A JP4931099B2 JP 4931099 B2 JP4931099 B2 JP 4931099B2 JP 2003339268 A JP2003339268 A JP 2003339268A JP 2003339268 A JP2003339268 A JP 2003339268A JP 4931099 B2 JP4931099 B2 JP 4931099B2
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catalyst
ruthenium
cycloolefin
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章喜 福澤
民邦 小松
方彦 古谷
敬三 友国
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Noguchi Institute
Asahi Kasei Chemicals Corp
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description

本発明は、単環芳香族炭化水素の部分水素化により、シクロオレフィンを製造するに際して用いる触媒及び、シクロオレフィンの製造方法に関するものであり、詳しくは、担体として比表面積が30〜800m/gの範囲内にある結晶性のメソポーラスジルコニア材料を用い、その担体にルテニウムを担持させて構成されるシクロオレフィン製造用触媒及び、その触媒を用い、単環芳香族炭化水素を水の存在下、液相にて部分水素化することを特徴とするシクロオレフィンの製造方法に関する。 The present invention relates to a catalyst used for producing a cycloolefin by partial hydrogenation of a monocyclic aromatic hydrocarbon, and a method for producing a cycloolefin. Specifically, the specific surface area of the support is 30 to 800 m 2 / g. A catalyst for cycloolefin production comprising a crystalline mesoporous zirconia material in the range of the above and having ruthenium supported on the carrier, and using the catalyst, liquid monocyclic aromatic hydrocarbons in the presence of water. The present invention relates to a process for producing cycloolefin, characterized by partial hydrogenation in a phase.

従来、単環芳香族炭化水素の部分水素化により、シクロオレフィンを製造する触媒としては、主にルテニウム触媒が用いられる。また、そのルテニウム触媒を用いる方法としては、水及び金属塩の存在下で用いる方法が一般的である。   Conventionally, ruthenium catalysts are mainly used as catalysts for producing cycloolefins by partial hydrogenation of monocyclic aromatic hydrocarbons. Moreover, as a method using the ruthenium catalyst, a method used in the presence of water and a metal salt is general.

公知の触媒としては、ルテニウム金属微粒子をそのまま使用する方法が特許文献1、2、3に、ルテニウム金属の微粒子の他に少なくとも1種の金属酸化物を添加して反応を行う方法が特許文献4、5、6に、シリカ、アルミナ、シリカ・ジルコニア等の担体にルテニウムを担持させた触媒を用いる方法が特許文献7、8、9、10に、メソポーラスシリカ材料にルテニウムを担持させた触媒を用いる方法が特許文献11に提案されている。   As a known catalyst, a method of using ruthenium metal fine particles as they are is disclosed in Patent Documents 1, 2, and 3, and a method in which at least one metal oxide is added in addition to ruthenium metal fine particles is reacted. Patent Documents 7, 8, 9, and 10 use a catalyst in which ruthenium is supported on a mesoporous silica material. A method is proposed in Patent Document 11.

しかし、従来の方法は何らかの問題点を抱えている。触媒としてルテニウム金属の微粒子をそのまま使用した場合やルテニウム金属の微粒子の他に少なくとも1種の金属酸化物を添加して反応を行う場合には、反応系で触媒粒子の凝集が起こるので触媒活性が低下し、シクロオレフィンの生産性が低下する。   However, the conventional method has some problems. When ruthenium metal fine particles are used as they are as a catalyst or when the reaction is carried out by adding at least one metal oxide in addition to the ruthenium metal fine particles, the catalyst particles agglomerate in the reaction system, so that the catalytic activity is increased. This lowers the productivity of cycloolefin.

一方、シリカ、アルミナ、シリカ・ジルコニア等の担体にルテニウムを担持した触媒は、ルテニウム当たりの初期の触媒活性は高いがシクロオレフィンの選択性が著しく低いという問題があると同時に、水及び金属塩の存在下での反応条件(水熱・酸性条件)で担体が溶解するという問題がある。   On the other hand, a catalyst in which ruthenium is supported on a carrier such as silica, alumina, silica / zirconia has a problem that the initial catalytic activity per ruthenium is high but the selectivity of cycloolefin is remarkably low. There is a problem that the carrier dissolves under the reaction conditions (hydrothermal and acidic conditions) in the presence.

本発明者らが先に考案したメソポーラスシリカ材料にルテニウムを高分散担持させた触媒を用いる方法(特許文献11)では、初期の触媒活性とシクロオレフィンの選択率も高いのであるが、水熱・酸性の反応条件下で担体であるメソポーラスシリカ材料が溶出するので、長時間後には触媒活性とシクロオレフィンの選択性が著しく低下し、反応系も汚染するという問題がある。   In the method using the catalyst in which ruthenium is highly dispersed and supported on the mesoporous silica material previously devised by the present inventors (Patent Document 11), the initial catalytic activity and the selectivity of cycloolefin are high. Since the mesoporous silica material as a carrier elutes under acidic reaction conditions, there is a problem that the catalytic activity and the selectivity of cycloolefin are remarkably lowered after a long time and the reaction system is contaminated.

特開昭61−50930JP 61-50930 特開昭62−45541JP-A 62-45541 特開昭62−45544JP 62-45544 A 特開昭62−201830JP 62-201830 A 特開昭63−17834JP-A-63-17834 特開昭63−63627JP-A-63-63627 特開昭57−130926JP-A-57-130926 特開昭61−40226JP 61-40226 特開平4−74141JP-A-4-74141 特開平7−285892JP-A-7-285892 特開2002−154990JP2002-154990

本発明は、上記の事情に鑑み、シクロオレフィン製造における水熱・酸性の反応条件下では溶解しない多孔質結晶性の担体を合成し、この担体にルテニウム触媒を高分散担持させた高活性・高選択性の触媒を調製し、この触媒によって単環芳香族炭化水素の水存在下での部分水素化によるシクロオレフィンの製造を効率的に行うことを目的とするものである。   In view of the above circumstances, the present invention synthesizes a porous crystalline carrier that does not dissolve under hydrothermal and acidic reaction conditions in cycloolefin production, and has a highly dispersed and highly supported ruthenium catalyst on this carrier. An object of the present invention is to prepare a selective catalyst and to efficiently produce cycloolefin by partial hydrogenation of monocyclic aromatic hydrocarbons in the presence of water.

本発明者らは、上記の目的を達成するために鋭意研究を重ねた結果、単環芳香族炭化水素の部分水素化によリ、シクロオレフィンを製造するに際して、以下に示される物性値を持ったメソポーラスジルコニア材料を担体として用い、その担体にルテニウムを担持させて構成される固体触媒が優れた性能を示すことを見いだし、この知見に基づいて本発明を完成するに至った。すなわち、本発明は、以下の通りである。   As a result of intensive studies to achieve the above object, the present inventors have the following physical properties when producing cycloolefins by partial hydrogenation of monocyclic aromatic hydrocarbons. The present inventors have found that a solid catalyst using a mesoporous zirconia material as a carrier and having ruthenium supported on the carrier exhibits excellent performance, and has completed the present invention based on this finding. That is, the present invention is as follows.

(1)単環芳香族炭化水素の部分水素化によ、シクロオレフィンを製造する触媒において、比表面積が30〜800m/gの範囲内にある単斜晶系の結晶性を有する結晶性メソポーラスジルコニア材料を担体として用い、その担体にルテニウムを担持させて構成されるシクロオレフィン製造用触媒。
(2)前記比表面積が80〜500m/gの範囲内にあることを特徴とする上記(1)のシクロオレフィン製造用触媒。
(3)前記シクロオレフィン製造用触媒が、亜鉛もしくは亜鉛化合物を含有していることを特徴とする上記(1)、(2)のシクロオレフィン製造用触媒。
(4)単環芳香族炭化水素の部分水素化によ、シクロオレフィンを製造するに際して、上記(1)〜(3)のいずれかに記載の触媒を用いて、水の存在下、液相にて単環芳香族炭化水素を部分水素化することを特徴とするシクロオレフィンの製造方法。
(5)前記液相に亜鉛化合物もしくは亜鉛イオン、またはその両方を存在させることを特徴とする上記(4)のシクロオレフィンの製造方法。
(1) Ri by the partial hydrogenation of monocyclic aromatic hydrocarbons, in the catalyst for producing a cycloolefin, crystalline having a specific surface area has a crystalline monoclinic that are within the scope of 30~800m 2 / g A catalyst for producing cycloolefin comprising a mesoporous zirconia material as a carrier and ruthenium supported on the carrier.
(2) The catalyst for producing cycloolefin according to the above (1), wherein the specific surface area is in the range of 80 to 500 m 2 / g.
(3) The cycloolefin production catalyst according to the above (1) or (2), wherein the cycloolefin production catalyst contains zinc or a zinc compound.
(4) Ri by the partial hydrogenation of monocyclic aromatic hydrocarbons, in manufacturing the cycloolefin using a catalyst according to any one of the above (1) to (3), the presence of water, the liquid phase A process for producing a cycloolefin, characterized in that monocyclic aromatic hydrocarbons are partially hydrogenated in the process.
(5) The method for producing a cycloolefin according to the above (4), wherein the liquid phase contains a zinc compound and / or zinc ions.

本発明の触媒は、担体としてメソポーラスジルコニア材料の物性を規定し、その担体にルテニウムを担持した担持型触媒(以下、担持型触媒を触媒と述べる)である。この触媒は、従来の触媒に対して水熱・酸性条件においても担体の溶解はなく、担体の結晶構造の変化も起こさず安定であり、従来のシリカ系及びシリカ・アルミナ系に担持した担持触媒では達成できなかった極めて高い触媒活性と格段に長い触媒ライフを示す。例えば、本発明における結晶性のメソポーラスジルコニア材料にルテニウムを担持した触媒は、同程度の比表面積を有するメソポーラスシリカ材料に同一の担持量で担持させた触媒と比較して、1〜2倍の高い触媒活性を示し、2〜10倍の触媒ライフを示す。   The catalyst of the present invention is a supported catalyst in which the physical properties of a mesoporous zirconia material are defined as a support and ruthenium is supported on the support (hereinafter, the supported catalyst is referred to as a catalyst). This catalyst does not dissolve the carrier even under hydrothermal and acidic conditions compared to conventional catalysts, is stable without causing a change in the crystal structure of the carrier, and is supported on conventional silica-based and silica-alumina-based catalysts. Shows extremely high catalytic activity and a much longer catalyst life that could not be achieved. For example, a catalyst in which ruthenium is supported on a crystalline mesoporous zirconia material in the present invention is 1-2 times higher than a catalyst supported on a mesoporous silica material having the same specific surface area at the same loading amount. Shows catalytic activity, 2-10 times longer catalyst life.

以下、本発明を詳細に説明する。
本発明は、単環芳香族炭化水素の部分水素化により、シクロオレフィンを製造するに際して、担体として比表面積が30〜800m/gの範囲内にある結晶性のメソポーラスジルコニア材料を用い、その担体にルテニウムを担持させて構成されるシクロオレフィン製造用触媒及び、その触媒を用い、単環芳香族炭化水素を水の存在下、液相にて部分水素化することを特徴とするシクロオレフィンの製造方法に関する。
Hereinafter, the present invention will be described in detail.
The present invention uses a crystalline mesoporous zirconia material having a specific surface area in the range of 30 to 800 m 2 / g as a carrier when producing a cycloolefin by partial hydrogenation of a monocyclic aromatic hydrocarbon. Of cycloolefin produced by supporting ruthenium on a catalyst, and cycloolefin production comprising using the catalyst to partially hydrogenate monocyclic aromatic hydrocarbons in the liquid phase in the presence of water Regarding the method.

本発明でいうルテニウムとは、ルテニウム金属、ルテニウム化合物、ルテニウムイオンも含まれる。また、表面とバルクの状態が異なったものや表面が電子的価数を持った状態も含めルテニウムと総称する。   In the present invention, ruthenium includes ruthenium metal, ruthenium compounds, and ruthenium ions. In addition, the term “ruthenium” is used as a generic term for the case where the surface and the bulk state are different and the surface has an electronic valence.

本発明でいうメソポーラスとは、メソ細孔を有する多孔質であることをいう。担体は、触媒の表面積を増やし微粒子の形で分散担持するためだけの単なる容器ではなく、化学的に担持した成分を安定化させ適切な反応場を提供するためのミクロの反応容器でもある。 したがって、固体触媒を作製する上で、担体の耐久性、構造、比表面積、細孔径、細孔容積は重要な設計要素である。多くのセラミックス系材料について水素化反応を行うための水熱・酸性条件での耐久性を調べた結果、本発明における結晶性のメソポーラスジルコニア材料が最も高い耐久性を有することがわかった。   The mesoporous as used in the present invention means a porous material having mesopores. The support is not merely a container for increasing the surface area of the catalyst and supporting the dispersion in the form of fine particles, but also a micro reaction container for stabilizing the chemically supported components and providing an appropriate reaction field. Therefore, the durability, structure, specific surface area, pore diameter, and pore volume of the support are important design factors in producing a solid catalyst. As a result of examining the durability under hydrothermal and acidic conditions for performing hydrogenation reaction on many ceramic materials, it was found that the crystalline mesoporous zirconia material in the present invention has the highest durability.

メソ細孔とは、IUPACで提唱される細孔分布領域を指し、本発明においては実質的に2〜50nmの細孔直径を有しているものをいう。実質的とは、気体吸着法により測定される細孔直径が1〜200nm範囲の細孔分布において、細孔直径が2〜50nmの範囲にある細孔の占める細孔容積が全細孔容積の50%以上であることを指す。担持型触媒における細孔特性は、担持させる成分の粒子成長の制御に効果があるほか、反応における原料物質及び生成物の物質移動プロセスに影響する。   The mesopore refers to a pore distribution region proposed by IUPAC, and in the present invention, has a pore diameter of substantially 2 to 50 nm. Substantial means that the pore volume occupied by pores having a pore diameter in the range of 2 to 50 nm is the total pore volume in the pore distribution having a pore diameter measured by the gas adsorption method in the range of 1 to 200 nm. It means 50% or more. The pore characteristics of the supported catalyst are effective in controlling the particle growth of the component to be supported, and also affect the mass transfer process of the raw material and product in the reaction.

細孔直径が2nm未満でも触媒成分の担持は可能であるが、原料物質及び生成物の物質移動プロセスが制限され、反応活性が低くなることや目的生成物の反応選択性が低くなる原因になるなど好ましくない。また、細孔直径が50nmを超える場合には、分散担持されたナノサイズの触媒微粒子が高温・水熱条件などによるシンタリングによって巨大粒子に成長しやすいので好ましくない。好ましくは、3〜20nmの細孔分布領域が全細孔容積の10%以上、特に好ましくは3〜15nmの細孔分布領域が全細孔容積の30%以上あることである。   Although the catalyst component can be supported even if the pore diameter is less than 2 nm, the mass transfer process of the raw material and the product is limited, which causes the reaction activity to be low and the reaction selectivity of the target product to be low. It is not preferable. In addition, when the pore diameter exceeds 50 nm, it is not preferable because the dispersed and supported nano-sized catalyst fine particles easily grow into giant particles by sintering under high temperature / hydrothermal conditions. Preferably, the pore distribution region of 3 to 20 nm is 10% or more of the total pore volume, and particularly preferably the pore distribution region of 3 to 15 nm is 30% or more of the total pore volume.

尚、細孔容積は、触媒担持量を好ましい範囲に維持するために、担体lg当たり、細孔容積が0.15〜1.2cm/g必要である。細孔容積は、触媒の担持量に関係する設計要素である。触媒担持量を好ましい範囲に維持するために、担体lg当たり、細孔容積が0.15〜1.2cm/g必要であり、好ましくは、0.2〜0.8cm/gである。0.15cm/g未満では触媒担持量が少ないので触媒活性が充分ではなく、1.2cm/gを超えると触媒担持量を大きくすることができるが細孔の物理的な破壊が起きやすくなるので好ましくない。 The pore volume is required to be 0.15 to 1.2 cm 3 / g per gram of carrier in order to maintain the catalyst loading in a preferable range. The pore volume is a design factor related to the amount of catalyst supported. To maintain the catalyst supported amount in a preferable range, per carrier lg, pore volume are required 0.15~1.2cm 3 / g, preferably, 0.2~0.8cm 3 / g. If the amount is less than 0.15 cm 3 / g, the amount of catalyst supported is small and the catalytic activity is not sufficient. If the amount exceeds 1.2 cm 3 / g, the amount of supported catalyst can be increased, but physical destruction of the pores is likely to occur. This is not preferable.

本発明では、担体材料として比表面積が30〜800m/gの範囲内にある結晶性のジルコニアを用いる。担体の比表面積は、担持する触媒成分の分散性を左右する大きな特性である。担体の比表面積を高めることにより、ナノサイズの触媒微粒子を担持する上で効果的である。30m/g未満では、ナノサイズの触媒微粒子を高分散担持する上で困難となる。 In the present invention, crystalline zirconia having a specific surface area in the range of 30 to 800 m 2 / g is used as the carrier material. The specific surface area of the support is a large characteristic that affects the dispersibility of the supported catalyst component. Increasing the specific surface area of the support is effective in supporting nanosized catalyst fine particles. If it is less than 30 m 2 / g, it becomes difficult to carry highly dispersed nano-sized catalyst fine particles.

また、結晶性のジルコニアを用いる効果は、水熱条件下で担体の結晶学的構造が安定であり、細孔の体積収縮を起こしにくいので、担持触媒が細孔内に安定に保持されることである。その結果として、熱などの物理的な要因による触媒性能の劣化が起こりにくい。比表面積が高く、結晶性があるジルコニアを担体に用いることが、触媒の使用条件下でのライフ性能に効果を発揮する。ただし、熱的安定性や反応条件下での安定性を上げるために担体に熱処理を加えると、ジルコニアの結晶化が進行するが、現実的には担体の持つ比表面積は減少する。   In addition, the effect of using crystalline zirconia is that the supported catalyst is stably held in the pores because the crystallographic structure of the support is stable under hydrothermal conditions and the volumetric shrinkage of the pores is difficult to occur. It is. As a result, the catalyst performance is hardly deteriorated due to physical factors such as heat. The use of zirconia having a high specific surface area and crystallinity as a support exerts an effect on the life performance under the use conditions of the catalyst. However, if heat treatment is applied to the support in order to increase the thermal stability or the stability under reaction conditions, zirconia crystallizes, but the specific surface area of the support actually decreases.

また、高比表面積を有するジルコニアは、非晶質であることが多く、実際上、比表面積が、800m/g以上の結晶性のメソポーラスジルコニアを製造することは困難である。一般にジルコニアの結晶構造としては、単斜晶系のほか、正方晶系、六方晶系、斜方晶系、等々が存在するが、中でも単斜晶系の結晶性を有していることが好ましい。 Further, zirconia having a high specific surface area is often amorphous, and it is practically difficult to produce crystalline mesoporous zirconia having a specific surface area of 800 m 2 / g or more. In general, the crystal structure of zirconia includes a monoclinic system, a tetragonal system, a hexagonal system, an orthorhombic system, and the like, and among them, it is preferable to have monoclinic crystallinity. .

単斜晶系の結晶性を有するとは、部分的にでも単斜晶系の構造が少量でもあることを指し、主体とする結晶構造が他の結晶系であってもよいし、非晶質と混ざり合った状態であってもよい。また、単斜晶系の結晶性を有しているジルコニアの比表面積は、80〜500m/gの範囲にあるものがより好ましく、特に好ましくは、100〜350m/gである。 “Having monoclinic crystallinity” means that the monoclinic structure is partially or even in a small amount, and the main crystal structure may be another crystal system or amorphous. It may be in a mixed state. Further, the specific surface area of zirconia having monoclinic crystallinity is more preferably in the range of 80 to 500 m 2 / g, particularly preferably 100 to 350 m 2 / g.

本発明においては、担持成分であるルテニウムの担持量は、ルテニウム金属に換算して担体重量の5〜30重量%の範囲に維持される。さらに好ましい範囲は10〜20重量%である。5重量%未満では、シクロオレフィンを製造するにあたって、水添活性のある触媒成分として少ないがために使用する全触媒量を増やさなくてはならなくなり、触媒当たりの生産性が低下する。また、反応場において、生じる被毒物質による触媒劣化を起こしやすいので好ましくない。一方、細孔内に30重量%を超える均一担持を行うのは実際上困難である。   In the present invention, the supported amount of ruthenium, which is a supported component, is maintained in the range of 5 to 30% by weight of the carrier weight in terms of ruthenium metal. A more preferred range is 10 to 20% by weight. If it is less than 5% by weight, the amount of the total catalyst used must be increased because the amount of the catalyst component having hydrogenation activity is small in producing cycloolefin, and the productivity per catalyst is lowered. Further, it is not preferable because the catalyst is liable to deteriorate due to the poisoning substance generated in the reaction field. On the other hand, it is practically difficult to uniformly support more than 30% by weight in the pores.

触媒の活性成分であるルテニウムは、単独でも使用できるが、他の金属成分を共担持して用いることは有効である。ルテニウム原料としては、ルテニウムのハロゲン化物、硝酸塩、水酸化物、ルテニウムカルボニル、ルテニウムアミン錯体等の錯体が用いられる。ルテニウムと共担持する成分としては、亜鉛、ニッケル、鉄、銅、コバルト、マンガン、アルカリ土類等が使用されるが、中でも亜鉛が最も好ましい共担持成分である。これらの化合物としては、各金属のハロゲン化物、硝酸塩、酢酸塩、硫酸塩、各金属を含む錯体化合物などが用いられる。亜鉛の含有量は、ルテニウムに対する原子比で、0.01〜20好ましくは0.05〜10程度である。   Ruthenium, which is an active component of the catalyst, can be used alone, but it is effective to co-support other metal components. As the ruthenium raw material, a ruthenium halide, a nitrate, a hydroxide, a ruthenium carbonyl, a complex such as a ruthenium amine complex is used. As the component co-supported with ruthenium, zinc, nickel, iron, copper, cobalt, manganese, alkaline earth, and the like are used. Among them, zinc is the most preferable co-support component. As these compounds, halides, nitrates, acetates, sulfates of each metal, complex compounds containing each metal, and the like are used. The zinc content is an atomic ratio with respect to ruthenium and is about 0.01 to 20, preferably about 0.05 to 10.

本発明における担体であるメソポーラスジルコニア材料の合成は、テンプレートを用いる従来の方法(例えば,特開平5−254827号公報及びStudies in Surface Science and Catalysis誌2002年143号1035−1044ページに記載の方法)に準じて行うことができる。主剤であるジルコニウム化合物としては、ジルコニウムテトラエトキシド、テトラプロポキシド、テトライソプロポキシド、テトラ(t−ブトキシド)などのジルコニウムテトラアルコキシドは好ましいが、ジクロロジルコニウムオキシドなどのハロゲンを含有するジルコニウム化合物は好ましくない。   The synthesis of the mesoporous zirconia material, which is a carrier in the present invention, is performed by a conventional method using a template (for example, a method described in JP-A-5-254827 and Studies in Surface Science and Catalysis 2002, No. 143, pages 1035-1044). It can be performed according to. Zirconium tetraalkoxides such as zirconium tetraethoxide, tetrapropoxide, tetraisopropoxide, and tetra (t-butoxide) are preferred as the zirconium compound as the main agent, but halogen-containing zirconium compounds such as dichlorozirconium oxide are preferred. Absent.

テンプレートとしては、従来のメソポア分子ふるいの作製に用いられているミセル形成の界面活性剤、例えば、長鎖の4級アンモニウム塩、長鎖のアルキルアミンN−オキシド、長鎖のスルホン酸塩、ポリエチレングリコールアルキルエーテル、ポリエテレングリコール脂肪酸エステル等のいずれであってもよい。溶媒として、通常、水、アルコール類、ジオールの1種以上が用いられるが、水系溶媒が好ましい。   Templates include micelle-forming surfactants used to make conventional mesopore molecular sieves, such as long-chain quaternary ammonium salts, long-chain alkylamine N-oxides, long-chain sulfonates, polyethylene Any of glycol alkyl ethers, polyethylene glycol fatty acid esters, and the like may be used. As the solvent, one or more of water, alcohols, and diols are usually used, and an aqueous solvent is preferable.

主剤として用いるジルコニウムのテトラアルキルアルコキシドは、メソポア分子ふるいの主剤として通常用いられているシリコン系のアルコキシドに比べて加水分解速度が速いので、高比表面積のジルコニア得るためには加水分解速度の制御が重要である。金属への配位能を有する化合物を反応系に添加することは、反応系の安定性を著しく高めることができるので好ましい。このような安定化剤としては、アセチルアセトン、テトラメチレンジアミン、エチレンジアミン四酢酸、ビリジン、ピコリンなどの金属配位能を有する化合物が好ましい。   The zirconium tetraalkyl alkoxide used as the main agent has a higher hydrolysis rate than the silicon-based alkoxides usually used as the main agent of mesopore molecular sieves. Therefore, in order to obtain zirconia with a high specific surface area, the hydrolysis rate must be controlled. is important. It is preferable to add a compound having a coordination ability to a metal to the reaction system because the stability of the reaction system can be remarkably improved. As such a stabilizer, compounds having metal coordination ability such as acetylacetone, tetramethylenediamine, ethylenediaminetetraacetic acid, pyridine and picoline are preferred.

ジルコニウム源としての主剤、テンプレート、溶媒、及び、安定化剤から成る反応系の組成は、主剤のモル比が0.01〜0.6、好ましくは0.02〜0.5、主剤/テンプレートのモル比が1〜30、好ましくは1〜10、溶媒/テンプレートのモル比が1から1000、好ましくは5〜500、安定化剤/主剤のモル比が、0.01〜1.0、好ましくは、0.2〜0.6である。   The composition of the reaction system comprising the main agent as a zirconium source, a template, a solvent, and a stabilizer has a molar ratio of the main agent of 0.01 to 0.6, preferably 0.02 to 0.5. The molar ratio is 1-30, preferably 1-10, the solvent / template molar ratio is 1-1000, preferably 5-500, and the stabilizer / main agent molar ratio is 0.01-1.0, preferably 0.2 to 0.6.

合成温度は、20〜180℃、好ましくは20〜100℃であり、合成時間は、5〜100時間、好ましくは10〜50時間である。反応生成物は、通常、濾過により分離し、十分に水洗後、乾燥し、次いで、含有しているテンプレートをアルコールなどの有機溶媒により抽出するなどの方法で除去することができる。   The synthesis temperature is 20 to 180 ° C., preferably 20 to 100 ° C., and the synthesis time is 5 to 100 hours, preferably 10 to 50 hours. The reaction product is usually separated by filtration, sufficiently washed with water, dried, and then removed by a method such as extraction of the contained template with an organic solvent such as alcohol.

この状態で得られるジルコニア材料は非晶質であるので、次に、結晶化を行う。
結晶化は、湿式で行う水熱処理法、ドライの雰囲気で加熱する乾熱処理法、等によって行うことができる。水熱処理法では、乾熱処理法に比べて、マイルドな温度条件にもかかわらず、より高い比表面積を有し、結晶構造的に単斜晶系を有する結晶性ジルコニア材料が得られる。水熱処理は、圧力容器に上記の非晶質ジルコニア材料を入れ、これに水溶液を加え、通常、100〜250℃で数分間から数十時間処理する。好ましい処理温度は130〜200℃であり、好ましい処理時間は20分から10時間である。
Since the zirconia material obtained in this state is amorphous, crystallization is performed next.
Crystallization can be performed by a hydrothermal treatment method performed in a wet manner, a dry heat treatment method in which heating is performed in a dry atmosphere, or the like. In the hydrothermal treatment method, a crystalline zirconia material having a higher specific surface area and a monoclinic crystal structure is obtained in spite of mild temperature conditions as compared with the dry heat treatment method. In the hydrothermal treatment, the above amorphous zirconia material is placed in a pressure vessel, an aqueous solution is added thereto, and the treatment is usually performed at 100 to 250 ° C. for several minutes to several tens of hours. A preferred treatment temperature is 130 to 200 ° C., and a preferred treatment time is 20 minutes to 10 hours.

水熱処理のための水溶液としては、水溶性の塩類を1〜30%程度溶解した水溶液を用いる。水溶液としては、例えば、硫酸亜鉛、塩化マグネシウム、硝酸カリウムなどの水溶液が好ましい。中でも、硫酸亜鉛水溶液は結晶化を著しく促進することができるので特に好ましい。
乾熱処理は、非晶質ジルコニア材料を、通常、空気中あるいは不活性ガスの雰囲気中、350〜600℃の温度で1時間から40時間加熱することによって行われる。
As an aqueous solution for hydrothermal treatment, an aqueous solution in which about 1 to 30% of water-soluble salts are dissolved is used. As the aqueous solution, for example, an aqueous solution of zinc sulfate, magnesium chloride, potassium nitrate or the like is preferable. Of these, an aqueous zinc sulfate solution is particularly preferred because it can significantly accelerate crystallization.
The dry heat treatment is performed by heating the amorphous zirconia material, usually in air or in an inert gas atmosphere, at a temperature of 350 to 600 ° C. for 1 to 40 hours.

本発明における触媒の調製は、多孔質結晶性ジルコニア材料に触媒を担持させることによって行う。触媒は一般に細かい粒子であるほど活性が高いので、実用触媒においてはいかにして微粒化を行うかが大きな課題である。また、触媒微粒子のシンタリングによる性能劣化を抑制することも課題となる。   In the present invention, the catalyst is prepared by supporting the catalyst on a porous crystalline zirconia material. In general, the finer the catalyst, the higher the activity. Therefore, in a practical catalyst, how to atomize is a big problem. It is also an issue to suppress performance deterioration due to sintering of catalyst fine particles.

本発明の重要な特徴の一つは、分散担持された触媒粒子の直径を1〜10nmとしたことである。本発明において、亜鉛とルテニウムの二元系触媒を用いる場合には、物理的・化学的に亜鉛元素とルテニウムの最適な混合状態を達成することが必要である。蒸発乾固法(触媒成分液に担体となる材料を浸漬した後、溶媒を蒸発させて活性成分を固定化する方法)、含浸法(触媒成分液を吸収した担体を乾燥して活性成分を固定化する方法)、共沈殿法(担体中に酸性の触媒成分液を吸収させ、アルカリ中に添加して触媒成分を沈殿させる方法)、その他、イオン交換法、混練法、など種々の方法を検討した結果、蒸発乾国法、含浸法、及び共沈殿法が担体に亜鉛とルテニウムを最適な共担持状態で担体上に分散させる上で効果的であることが分かった。尚、亜鉛とルテニウムの共担持は、別々に担持してもよいし、同時に担持してもよい。担体に担持された状態が、ルテニウムと亜鉛が近傍にいることが好ましく、特に亜鉛を担持してからルテニウムを担持するのが好ましい。   One important feature of the present invention is that the diameter of the dispersed and supported catalyst particles is 1 to 10 nm. In the present invention, when a binary catalyst of zinc and ruthenium is used, it is necessary to achieve an optimal mixed state of zinc element and ruthenium physically and chemically. Evaporation to dryness (method to immerse the carrier material in the catalyst component liquid and then evaporate the solvent to fix the active ingredient), impregnation method (dry the carrier that has absorbed the catalyst component liquid to fix the active ingredient) ), Coprecipitation method (method in which acidic catalyst component liquid is absorbed in the carrier and added to the alkali to precipitate the catalyst component), and other methods such as ion exchange and kneading methods are studied. As a result, it was found that the evaporative dry method, the impregnation method, and the coprecipitation method are effective in dispersing zinc and ruthenium on the support in an optimal co-supported state. The co-supporting of zinc and ruthenium may be supported separately or simultaneously. It is preferable that ruthenium and zinc be in the vicinity of the state of being supported on the carrier, and it is particularly preferable that ruthenium is supported after zinc is supported.

このように担体に分散担持されたルテニウム含有の触媒成分は、気相あるいは液相で還元活性化する。還元剤としては、水素、ヒドラジン、ホルマリン、水素化ホウ素ナトリウム等、従来公知の還元剤が使用できる。好ましくは水素が用いられる。通常、80〜450℃、好ましくは、100〜300℃の条件で活性化される。本発明で用いられる触媒は、反応前に水中で予備還元処理して用いるのが好ましい。   Thus, the ruthenium-containing catalyst component dispersed and supported on the carrier is reduced and activated in a gas phase or a liquid phase. As the reducing agent, conventionally known reducing agents such as hydrogen, hydrazine, formalin, sodium borohydride and the like can be used. Preferably hydrogen is used. Usually, it is activated at 80 to 450 ° C, preferably 100 to 300 ° C. The catalyst used in the present invention is preferably preliminarily reduced in water before the reaction.

本発明の固体触媒が部分水素化触媒として従来の触媒よりも高活性、高選択率で長期間触媒性能が維持されるのは、水熱・酸性の反応条件でも担体が安定であること、担体の細孔内にルテニウム触媒が均一に高分散担持されていること、細孔内に担持されたルテニウム触媒は担体に強く吸着しているので水熱条件でも触媒のシンタリングによる触媒劣化を起こし難いこと、担体lg当たりの触媒担持量を高くすることができるので従来の低担持率の触媒よりも被毒作用を受けにくいこと、等が影響しているものと考えられる。   The solid catalyst of the present invention has a higher activity and higher selectivity than conventional catalysts as a partial hydrogenation catalyst, and the catalyst performance is maintained for a long time because the support is stable even under hydrothermal and acidic reaction conditions. The ruthenium catalyst is uniformly and highly dispersed in the pores of the catalyst, and the ruthenium catalyst supported in the pores is strongly adsorbed on the carrier, so it is difficult to cause catalyst degradation due to catalyst sintering even under hydrothermal conditions. In addition, since the amount of the catalyst supported per gram of the carrier can be increased, it is considered that it is less susceptible to poisoning than the conventional catalyst having a low loading rate, and the like.

本発明の触媒の使用形態としては、スラリー懸濁方式あるいは成型触媒として固定層流通方式など、通常固体触媒を用いる方式が適用できる。また、本発明においては、水を反応系に存在させることが必要であり、水の存在量は、芳香族炭化水素に対して通常、0.01〜100重量倍が用いられる。ただし、反応条件下において、原料及び生成物を主成分とする有機物と水を含む液相が2液相を形成することが好ましく、実質的には0.5〜20重量倍がより好ましい。   As a usage form of the catalyst of the present invention, a system using a normal solid catalyst such as a slurry suspension system or a fixed bed circulation system as a molded catalyst can be applied. Moreover, in this invention, it is necessary to make water exist in a reaction system, and 0.01-100 weight times is normally used for the amount of water present with respect to an aromatic hydrocarbon. However, it is preferable that the liquid phase containing the organic substance mainly composed of the raw material and the product and water forms two liquid phases under the reaction conditions, and more preferably 0.5 to 20 times by weight.

さらに、本発明においては、触媒成分以外に金属化合物を反応系に存在させる方法が用いられる。この金属化合物としては、リチウム、ナトリウム、カリウムなどの周期律第1族元素、マグネシウム、カルシウム、ストロンチュームなどの第2族元素、及びマンガン、鉄、ニッケル、コバルト、亜鉛、銅などの金属化合物が例示される。   Furthermore, in the present invention, a method in which a metal compound is present in the reaction system in addition to the catalyst component is used. Examples of the metal compound include periodic group 1 elements such as lithium, sodium, and potassium; group 2 elements such as magnesium, calcium, and strontium; and metal compounds such as manganese, iron, nickel, cobalt, zinc, and copper. Illustrated.

金属化合物の種類としては、炭酸塩、酢酸塩、塩酸塩、硫酸塩、硝酸塩、酸化物、水酸化物が使用できる。特に有効な金属化合物としては、硫酸亜鉛、水酸化亜鉛、酸化亜鉛が好ましく、中でも硫酸亜鉛が最も好ましい。これらの金属化合物の添加量としては、反応系に存在する水に対して0.1重量倍〜飽和溶解量である。これらの金属化合物は単独で用いてもよく、2種以上を同時に用いてもよい。尚、反応系に存在させる金属化合物は、反応系内において、全てイオンとして存在してもよいし、化合物として存在してもよいし、その両方が混ざり合った状態でもよい。   As the types of metal compounds, carbonates, acetates, hydrochlorides, sulfates, nitrates, oxides and hydroxides can be used. As particularly effective metal compounds, zinc sulfate, zinc hydroxide, and zinc oxide are preferable, and zinc sulfate is most preferable. The addition amount of these metal compounds is 0.1 weight times to the saturated dissolution amount with respect to water present in the reaction system. These metal compounds may be used alone or in combination of two or more. In addition, all the metal compounds to be present in the reaction system may exist as ions in the reaction system, may exist as a compound, or may be in a state where both of them are mixed.

本発明においては、共存する水相を中性もしくは酸性条件下に保ち反応させることが好ましい。水相がアルカリ性になると特に反応速度が著しく低下するので好ましくない。好ましくは、水和のPHは0.5ないし7未満、さらに好ましくは2〜6.5である。   In the present invention, it is preferable to carry out the reaction by keeping the coexisting aqueous phase under neutral or acidic conditions. When the aqueous phase becomes alkaline, the reaction rate is particularly lowered, which is not preferable. Preferably the pH of hydration is 0.5 to less than 7, more preferably 2 to 6.5.

本発明の原料となる単環芳香族炭化水素とは、ベンゼン、トルエン、キシレン類、低級アルキルベンゼン類をいう。部分水素化反応の条件は、使用する触媒や添加物の種類、量によって適宜選択されるが、通常水素圧は0.1〜20MPa、好ましくは1〜10MPaの範囲であり、反応温度は50〜250℃、好ましくは100〜200℃の範囲である。また、反応時間は、目的とするシクロオレフィンの選択率や収率の実質的な目標を定め、適宜選択すればよく、特に制限はないが、通常数秒から数時間程度である。   The monocyclic aromatic hydrocarbon used as the raw material of the present invention refers to benzene, toluene, xylenes, and lower alkylbenzenes. The conditions for the partial hydrogenation reaction are appropriately selected depending on the type and amount of the catalyst and additives to be used. Usually, the hydrogen pressure is 0.1 to 20 MPa, preferably 1 to 10 MPa, and the reaction temperature is 50 to 50. 250 degreeC, Preferably it is the range of 100-200 degreeC. The reaction time may be appropriately selected by setting a substantial target of the selectivity and yield of the target cycloolefin, and is not particularly limited, but is usually about several seconds to several hours.

以下に実施例などを挙げて本発明を具体的に説明するが、本発明はこれら実施例などにより何ら限定されるものではない。   EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

まず、実施例等で得られたサンプルの評価方法について述べる。
粉末X線回折は理学電機社製RINT2000型X線回折装置により測定した。尚、ルテニウム金属の平均結晶子径は、ルテニウム金属の回折角(2θ)44°の回折ピークの広がりからシェラーの式により求めた。
First, a method for evaluating samples obtained in Examples and the like will be described.
Powder X-ray diffraction was measured with a RINT2000 X-ray diffractometer manufactured by Rigaku Corporation. The average crystallite diameter of ruthenium metal was determined by Scherrer's equation from the broadening of the diffraction peak of ruthenium metal having a diffraction angle (2θ) of 44 °.

比表面積及び細孔分布は、吸脱着の気体として窒素を用い、カルロエルパ社製ソープトマチック1800型装置によって測定した。尚、比表面積はBET法によって求め、細孔分布はBJH法で求められる微分分布で示される値を用いた。   The specific surface area and pore distribution were measured with a Sorpmatic 1800 type apparatus manufactured by Carlo Elpa, using nitrogen as the gas for adsorption and desorption. In addition, the specific surface area was calculated | required by BET method, and the value shown by the differential distribution calculated | required by BJH method was used for pore distribution.

触媒金属組成は蛍光X線分析によって測定した。反応場における溶出成分の測定は、理学JY−138−ICP発光分析装置により測定した。
熱分析は、島津製作所製DTA−50型熱分析装置によって昇温速度15℃/minで測定した。
The catalytic metal composition was measured by fluorescent X-ray analysis. The elution component in the reaction field was measured with a Rigaku JY-138-ICP emission spectrometer.
Thermal analysis was measured with a DTA-50 type thermal analyzer manufactured by Shimadzu Corporation at a temperature elevation rate of 15 ° C./min.

反応評価は、オートクレーブを用いたバッチ方式を採用し、経時的に抜き出した反応液をFID検知器付きのガスクロマトグラフ(島津製作所製GC−14A)にて分析することにより実施した。   The reaction evaluation was carried out by employing a batch method using an autoclave and analyzing the reaction liquid extracted over time with a gas chromatograph (GC-14A manufactured by Shimadzu Corporation) equipped with an FID detector.

なお、以下に記載するベンゼンの転化率及びシクロヘキセンの選択率は、実験の濃度分析値をもとに、次に示す式により算出したものである。
ベンゼンの転化率(%)=(反応により消費されたベンゼンのモル数)×100/(反応へ供給したベンゼンのモル数)
シクロヘキセン選択率(%)=(反応により生成したシクロヘキセンのモル数)×100/P
ただし、P(モル数)=(反応により生成したシクロヘキセンのモル数)+(反応により生成したシクロヘキサンのモル数)
The benzene conversion rate and cyclohexene selectivity described below were calculated by the following formula based on the experimental concentration analysis values.
Benzene conversion (%) = (number of moles of benzene consumed by reaction) × 100 / (number of moles of benzene supplied to the reaction)
Cyclohexene selectivity (%) = (number of moles of cyclohexene produced by reaction) × 100 / P
However, P (number of moles) = (number of moles of cyclohexene produced by the reaction) + (number of moles of cyclohexane produced by the reaction)

また、ルテニウム当たりの活性とは、触媒中に含まれるRu金属(g)当たりのベンゼン転化速度(g/Hr)を示したものであり、転化率50%を基準にして以下の計算式にて算出したものである。
Ru1g当たりの活性=使用したベンゼン量[g]×(1/2)×(1/転化率50%になるまでにかかった時間[Hr])×(1/使用したルテニウムの重量[g])
The activity per ruthenium indicates the benzene conversion rate (g / Hr) per Ru metal (g) contained in the catalyst, and is calculated by the following formula based on a conversion rate of 50%. It is calculated.
Activity per gram of Ru = amount of benzene used [g] × (1/2) × (1 / time taken to reach 50% conversion [Hr]) × (1 / weight of ruthenium [g] used)

(1)メソポーラスジルコニア材料の合成
蒸留水140ml、エタノール76ml、1−ヘキサデシルトリメチルアミンブロマイド21.8gの溶液を1Lのガラスビーカー中で攪拌しながら、これに、70%ジルコニウムテトラプロポキシド93.4g、エタノール100ml、アセチルアセトン8mlの混合溶液をゆっくり滴下し、室温でよく攪拌混合した後、次いで80℃に昇温した状態で静置した。その後120℃に温度を上げで16時間後に反応混合物を得た。反応混合物を濾過、水洗、乾燥を行った後、テンプレートをエタノールで抽出し、乾燥を行い白色の微粉末状生成物を20g得た。窒素吸脱着法による比表面積及び細孔分布を測定した結果、比表面積が546m/g、直径が2〜50nmの細孔が占める容積が0.77cm/gであり、全細孔容積の80%であった。粉末X線回折の結果、無秩序の細孔を有する非晶質のジルコニア材料であった。
(1) Synthesis of mesoporous zirconia material While stirring a solution of 140 ml of distilled water, 76 ml of ethanol, and 21.8 g of 1-hexadecyltrimethylamine bromide in a 1 L glass beaker, to this, 93.4 g of 70% zirconium tetrapropoxide, A mixed solution of 100 ml of ethanol and 8 ml of acetylacetone was slowly added dropwise and stirred and mixed well at room temperature, and then allowed to stand with the temperature raised to 80 ° C. Thereafter, the temperature was raised to 120 ° C., and a reaction mixture was obtained after 16 hours. The reaction mixture was filtered, washed with water and dried, and then the template was extracted with ethanol and dried to obtain 20 g of a white fine powder product. As a result of measuring the specific surface area and pore distribution by the nitrogen adsorption / desorption method, the specific surface area was 546 m 2 / g, the volume occupied by pores having a diameter of 2 to 50 nm was 0.77 cm 3 / g, and the total pore volume was 80%. As a result of powder X-ray diffraction, it was an amorphous zirconia material having disordered pores.

(2)メソポーラスジルコニアの結晶化
上記、非晶質材料10gを100ccのオートクレーブに入れ、10重量パーセントの硫酸亜鉛水溶液50gを加え、160℃で水熱処理をおこなった。処理後の粉末を濾過、水洗、乾燥し、9.8gの白色微粉末を得た。この白色微粉末の窒素吸脱着法による比表面積及び細孔分布を測定した結果、比表面積が424m/g、2〜50nmの細孔が占める細孔容積が1.04cm/g、全細孔容積が1.09cm/gであった。X線回折測定の結果、単斜晶系の相を有する結晶性パターンをわずかに示した。DTA測定の結果は、水熱処理する前の試料である非晶質ジルコニア材料は474℃において結晶化による発熱ピークを示したが、上記水熱処理を行った試料には、非晶質ジルコニアに由来する発熱ピークは観測されなかった。
(2) Crystallization of mesoporous zirconia 10 g of the above amorphous material was placed in a 100 cc autoclave, 50 g of 10 weight percent zinc sulfate aqueous solution was added, and hydrothermal treatment was performed at 160 ° C. The treated powder was filtered, washed with water and dried to obtain 9.8 g of white fine powder. As a result of measuring the specific surface area and pore distribution of this white fine powder by the nitrogen adsorption / desorption method, the specific surface area was 424 m 2 / g, the pore volume occupied by pores of 2 to 50 nm was 1.04 cm 3 / g, The pore volume was 1.09 cm 3 / g. As a result of X-ray diffraction measurement, a slightly crystalline pattern having a monoclinic phase was shown. The results of DTA measurement showed that the amorphous zirconia material, which was a sample before hydrothermal treatment, showed an exothermic peak due to crystallization at 474 ° C., but the hydrothermal treatment sample was derived from amorphous zirconia. An exothermic peak was not observed.

(3)固体触媒の調製
300mlの蒸発皿に、上記の結晶質ジルコニア材料5g、塩化ルテニウム塩酸水溶液(田中貴金属社製、ルテニウム8.39重量%含有)7. 5g、2重量%硝酸亜鉛水溶液7.5gを入れ、攪拌しながらウオーターバス上で充分に蒸発乾固した後、石英管に入れ、水素気流下で200℃還元処理を行った。次に、これを0.1N水酸化ナトリウム水溶液で洗浄し、濾過、水洗する処理を繰り返した後、乾燥した。得られた触媒を蛍光X線分析装置で分析したところルテニウムの担持量が10.4重量%であり、亜鉛/ルテニウムの原子比は0.11であった。X線回折の結果、約44°(2θ)の位置に触媒に由来するブロードなピークが現れ、このピークの半値幅から求めた一次粒子の直径は2.8nmであった。
(3) Preparation of solid catalyst In a 300 ml evaporating dish, 5 g of the above crystalline zirconia material, ruthenium chloride aqueous solution (manufactured by Tanaka Kikinzoku Co., Ltd., containing 8.39% by weight of ruthenium) 5 g of a 2% by weight zinc nitrate aqueous solution (7.5 g) was added, and the mixture was sufficiently evaporated and dried on a water bath with stirring, then placed in a quartz tube and subjected to a reduction treatment at 200 ° C. in a hydrogen stream. Next, this was washed with a 0.1N aqueous sodium hydroxide solution, filtered and washed repeatedly with water, and then dried. When the obtained catalyst was analyzed with a fluorescent X-ray analyzer, the supported amount of ruthenium was 10.4% by weight and the atomic ratio of zinc / ruthenium was 0.11. As a result of X-ray diffraction, a broad peak derived from the catalyst appeared at a position of about 44 ° (2θ), and the diameter of the primary particle obtained from the half width of this peak was 2.8 nm.

(4)ベンゼンの部分水素化
上記の固体触媒0.5gと10重量%の硫酸亜鉛水溶液280mlを1リットルのハステロイ製のオートクレーブに入れ、攪拌しながら水素で置換し、150℃に昇温した後、そのままの状態で22時間保持し、触媒スラリーの前処理をおこなった。次いでベンゼン140mlを圧入した後、全圧5MPaで高速攪拌しながら反応させた。この反応液を経時的に抜きだし、ガスクロマトグラフイーにより液相の組成を分析した。ベンゼンの転化率が50%時のシクロヘキセンの選択率と、ルテニウム当たりの活性を求めた。表1に反応成績を示す。
(4) Partial hydrogenation of benzene 0.5 g of the above solid catalyst and 280 ml of 10% by weight zinc sulfate aqueous solution were placed in a 1 liter Hastelloy autoclave, replaced with hydrogen while stirring, and heated to 150 ° C. Then, the catalyst slurry was kept for 22 hours, and the catalyst slurry was pretreated. Next, 140 ml of benzene was injected, and the reaction was carried out with high pressure stirring at a total pressure of 5 MPa. The reaction solution was extracted over time, and the composition of the liquid phase was analyzed by gas chromatography. The selectivity for cyclohexene at a benzene conversion of 50% and the activity per ruthenium were determined. Table 1 shows the reaction results.

実施例1の3で調製した固体触媒0.5gと10重量%の硫酸亜鉛水溶液280mlを1リットルのハステロイ製のオートクレーブに入れ、攪拌しながら水素で置換し、さらに150℃に昇温後、350時間保持し、触媒スラリーの前処理をおこなった。次いでベンゼン140mlを圧入した後、全圧5MPaで高速攪拌しながら反応させた。この反応液を経時的に抜きだし、ガスクロマトグラフイーにより油相の組成を分析した。ベンゼンの転化率が50%時のシクロヘキセンの選択率と、ルテニウム当たりの活性を求めた。表1に、反応成績を示す。   0.5 g of the solid catalyst prepared in 3 of Example 1 and 280 ml of a 10 wt% aqueous zinc sulfate solution were placed in a 1 liter Hastelloy autoclave, and replaced with hydrogen while stirring. The catalyst slurry was pretreated by holding for a period of time. Next, 140 ml of benzene was injected, and the reaction was carried out with high pressure stirring at a total pressure of 5 MPa. This reaction solution was extracted over time, and the composition of the oil phase was analyzed by gas chromatography. The selectivity for cyclohexene at a benzene conversion of 50% and the activity per ruthenium were determined. Table 1 shows the reaction results.

(1)メソポーラスジルコニア材料の合成
蒸留水427ml、エタノール427ml、1−ヘキサデシルトリメチルアミンブロマイド93.1gの溶液を3Lガラスビーカー中で攪拌しながら、これに、70%ジルコニウムテトラプロポキシド398.8g、エタノール427ml、アセチルアセトン17.1mlの混合溶液をゆっくり滴下し、室温で十分に攪拌混合した後、オートクレーブを用いて120℃で攪拌処理した。その後、オートクレーブより反応混合物を取り出し、エタノールによってテンプレートを抽出し、乾燥を行い白色の微粉末状生成物を98g得た。窒素吸脱着法による比表面積及び細孔分布を測定した結果、比表面積が456m/g、直径が2〜50nmの細孔が占める容積が0.63cm/gであり、全細孔容積の75%であった。粉末X線回折の結果、無秩序の細孔を有する非晶質のジルコニア材料であった。
(1) Synthesis of mesoporous zirconia material While stirring a solution of 427 ml of distilled water, 427 ml of ethanol, and 93.1 g of 1-hexadecyltrimethylamine bromide in a 3 L glass beaker, 398.8 g of 70% zirconium tetrapropoxide and ethanol A mixed solution of 427 ml and acetylacetone 17.1 ml was slowly added dropwise and the mixture was sufficiently stirred and mixed at room temperature, and then stirred at 120 ° C. using an autoclave. Thereafter, the reaction mixture was taken out of the autoclave, the template was extracted with ethanol, and dried to obtain 98 g of a white fine powder product. As a result of measuring the specific surface area and pore distribution by the nitrogen adsorption / desorption method, the specific surface area was 456 m 2 / g, the volume occupied by pores having a diameter of 2 to 50 nm was 0.63 cm 3 / g, and the total pore volume was 75%. As a result of powder X-ray diffraction, it was an amorphous zirconia material having disordered pores.

(2)メソポーラスジルコニアの結晶化
次に、この非晶質材料85gをステンレス製の1Lオートクレーブに入れ、10重量パーセントの硫酸亜鉛水溶液500gを加え、160℃で水熱処理した。処理後の粉末の濾過、水洗を繰り返し行い、その後、乾燥し、81gの白色微粉末を得た。この白色微粉末の窒素吸脱着法による比表面積及び細孔分布を測定した結果、比表面積が343m/g、2〜50nmの細孔が占める細孔容積が0.81cm/g、全細孔容積が1.0cm/gであった。X線回折測定の結果、単斜晶系の結晶相ピークが発現していることが確認された。
(2) Crystallization of mesoporous zirconia Next, 85 g of this amorphous material was put into a 1 L autoclave made of stainless steel, 500 g of a 10 weight percent zinc sulfate aqueous solution was added, and hydrothermal treatment was performed at 160 ° C. The treated powder was repeatedly filtered and washed with water, and then dried to obtain 81 g of white fine powder. As a result of measuring the specific surface area and pore distribution of this white fine powder by the nitrogen adsorption / desorption method, the specific surface area was 343 m 2 / g, the pore volume occupied by pores of 2 to 50 nm was 0.81 cm 3 / g, The pore volume was 1.0 cm 3 / g. As a result of X-ray diffraction measurement, it was confirmed that a monoclinic crystal phase peak was developed.

(3)固体触媒の調製
上記の結晶質ジルコニア材料80gに硝酸亜鉛の水和物24.6gを蒸留水75cc中に溶解した液を含浸し、減圧乾燥した後、焼成処理を実施した。さらに焼成処理を行った担体のうち60gを取り出し、塩化ルテニウム塩酸水溶液(田中貴金属社製、ルテニウム9.99重量%含有)55.3gに蒸留水18.5gを加えた液中に入れ、エバポレーターを使用して減圧乾固した後、石英管に入れ、水素気流下で200℃にて還元処理を行った。次に、これを0.1N水酸化ナトリウム水溶液で洗浄、さらに、濾過、水洗を繰り返した後乾燥した。得られた触媒を蛍光X線分析装置で分析したところルテニウムの担持量が10.1重量%であり、亜鉛/ルテニウムの原子比は0.21であった。尚、X線回折の結果、約44°(2θ)の位置に触媒に由来するブロードなピークが現れ、このピークの半値幅から求めた一次粒子の直径は2.9nmであった。
(3) Preparation of Solid Catalyst 80 g of the above crystalline zirconia material was impregnated with a solution obtained by dissolving 24.6 g of zinc nitrate hydrate in 75 cc of distilled water, dried under reduced pressure, and then subjected to a firing treatment. Further, 60 g of the carrier subjected to the calcination treatment was taken out and placed in a solution obtained by adding 18.5 g of distilled water to 55.3 g of a ruthenium chloride aqueous solution (produced by Tanaka Kikinzoku Co., Ltd., containing 9.99% by weight of ruthenium). After use and drying under reduced pressure, it was put into a quartz tube and subjected to reduction treatment at 200 ° C. under a hydrogen stream. Next, this was washed with a 0.1N aqueous sodium hydroxide solution, further filtered, washed with water and then dried. When the obtained catalyst was analyzed with a fluorescent X-ray analyzer, the supported amount of ruthenium was 10.1% by weight and the atomic ratio of zinc / ruthenium was 0.21. As a result of X-ray diffraction, a broad peak derived from the catalyst appeared at a position of about 44 ° (2θ), and the diameter of the primary particle obtained from the half width of this peak was 2.9 nm.

(4)ベンゼンの部分水素化
実施例1の3と同様に触媒を22Hr前処理した後、反応を行った。ベンゼンの転化率が50%時のシクロヘキセンの選択率と、ルテニウム当たりの活性を求めた。表1に反応成績を示す。
(4) Partial hydrogenation of benzene In the same manner as in Example 1-3, the catalyst was pretreated for 22 hours and then reacted. The selectivity for cyclohexene at a benzene conversion of 50% and the activity per ruthenium were determined. Table 1 shows the reaction results.

実施例3の(1)〜(3)と同様の方法により調製した触媒を用いて、実施例2と同様に触媒を350時間前処理した後、反応を行った。ベンゼンの転化率が50%時のシクロヘキセンの選択率と、ルテニウム当たりの活性を求めた。表1に反応成績を示す。   Using the catalyst prepared by the same method as in Example 3 (1) to (3), the catalyst was pretreated for 350 hours in the same manner as in Example 2 and then reacted. The selectivity for cyclohexene at a benzene conversion of 50% and the activity per ruthenium were determined. Table 1 shows the reaction results.

[比較例1]
(1)メソポーラスジルコニア材料の合成
蒸留水50ml、エタノール50ml、1−ヘキサデシルトリメチルアミンブロマイド10.9gの溶液を攪拌しながら、これに、70%ジルコニウムテトラプロポキシド46.7g、エタノール50ml、アセチルアセトン8mlの混合溶液をゆっくり滴下し、室温十分混合攪拌後、80℃で静置した。これをステンレス製のオートクレーブに移し、160℃で攪拌処理を行い反応混合物を得た。反応混合物を濾過、水洗、乾燥を行った後、エタノールによってテンプレートを抽出し、再度乾燥処理を行い白色の微粉末状生成物を9.6g得た。窒素吸脱着法による比表面積及び細孔分布を測定した結果、比表面積が655m/g、直径が2〜50nmの細孔が占める容積が0.84cm/gであり、全細孔容積の73%であった。粉末X線回折の結果、無秩序の細孔を有する非晶質のジルコニア材料であった。
[Comparative Example 1]
(1) Synthesis of mesoporous zirconia material While stirring a solution of 50 ml of distilled water, 50 ml of ethanol, and 10.9 g of 1-hexadecyltrimethylamine bromide, 46.7 g of 70% zirconium tetrapropoxide, 50 ml of ethanol, and 8 ml of acetylacetone were added. The mixed solution was slowly added dropwise, and the mixture was sufficiently stirred at room temperature and then allowed to stand at 80 ° C. This was transferred to a stainless steel autoclave and stirred at 160 ° C. to obtain a reaction mixture. The reaction mixture was filtered, washed with water and dried, and then the template was extracted with ethanol and dried again to obtain 9.6 g of a white fine powdery product. As a result of measuring the specific surface area and pore distribution by the nitrogen adsorption / desorption method, the specific surface area was 655 m 2 / g, the volume occupied by pores having a diameter of 2 to 50 nm was 0.84 cm 3 / g, and the total pore volume was It was 73%. As a result of powder X-ray diffraction, it was an amorphous zirconia material having disordered pores.

(2)固体触媒の調製
300mlの蒸発皿に、上記の結晶質ジルコニア材料5g、塩化ルテニウム塩酸水溶液(田中貴金属社製、ルテニウム8.39重量%含有)7. 5g、2%硝酸亜鉛水溶液7.5gを入れ、攪拌しながらウオーターバス上で充分に蒸発乾固した後、石英管に入れ、水素気流下で200℃にて還元処理を行った。次に、これを0.1N水酸化ナトリウム水溶液で洗浄、濾過、水洗する処理を十分実施した後、真空乾燥し、ルテニウムの担持量が10.2重量%の固体触媒を得た。亜鉛/ルテニウムの原子比は0.07であった。X線回折の結果、約44°(2θ)の位置に触媒に由来するブロードなピークが現れ、このピークの半値幅から求めた一次粒子の直径は2.7nmであった。
(2) Preparation of solid catalyst In a 300 ml evaporating dish, 5 g of the above crystalline zirconia material, ruthenium chloride aqueous solution (manufactured by Tanaka Kikinzoku Co., Ltd., containing 8.39% by weight of ruthenium) 5 g of a 2% zinc nitrate aqueous solution (5 g) was added, and the mixture was sufficiently evaporated and dried on a water bath with stirring. Then, the solution was placed in a quartz tube and subjected to reduction treatment at 200 ° C. under a hydrogen stream. Next, this was sufficiently washed with a 0.1N aqueous sodium hydroxide solution, filtered, and washed with water, followed by vacuum drying to obtain a solid catalyst having a ruthenium loading of 10.2% by weight. The atomic ratio of zinc / ruthenium was 0.07. As a result of X-ray diffraction, a broad peak derived from the catalyst appeared at a position of about 44 ° (2θ), and the diameter of the primary particle obtained from the half width of this peak was 2.7 nm.

(3)ベンゼンの部分水素化
上記の固体触媒0.5gと10重量%の硫酸亜鉛水溶液280mlを1Lのハステロイ製のオートクレーブに入れ、攪拌しながら水素で置換し、150℃に昇温した後、そのままの状態で22時間保持し、触媒スラリーの前処理をおこなった。次いでベンゼン140mlを圧入した後、全圧5MPaで高速攪拌しながら反応させた。この反応液を経時的に抜きだし、ガスクロマトグラフイーにより液相の組成を分析した。ベンゼンの転化率が50%時のシクロヘキセンの選択率と、ルテニウム当たりの活性を求めた。表1に反応成績を示す。
(3) Partial hydrogenation of benzene 0.5 g of the above solid catalyst and 280 ml of 10% by weight zinc sulfate aqueous solution were placed in a 1 L Hastelloy autoclave, replaced with hydrogen while stirring, and heated to 150 ° C. The catalyst slurry was kept for 22 hours in this state, and the catalyst slurry was pretreated. Next, 140 ml of benzene was injected, and the reaction was carried out with high pressure stirring at a total pressure of 5 MPa. The reaction solution was extracted over time, and the composition of the liquid phase was analyzed by gas chromatography. The selectivity for cyclohexene at a benzene conversion of 50% and the activity per ruthenium were determined. Table 1 shows the reaction results.

[比較例2]
比較例1の(1)、(2)と同様の方法により調製した触媒を用いて、実施例2と同様に触媒を350時間前処理した後、反応を行った。ベンゼンの転化率が50%時のシクロヘキセンの選択率と、ルテニウム当たりの活性を求めた。表1に反応成績を示す。
[Comparative Example 2]
Using a catalyst prepared by the same method as in (1) and (2) of Comparative Example 1, the catalyst was pretreated for 350 hours in the same manner as in Example 2 and then reacted. The selectivity for cyclohexene at a benzene conversion of 50% and the activity per ruthenium were determined. Table 1 shows the reaction results.

[比較例3]
(1)メソポーラスシリカ材料の合成
1リットルのビーカーに、蒸留水200g、エタノール160g及びドデシルアミン20gを入れ溶解させた。攪拌下でテトラエチルオルトシリケート83gを加えて十分攪拌した後、室温にて静置した。生成物を濾過、水洗し、乾燥した後、空気中でにて50で仮焼して、含有するドデシルアミンを除去した。これを、空気中で、600℃で焼成して、結晶質のメソポーラスシリカ材料を得た。窒素吸脱着法による比表面積及び細孔分布の結果、このシリカ材料はメソ細孔を有し、比表面積が650m/g、2〜50nmの細孔が占める容積は1.04cm/g、全細孔容積が1.22cm/gであった。
[Comparative Example 3]
(1) Synthesis of mesoporous silica material 200 g of distilled water, 160 g of ethanol, and 20 g of dodecylamine were dissolved in a 1 liter beaker. Under stirring, 83 g of tetraethylorthosilicate was added and stirred sufficiently, and then allowed to stand at room temperature. The product was filtered, washed with water, dried and calcined at 50 in air to remove the contained dodecylamine. This was fired in air at 600 ° C. to obtain a crystalline mesoporous silica material. As a result of the specific surface area and pore distribution by the nitrogen adsorption / desorption method, this silica material has mesopores, the specific surface area is 650 m 2 / g, the volume occupied by the pores of 2 to 50 nm is 1.04 cm 3 / g, The total pore volume was 1.22 cm 3 / g.

(2)固体触媒の調製
上記の結晶質シリカ材料5gを用いた以外には、実施例1の(3)に記載の触媒調製法と同様の方法で処理することにより、ルテニウム担持の固体触媒を得た。得られた固体触媒は、ルテニウムの担持率が9.9重量%、亜鉛/ルテニウムの原子比は0.10であった。
(2) Preparation of solid catalyst Except for using 5 g of the above-described crystalline silica material, a ruthenium-supported solid catalyst was obtained by treating in the same manner as the catalyst preparation method described in (1) of Example 1. Obtained. The obtained solid catalyst had a ruthenium loading of 9.9% by weight and a zinc / ruthenium atomic ratio of 0.10.

(3)ベンゼンの部分水素化
上記の固体触媒を0.5g用いた以外には実施例1の(4)と同様の方法でベンゼンの部分水素化を行った。表1に、反応成績を示す。
(3) Partial hydrogenation of benzene Partial hydrogenation of benzene was performed in the same manner as in (4) of Example 1 except that 0.5 g of the above solid catalyst was used. Table 1 shows the reaction results.

[比較例4]
比較例1の2で得た触媒0.5gを用いた以外には実施例2と同様の方法でベンゼンの部分水素化を行った。表1に反応成績を示す。
[Comparative Example 4]
Partial hydrogenation of benzene was performed in the same manner as in Example 2 except that 0.5 g of the catalyst obtained in 2 of Comparative Example 1 was used. Table 1 shows the reaction results.

Figure 0004931099
Figure 0004931099

本発明の固体触媒は、比較例の触媒と比較して、ルテニウム当たりの活性とシクロヘキセンの選択率が高く、反応前に水熱・酸性条件下に長時間浸漬した後でも高い活性と選択率が維持されることがわかった。   The solid catalyst of the present invention has higher activity per ruthenium and selectivity of cyclohexene than the catalyst of the comparative example, and has high activity and selectivity even after being immersed in hydrothermal / acidic conditions for a long time before the reaction. It was found that it was maintained.

[担体の水熱安定性試験]
実施例1の1で合成した結晶性ジルコニア材料2gと10重量%の硫酸亜鉛水溶液50g(該水溶液のPHは室温で5.5である)を200mlのオートクレーブに入れ、160℃にて攪拌処理した。室温に放冷後、溶液をメンブレンフイルターで濾過し、濾液をサンプリングし、濾液に含まれるジルコニウム溶出量を求めた。その結果、水溶液中に含まれるジルコニウムの量は、分析法の検出限界である2ppm以下であった。比較のために、比較例3の1で合成したシリカ材料2gを同様の方法で処理し、濾液に含まれるケイ素の溶出量を求めた。その結果、水溶液中に含まれるケイ素の量は830PPMであった。
[Hydrothermal stability test of carrier]
2 g of the crystalline zirconia material synthesized in 1 of Example 1 and 50 g of a 10 wt% aqueous zinc sulfate solution (PH of the aqueous solution is 5.5 at room temperature) were placed in a 200 ml autoclave and stirred at 160 ° C. . After cooling to room temperature, the solution was filtered through a membrane filter, the filtrate was sampled, and the amount of zirconium eluted contained in the filtrate was determined. As a result, the amount of zirconium contained in the aqueous solution was 2 ppm or less, which is the detection limit of the analytical method. For comparison, 2 g of the silica material synthesized in 1 of Comparative Example 3 was treated in the same manner, and the elution amount of silicon contained in the filtrate was determined. As a result, the amount of silicon contained in the aqueous solution was 830 PPM.

本発明の触媒は、担体として特定の比表面積を有するメソポーラスジルコニア材料を用いているため、従来の触媒に比べると水熱・酸性条件においても担体の溶解がなく、担体の結晶構造の変化も起こさず安定しているため、極めて高い触媒活性と格段に長い触媒ライフを示すので、単環芳香族炭化水素の水存在下での部分水素化によるシクロオレフィンの製造用触媒としての利用性が高い。   Since the catalyst of the present invention uses a mesoporous zirconia material having a specific specific surface area as a support, the support does not dissolve even under hydrothermal and acidic conditions, and the crystal structure of the support changes. Since it is very stable, it exhibits an extremely high catalytic activity and an extremely long catalyst life, so that it is highly usable as a catalyst for producing cycloolefin by partial hydrogenation of monocyclic aromatic hydrocarbons in the presence of water.

Claims (5)

単環芳香族炭化水素の部分水素化により、シクロオレフィンを製造する触媒において、比表面積が30〜800m/gの範囲内にある単斜晶系の結晶性を有する結晶性メソポーラスジルコニア材料を担体として用い、その担体にルテニウムを担持させて構成されるシクロオレフィン製造用触媒。 In a catalyst for producing cycloolefin by partial hydrogenation of monocyclic aromatic hydrocarbon , a crystalline mesoporous zirconia material having a monoclinic crystallinity having a specific surface area in the range of 30 to 800 m 2 / g is supported. A catalyst for producing cycloolefin comprising ruthenium supported on the carrier. 前記比表面積が80〜500m/gの範囲内にあることを特徴とする請求項1記載のシクロオレフィン製造用触媒。 Cyclo olefin production catalyst according to claim 1, wherein the specific surface area, characterized in that in the range of 80~500m 2 / g. 前記シクロオレフィン製造用触媒が、亜鉛もしくは亜鉛化合物を含有していることを特徴とする請求項1又は2記載のシクロオレフィン製造用触媒。   The catalyst for producing cycloolefin according to claim 1 or 2, wherein the catalyst for producing cycloolefin contains zinc or a zinc compound. 単環芳香族炭化水素の部分水素化によ、シクロオレフィンを製造するに際して、請求項1〜3のいずれかに記載の触媒を用いて、水の存在下、液相にて単環芳香族炭化水素を部分水素化することを特徴とするシクロオレフィンの製造方法。 Ri by the partial hydrogenation of monocyclic aromatic hydrocarbons, in manufacturing the cycloolefin using a catalyst according to any one of claims 1 to 3, the presence of water, monocyclic aromatic in the liquid phase A process for producing a cycloolefin, characterized by partially hydrogenating a hydrocarbon. 前記液相に亜鉛化合物もしくは亜鉛イオン、またはその両方を存在させることを特徴とする請求項4記載のシクロオレフィンの製造方法。   The method for producing a cycloolefin according to claim 4, wherein a zinc compound or zinc ions or both are present in the liquid phase.
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