WO2018159436A1 - Catalyst for nuclear hydrogenation reaction - Google Patents
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- WO2018159436A1 WO2018159436A1 PCT/JP2018/006392 JP2018006392W WO2018159436A1 WO 2018159436 A1 WO2018159436 A1 WO 2018159436A1 JP 2018006392 W JP2018006392 W JP 2018006392W WO 2018159436 A1 WO2018159436 A1 WO 2018159436A1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/16—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring
- C07C13/18—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring with a cyclohexane ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- the present invention relates to a catalyst used for a nuclear hydrogenation reaction of an aromatic compound.
- a ruthenium catalyst is known as a catalyst used in the nuclear hydrogenation reaction of an aromatic compound.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2009-286747 efficiently discloses N, N-dimethylcyclohexylamines that are useful as catalysts for polyurethane foam production, epoxy curing agents, resist stripping agents, and corrosion inhibitors for steel.
- an aromatic compound is subjected to a nuclear hydrogenation reaction in the presence of a ruthenium catalyst or the like and hydrogen, and the resulting cyclohexyl compound is converted into the above-mentioned noble metal catalyst, formaldehyde derivative and hydrogen.
- Patent Document 1 [Summary]
- ruthenium catalyst in which 5% of ruthenium is supported on alumina (support) is disclosed (Patent Document 1, [0032] Example 1 and [0034] Example 2).
- An object of the present invention is to provide a catalyst for nuclear hydrogenation reaction having catalytic activity.
- the inventors of the present invention focused on the state of ruthenium contained in the catalyst particles supported on the support, and conducted intensive studies on a configuration that further improves the catalytic activity. It was.
- the ratio of Ru (zero valence) to the ratio R RuOx in the analysis region near the surface of the ruthenium catalyst measured by X-ray photoelectron spectroscopy (XPS) satisfies the following conditions:
- the present inventors have found that it is effective for improving the catalytic activity and have completed the present invention.
- this invention is comprised by the following technical matters. That is, the present invention A nuclear hydrogenation catalyst used in a nuclear hydrogenation reaction for hydrogenating at least one ⁇ bond of an aromatic ring of an aromatic compound, A support, and catalyst particles supported on the support, The catalyst particles contain Ru (zero valence) and Ru oxide as constituent components, The ratio R Ru (atom%) of Ru (zero valence) and the ratio R RuOx (atom%) of Ru oxide in the analysis region near the surface measured by X-ray photoelectron spectroscopy (XPS) are as follows. Satisfies the condition of equation (1), Provided is a catalyst for nuclear hydrogenation reaction. 0.50 ⁇ (R Ru / R RuOx ) ⁇ 4.00 (1)
- the Ru (zero valence) ratio R Ru (atom%) and the Ru oxide ratio R RuOx (atom%) in the analysis region near the surface of the nuclear hydrogenation reaction catalyst observed by XPS. %) Is a numerical value calculated under the condition that the sum of these two components is 100%.
- the nuclear hydrogenation reaction catalyst of the present invention when the value of (R Ru / R RuOx ) represented by the above formula (1) is 0.50 or more and 4.00 or less, the nuclear hydrogenation reaction catalyst of the present invention is In the nuclear hydrogenation reaction of an aromatic compound, it is possible to exhibit an excellent catalytic activity capable of obtaining a conversion ratio of a reactant superior to that of a conventional ruthenium catalyst.
- the catalyst for nuclear hydrogenation reaction of the present invention has an excellent catalytic activity has not been sufficiently elucidated, but the present inventors consider as follows. That is, the nuclear hydrogenation reaction catalyst having a structure satisfying the formula (1) has a higher ratio of Ru (0 valence) to Ru oxide than the conventional nuclear hydrogenation reaction catalyst. It is presumed that the activity against the reaction is improved.
- the measurement conditions by XPS are the following (A1) to (A5).
- (A1) X-ray source: Monochromatic AlK ⁇ (A2) Photoelectron extraction accuracy: ⁇ 75 ° C. (see FIG. 1 described later)
- the support is preferably an alumina support.
- the pore size PS required by the BJH method for the alumina support is 8.00 nm to 12.00 nm. it is preferred pore volume PV obtained by BJH method is 0.250cm 3 /g ⁇ 0.400cm 3 / g.
- the pore diameter PS is determined from the desorption isotherm, which is the relationship between the relative pressure and the adsorption amount when the adsorbate (gas molecule) is desorbed from the solid surface by the BJH (Barrett, Joyner, Hallender) method. This is the required value (BJH Desorption average pore diameter).
- the pore volume PV is also a value determined by the BJH method (BJH Desorption cumulative volume of pores between 1.7000 nm and 300.0000 nm diameter).
- the nuclear hydrogenation reaction catalyst which has the outstanding catalytic activity which can obtain the conversion ratio of the reaction material superior to the conventional ruthenium catalyst in the nuclear hydrogenation reaction of an aromatic compound is provided. .
- FIG. 1 It is a schematic diagram which shows schematic structure of the XPS apparatus for demonstrating the analysis conditions of the X-ray photoelectron spectroscopy (XPS) in this invention.
- the hydrogenation reaction catalyst of the present invention is used for a nuclear hydrogenation reaction.
- the aromatic ring ⁇ bond of diphenylmethane (compound 1 in reaction formula (1)) represented by the following chemical reaction formula (1) is hydrogenated to form ⁇ -cyclohexyltoluene (reaction formula (1) It can be used for the nuclear hydrogenation reaction to convert compound 2) in 1) and dicyclohexylmethane (compound 3 in reaction formula (1)).
- the nuclear hydrogenation reaction catalyst of the present invention includes a support and catalyst particles supported on the support, and the catalyst particles include Ru (zero-valent) and Ru oxide as constituent components.
- Ru zero-valent
- Ru oxide as constituent components.
- XPS X-ray photoelectron spectroscopy
- Ru (zero valence) ratio R Ru (atom%) and Ru oxide ratio R RuO x (atom%) Satisfies the condition of the following formula (1). 0.50 ⁇ (R Ru / R RuOx ) ⁇ 4.00 (1)
- the catalyst for nuclear hydrogenation reaction of the present invention only needs to contain a support and catalyst particles supported on the support, and there is no particular limitation on the form of support of the catalyst particles, and various structures are adopted. obtain.
- the support is not particularly limited as long as it can support catalyst particles and has a relatively large surface area, but it has good dispersibility in a solution containing catalyst particles and is inert. preferable.
- the inert carrier for example, carbon-based material (carbon), silica, alumina, AMD carmina, magnesia and the like are preferable, and alumina (alumina carrier) is particularly preferable.
- carbon-based material include glassy carbon (GC), fine carbon, carbon black, graphite, carbon fiber, activated carbon, pulverized activated carbon, carbon nanofiber, and carbon nanotube.
- conductive carbon is preferable, and as the conductive carbon, conductive carbon black is particularly preferable.
- conductive carbon black include trade names “Ketjen Black EC300J”, “Ketjen Black EC600”, “Carbon EPC” and the like (manufactured by Lion Chemical Co., Ltd.).
- alumina support with a pore size PS obtained by BJH method is 8.00nm ⁇ 12.00nm
- a pore volume PV obtained by BJH method 0.250cm 3 /g ⁇ 0.400cm 3 / g It is preferable that
- the pore diameter PS is a value obtained from a desorption isotherm (BJH) which is a relationship between a relative pressure and an adsorption amount when an adsorbate (gas molecule) desorbs from a solid surface by the BJH (Barrett, Joyner, Hallender) method. Desorption average pore diameter).
- the pore volume PV is also a value determined by the BJH method (BJH Desorption cumulative volume of pores between 1.7000 nm and 300.0000 nm diameter).
- the catalyst particles supported on the carrier in the present invention contain Ru (zero valence) and Ru oxide as constituent components, and are measured by X-ray photoelectron spectroscopy (XPS) as described above.
- XPS X-ray photoelectron spectroscopy
- the Ru (zero valence) ratio R Ru (atom%) and the Ru oxide ratio R RuOx (atom%) satisfy the condition of the following formula (1). 0.50 ⁇ (R Ru / R RuOx ) ⁇ 4.00 (1)
- the amount of the catalyst particles supported on the carrier is not particularly limited as long as the effects of the present invention are not impaired, and the reaction system, reaction conditions, and the like in which the catalyst for nuclear hydrogenation reaction of the present invention is employed. It is appropriately set depending on the manufacturing cost. Usually, it may be about 0.5 to 10% by mass.
- the supported amount refers to a value (rate) obtained by the formula: ⁇ mass of catalyst particles / (mass of catalyst particles + mass of support) ⁇ ⁇ 100.
- the catalyst for nuclear hydrogenation reaction can exhibit an excellent catalytic activity capable of obtaining a conversion rate of a reactant superior to that of a conventional ruthenium catalyst in the nuclear hydrogenation reaction of an aromatic compound.
- the value of (R Ru / R RuOx ) is the ratio R Ru (0 valence) of Ru (zero valence) in the analysis region in the vicinity of the surface of the catalyst particle for nuclear hydrogenation reaction measured by X-ray photoelectron spectroscopy (XPS). atom%) and the Ru oxide ratio R RuOx (atom%), which indicates the supported ratio of Ru (zero valence) and Ru oxide.
- X-ray photoelectron spectroscopy is carried out under the following analysis conditions (A1) to (A5).
- A1 X-ray source: Monochromatic AlK ⁇
- A3) Charging correction: C1s peak energy is corrected to 284.8 eV
- A4) Analysis area: 200 ⁇ m
- A5) Analysis chamber pressure: about 1 ⁇ 10 ⁇ 6 Pa
- the photoelectron extraction accuracy ⁇ of (A2) is, as shown in FIG. 1, the X-ray emitted from the X-ray source 32 is irradiated to the sample set on the sample stage 34 and is emitted from the sample.
- the angle ⁇ when the photoelectron is received by the spectroscope 36 corresponds to the angle between the light receiving axis of the spectrometer 36 and the surface of the sample layer of the sample stage 34.
- the method for producing the catalyst for nuclear hydrogenation reaction of the present invention is not particularly limited as long as the catalyst particles can be supported on a carrier.
- an impregnation method in which a solution containing a Ru compound is brought into contact with a support and a catalyst component is impregnated in the support
- a liquid phase reduction method in which a reducing agent is added to a solution containing the catalyst component
- an electrochemical deposition method a chemical
- the production method include a reduction method, a reduction precipitation method using adsorbed hydrogen, and the like.
- the production conditions in the production of the catalyst for nuclear hydrogenation reaction are the ratio R Ru (atom%) of Ru (zero valence) in the analysis region near the surface measured by X-ray photoelectron spectroscopy (XPS),
- the Ru oxide ratio R RuOx (atom%) is adjusted so as to satisfy the condition of the following formula (1). 0.50 ⁇ (R Ru / R RuOx ) ⁇ 4.00 (1)
- the catalyst for nuclear hydrogenation reaction of the present invention has the conditions indicated by the above-mentioned formula (1) and the average value of crystallite size measured by powder X-ray diffraction (XRD) (preferably 3 to There are no particular restrictions on the method for producing the film so as to satisfy the conditions for adjusting to 16.0 nm.
- XRD powder X-ray diffraction
- the chemical composition and structure of a product (catalyst) are analyzed using various known analysis techniques, and the obtained analysis results are fed back to the production process, and the raw material to be selected and the raw material are selected. And a method of preparing / changing the compounding ratio, the synthesis reaction to be selected, the reaction conditions of the synthesis reaction, and the like.
- Example 1 As a catalyst for nuclear hydrogenation reaction of Example 1 in which catalyst particles containing Ru (0 valence) and Ru oxide are supported on alumina (Al 2 O 3 ) particles as a support at a support ratio of 5 mass%, The name “HYAc-5E A-type” (manufactured by NE CHEMCAT) was produced. Table 1 shows the (R Ru / R RuOx ) value of the nuclear hydrogenation reaction catalyst 1 determined as described below, and the pore diameter PS and pore volume PV of the alumina particles of the support.
- Example 2 and Example 3 The catalyst for nuclear hydrogenation reaction of Example 2 (Example 2) was changed in the same manner as in Example 1 except that the value of (R Ru / R RuOx ) in the obtained catalyst for nuclear hydrogenation reaction was changed to that shown in Table 1.
- Product name “HYAc-5E B-type” (manufactured by NE CHEMCAT) and catalyst for nuclear hydrogenation reaction of Example 3 (trade name “HYAc-5E C-type”, manufactured by NE CHEMCAT) Manufactured.
- Example 4 The catalyst for nuclear hydrogenation reaction of Example 4 (trade name “HYAc-5E F” was used in the same manner as in Example 1 except that the carrier having the pore diameter PS and pore volume PV shown in Table 1 was used as the carrier. -Type ", manufactured by NE CHEMCAT).
- the amount of the nuclear hydrogenation reaction catalyst used is 0.4 mol% of the raw material diphenylmethane (compound 1 in the reaction formula (1)), and hydrogen gas is supplied so that the pressure becomes 0.2 MPa. While raising the temperature to 50 ° C., the reaction was carried out under the conditions of the temperature rise holding time shown in Table 1.
- the conversion rate (%) of diphenylmethane was calculated by measuring the content ratio (mass) of diphenylmethane, ⁇ -cyclohexyltoluene and dicyclohexylmethane in the mixed composition after the reaction. It was shown to.
- the catalyst for nuclear hydrogenation reaction of the present invention has an excellent catalytic activity, and can obtain an excellent conversion rate of a reactant in the nuclear hydrogenation reaction of an aromatic compound. Accordingly, the present invention is a nuclear hydrogenation reaction catalyst that can be applied to the synthesis of epoxy resins, polyamideimide resins, and the like, which are raw materials for high-performance plastic products, and contributes to the development of various industries.
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Abstract
The purpose of the present invention is to provide a catalyst for a nuclear hydrogenation reaction having superior catalytic activity that can give a conversion rate for reaction products superior to conventional ruthenium catalysts in a nuclear hydrogenation reaction for an aromatic compound. Provided is a catalyst for a nuclear hydrogenation reaction used in a nuclear hydrogenation reaction for hydrogenation of at least one π bond of an aromatic ring in an aromatic compound, wherein the catalyst includes a carrier and catalyst particles supported on that carrier. The catalyst particles include Ru (0 valence) and Ru oxide as constituent components. In analyzed areas in the vicinity of the surface measured by x-ray photoelectron spectroscopy (XPS) the proportion RRu (atom%) of Ru (0 valence) and the proportion RRuOx (atom%) of Ru oxide satisfy the conditions in Equation (1). 0.50 ≤ (RRu/RRuOx) ≤ 4.00 ... Equation (1)
Description
本発明は、芳香族化合物の核水添反応に使用される触媒に関する。
The present invention relates to a catalyst used for a nuclear hydrogenation reaction of an aromatic compound.
従来から、芳香族化合物の核水添反応は、高機能プラスチック製品の原料となるエポキシ樹脂やポリアミドイミド樹脂等を合成するために利用されている。そして、芳香族化合物の核水添反応に使用される触媒としてはルテニウム触媒が知られている。
Conventionally, the nuclear hydrogenation reaction of aromatic compounds has been used to synthesize epoxy resins, polyamideimide resins, and the like, which are raw materials for high-performance plastic products. A ruthenium catalyst is known as a catalyst used in the nuclear hydrogenation reaction of an aromatic compound.
例えば、特許文献１（特開２００９－２８６７４７号公報）には、ポリウレタンフォーム製造用触媒、エポキシ硬化剤、レジスト剥離剤、鋼用腐食防止剤として有用なＮ，Ｎ－ジメチルシクロヘキシルアミン類を効率的に経済性良く製造する方法を提供することを目的とし、芳香族化合物をルテニウム触媒等及び水素の存在下で核水添反応させ、得られたシクロヘキシル化合物を、前記貴金属触媒、ホルムアルデヒド誘導体及び水素の存在下で還元メチル化反応させるＮ，Ｎ－ジメチルシクロへキシルアミン類の製造法が開示されている（特許文献１、［要約］）。
For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2009-286747) efficiently discloses N, N-dimethylcyclohexylamines that are useful as catalysts for polyurethane foam production, epoxy curing agents, resist stripping agents, and corrosion inhibitors for steel. For the purpose of providing a process for producing a product economically, an aromatic compound is subjected to a nuclear hydrogenation reaction in the presence of a ruthenium catalyst or the like and hydrogen, and the resulting cyclohexyl compound is converted into the above-mentioned noble metal catalyst, formaldehyde derivative and hydrogen. A method for producing N, N-dimethylcyclohexylamines by reductive methylation reaction in the presence is disclosed (Patent Document 1, [Summary]).
より具体的には、アルミナ（担体）にルテニウムが５％担持されたルテニウム触媒が開示されている（特許文献１、［００３２］実施例１及び［００３４］実施例２等）。
More specifically, a ruthenium catalyst in which 5% of ruthenium is supported on alumina (support) is disclosed (Patent Document 1, [0032] Example 1 and [0034] Example 2).
しかしながら、上記のような従来のルテニウム触媒では、芳香族化合物の核水添反応において反応物の転化率をより向上させるという観点からは、未だ改善の余地があることを本発明者らは見出した。
However, the present inventors have found that there is still room for improvement in the conventional ruthenium catalyst as described above from the viewpoint of further improving the conversion rate of the reactant in the nuclear hydrogenation reaction of the aromatic compound. .
そこで、本発明は、かかる技術的事情に鑑みてなされたものであって、芳香族化合物の核水添反応において、従来のルテニウム触媒よりも優れた反応物の転化率を得ることのできる優れた触媒活性を有する核水添反応用触媒を提供することを目的とする。
Therefore, the present invention has been made in view of such technical circumstances, and in the nuclear hydrogenation reaction of an aromatic compound, the conversion rate of the reaction product superior to that of a conventional ruthenium catalyst can be obtained. An object of the present invention is to provide a catalyst for nuclear hydrogenation reaction having catalytic activity.
本件発明者らは、核水添反応に用いられるルテニウム触媒において、担体上に担持される触媒粒子に含まれるルテニウムの状態に着目し、触媒活性の更なる向上を実現する構成について鋭意検討を行った。
In the ruthenium catalyst used in the nuclear hydrogenation reaction, the inventors of the present invention focused on the state of ruthenium contained in the catalyst particles supported on the support, and conducted intensive studies on a configuration that further improves the catalytic activity. It was.
その結果、Ｘ線光電子分光分析法（ＸＰＳ）により測定されるルテニウム触媒の表面近傍の分析領域におけるＲｕ酸化物の割合ＲＲｕＯｘに対するＲｕ（０価）の割合が下記の条件を満たしていることが触媒活性の向上に有効であることを見出し、本発明を完成するに至った。
As a result, the ratio of Ru (zero valence) to the ratio R RuOx in the analysis region near the surface of the ruthenium catalyst measured by X-ray photoelectron spectroscopy (XPS) satisfies the following conditions: The present inventors have found that it is effective for improving the catalytic activity and have completed the present invention.
より具体的には、本発明は、以下の技術的事項により構成される。
即ち、本発明は、
芳香族化合物の芳香環のπ結合の少なくとも１つを水素化する核水添反応に使用される核水添反応用触媒であって、
担体と、前記担体上に担持される触媒粒子と、を含んでおり、
前記触媒粒子が、Ｒｕ（０価）とＲｕ酸化物とを構成成分として含んでおり、
Ｘ線光電子分光分析法（ＸＰＳ）により測定される表面近傍の分析領域における、Ｒｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）と、Ｒｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）とが、下記式（１）の条件を満たしている、
核水添反応用触媒を提供する。
０．５０≦（ＲＲｕ／ＲＲｕＯｘ）≦４．００・・・式（１） More specifically, this invention is comprised by the following technical matters.
That is, the present invention
A nuclear hydrogenation catalyst used in a nuclear hydrogenation reaction for hydrogenating at least one π bond of an aromatic ring of an aromatic compound,
A support, and catalyst particles supported on the support,
The catalyst particles contain Ru (zero valence) and Ru oxide as constituent components,
The ratio R Ru (atom%) of Ru (zero valence) and the ratio R RuOx (atom%) of Ru oxide in the analysis region near the surface measured by X-ray photoelectron spectroscopy (XPS) are as follows. Satisfies the condition of equation (1),
Provided is a catalyst for nuclear hydrogenation reaction.
0.50 ≦ (R Ru / R RuOx ) ≦ 4.00 (1)
即ち、本発明は、
芳香族化合物の芳香環のπ結合の少なくとも１つを水素化する核水添反応に使用される核水添反応用触媒であって、
担体と、前記担体上に担持される触媒粒子と、を含んでおり、
前記触媒粒子が、Ｒｕ（０価）とＲｕ酸化物とを構成成分として含んでおり、
Ｘ線光電子分光分析法（ＸＰＳ）により測定される表面近傍の分析領域における、Ｒｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）と、Ｒｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）とが、下記式（１）の条件を満たしている、
核水添反応用触媒を提供する。
０．５０≦（ＲＲｕ／ＲＲｕＯｘ）≦４．００・・・式（１） More specifically, this invention is comprised by the following technical matters.
That is, the present invention
A nuclear hydrogenation catalyst used in a nuclear hydrogenation reaction for hydrogenating at least one π bond of an aromatic ring of an aromatic compound,
A support, and catalyst particles supported on the support,
The catalyst particles contain Ru (zero valence) and Ru oxide as constituent components,
The ratio R Ru (atom%) of Ru (zero valence) and the ratio R RuOx (atom%) of Ru oxide in the analysis region near the surface measured by X-ray photoelectron spectroscopy (XPS) are as follows. Satisfies the condition of equation (1),
Provided is a catalyst for nuclear hydrogenation reaction.
0.50 ≦ (R Ru / R RuOx ) ≦ 4.00 (1)
ここで、本発明においては、ＸＰＳで観察される核水添反応用触媒の表面近傍の分析領域におけるＲｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）と、Ｒｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）とは、これら２つの成分の合計が１００％となる条件で算出される数値としている。
Here, in the present invention, the Ru (zero valence) ratio R Ru (atom%) and the Ru oxide ratio R RuOx (atom%) in the analysis region near the surface of the nuclear hydrogenation reaction catalyst observed by XPS. %) Is a numerical value calculated under the condition that the sum of these two components is 100%.
本発明において、上記式（１）に示される（ＲＲｕ／ＲＲｕＯｘ）の値が０．５０以上で４．００以下となる構成とすることにより、本発明の核水添反応用触媒は、芳香族化合物の核水添反応において、従来のルテニウム触媒よりも優れた反応物の転化率を得ることのできる優れた触媒活性を発揮することができる。
In the present invention, when the value of (R Ru / R RuOx ) represented by the above formula (1) is 0.50 or more and 4.00 or less, the nuclear hydrogenation reaction catalyst of the present invention is In the nuclear hydrogenation reaction of an aromatic compound, it is possible to exhibit an excellent catalytic activity capable of obtaining a conversion ratio of a reactant superior to that of a conventional ruthenium catalyst.
本発明の核水添反応用触媒が優れた触媒活性を有することについて詳細な理由は十分に解明されていないが、本発明者らは、以下のように考えている。即ち、式（１）を満たす構造の核水添反応用触媒は、Ｒｕ酸化物に対するＲｕ（０価）の割合が従来の核水添反応用触媒よりも高いので、芳香族化合物の核水添反応に対する活性が向上していると推察している。
The detailed reason why the catalyst for nuclear hydrogenation reaction of the present invention has an excellent catalytic activity has not been sufficiently elucidated, but the present inventors consider as follows. That is, the nuclear hydrogenation reaction catalyst having a structure satisfying the formula (1) has a higher ratio of Ru (0 valence) to Ru oxide than the conventional nuclear hydrogenation reaction catalyst. It is presumed that the activity against the reaction is improved.
ここで、本発明において、ＸＰＳによる測定条件は以下の（Ａ１）～（Ａ５）であるものとする。
（Ａ１）Ｘ線源：単色化ＡｌＫα
（Ａ２）光電子取出確度：θ＝７５℃（後述する図１を参照）
（Ａ３）帯電補正：Ｃ１ｓピークエネルギーを２８４．８ｅＶとして補正
（Ａ４）分析領域：２００μｍ
（Ａ５）分析時のチャンバ圧力：約１×１０－６Ｐａ Here, in the present invention, the measurement conditions by XPS are the following (A1) to (A5).
(A1) X-ray source: Monochromatic AlKα
(A2) Photoelectron extraction accuracy: θ = 75 ° C. (see FIG. 1 described later)
(A3) Charging correction: C1s peak energy is corrected to 284.8 eV (A4) Analysis area: 200 μm
(A5) Chamber pressure during analysis: about 1 × 10 −6 Pa
（Ａ１）Ｘ線源：単色化ＡｌＫα
（Ａ２）光電子取出確度：θ＝７５℃（後述する図１を参照）
（Ａ３）帯電補正：Ｃ１ｓピークエネルギーを２８４．８ｅＶとして補正
（Ａ４）分析領域：２００μｍ
（Ａ５）分析時のチャンバ圧力：約１×１０－６Ｐａ Here, in the present invention, the measurement conditions by XPS are the following (A1) to (A5).
(A1) X-ray source: Monochromatic AlKα
(A2) Photoelectron extraction accuracy: θ = 75 ° C. (see FIG. 1 described later)
(A3) Charging correction: C1s peak energy is corrected to 284.8 eV (A4) Analysis area: 200 μm
(A5) Chamber pressure during analysis: about 1 × 10 −6 Pa
また、本発明の効果をより確実に得る観点から、本発明の核水添反応用触媒においては、前記担体がアルミナ担体であることが好ましい。
更に、本発明の効果をより確実に得る観点から、本発明の核水添反応用触媒においては、前記アルミナ担体について、ＢＪＨ法により求められる細孔径ＰＳが８．００ｎｍ～１２．００ｎｍであり、ＢＪＨ法により求められる細孔容積ＰＶが０．２５０ｃｍ３／ｇ～０．４００ｃｍ３／ｇであることが好ましい。 In addition, from the viewpoint of more reliably obtaining the effects of the present invention, in the nuclear hydrogenation reaction catalyst of the present invention, the support is preferably an alumina support.
Furthermore, from the viewpoint of more reliably obtaining the effects of the present invention, in the catalyst for nuclear hydrogenation reaction of the present invention, the pore size PS required by the BJH method for the alumina support is 8.00 nm to 12.00 nm. it is preferred pore volume PV obtained by BJH method is 0.250cm 3 /g~0.400cm 3 / g.
更に、本発明の効果をより確実に得る観点から、本発明の核水添反応用触媒においては、前記アルミナ担体について、ＢＪＨ法により求められる細孔径ＰＳが８．００ｎｍ～１２．００ｎｍであり、ＢＪＨ法により求められる細孔容積ＰＶが０．２５０ｃｍ３／ｇ～０．４００ｃｍ３／ｇであることが好ましい。 In addition, from the viewpoint of more reliably obtaining the effects of the present invention, in the nuclear hydrogenation reaction catalyst of the present invention, the support is preferably an alumina support.
Furthermore, from the viewpoint of more reliably obtaining the effects of the present invention, in the catalyst for nuclear hydrogenation reaction of the present invention, the pore size PS required by the BJH method for the alumina support is 8.00 nm to 12.00 nm. it is preferred pore volume PV obtained by BJH method is 0.250cm 3 /g~0.400cm 3 / g.
ここで、本発明においては、細孔径ＰＳはＢＪＨ（Barrett, Joyner, Hallender）法により吸着質（気体分子）が固体表面から脱離するときの相対圧と吸着量の関係である脱着等温線から求められる値（BJH Desorption average pore diameter）である。
また、本発明において、細孔容積ＰＶも、ＢＪＨ法により求められる値（BJH Desorption cumulative volume of pores between 1.7000 nm and 300.0000 nm diameter）である。 Here, in the present invention, the pore diameter PS is determined from the desorption isotherm, which is the relationship between the relative pressure and the adsorption amount when the adsorbate (gas molecule) is desorbed from the solid surface by the BJH (Barrett, Joyner, Hallender) method. This is the required value (BJH Desorption average pore diameter).
In the present invention, the pore volume PV is also a value determined by the BJH method (BJH Desorption cumulative volume of pores between 1.7000 nm and 300.0000 nm diameter).
また、本発明において、細孔容積ＰＶも、ＢＪＨ法により求められる値（BJH Desorption cumulative volume of pores between 1.7000 nm and 300.0000 nm diameter）である。 Here, in the present invention, the pore diameter PS is determined from the desorption isotherm, which is the relationship between the relative pressure and the adsorption amount when the adsorbate (gas molecule) is desorbed from the solid surface by the BJH (Barrett, Joyner, Hallender) method. This is the required value (BJH Desorption average pore diameter).
In the present invention, the pore volume PV is also a value determined by the BJH method (BJH Desorption cumulative volume of pores between 1.7000 nm and 300.0000 nm diameter).
本発明によれば、芳香族化合物の核水添反応において、従来のルテニウム触媒よりも優れた反応物の転化率を得ることのできる優れた触媒活性を有する核水添反応用触媒が提供される。
ADVANTAGE OF THE INVENTION According to this invention, the nuclear hydrogenation reaction catalyst which has the outstanding catalytic activity which can obtain the conversion ratio of the reaction material superior to the conventional ruthenium catalyst in the nuclear hydrogenation reaction of an aromatic compound is provided. .
＜核水添反応用触媒＞
以下、本発明の核水添反応用触媒の好適な実施形態について詳細に説明する。本発明の水添反応用触媒は核水添反応に使用されるものである。例えば、下記の化学反応式（１）で示される、芳香族化合物であるジフェニルメタン（反応式（１）中の化合物１）の芳香環のπ結合を水素化して、α－シクロヘキシルトルエン（反応式（１）中の化合物２）及びジシクロヘキシルメタン（反応式（１）中の化合物３）に転化する核水添反応に使用することができる。
<Nuclear hydrogenation catalyst>
Hereinafter, preferred embodiments of the catalyst for nuclear hydrogenation reaction of the present invention will be described in detail. The hydrogenation reaction catalyst of the present invention is used for a nuclear hydrogenation reaction. For example, the aromatic ring π bond of diphenylmethane (compound 1 in reaction formula (1)) represented by the following chemical reaction formula (1) is hydrogenated to form α-cyclohexyltoluene (reaction formula (1) It can be used for the nuclear hydrogenation reaction to convert compound 2) in 1) and dicyclohexylmethane (compound 3 in reaction formula (1)).
以下、本発明の核水添反応用触媒の好適な実施形態について詳細に説明する。本発明の水添反応用触媒は核水添反応に使用されるものである。例えば、下記の化学反応式（１）で示される、芳香族化合物であるジフェニルメタン（反応式（１）中の化合物１）の芳香環のπ結合を水素化して、α－シクロヘキシルトルエン（反応式（１）中の化合物２）及びジシクロヘキシルメタン（反応式（１）中の化合物３）に転化する核水添反応に使用することができる。
Hereinafter, preferred embodiments of the catalyst for nuclear hydrogenation reaction of the present invention will be described in detail. The hydrogenation reaction catalyst of the present invention is used for a nuclear hydrogenation reaction. For example, the aromatic ring π bond of diphenylmethane (compound 1 in reaction formula (1)) represented by the following chemical reaction formula (1) is hydrogenated to form α-cyclohexyltoluene (reaction formula (1) It can be used for the nuclear hydrogenation reaction to convert compound 2) in 1) and dicyclohexylmethane (compound 3 in reaction formula (1)).
本発明の核水添反応用触媒は、担体と、前記担体上に担持される触媒粒子と、を含んでおり、前記触媒粒子が、Ｒｕ（０価）とＲｕ酸化物とを構成成分として含んでおり、Ｘ線光電子分光分析法（ＸＰＳ）により測定される表面近傍の分析領域における、Ｒｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）と、Ｒｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）とが、下記式（１）の条件を満たしている。
０．５０≦（ＲＲｕ／ＲＲｕＯｘ）≦４．００・・・式（１） The nuclear hydrogenation reaction catalyst of the present invention includes a support and catalyst particles supported on the support, and the catalyst particles include Ru (zero-valent) and Ru oxide as constituent components. In the analysis region in the vicinity of the surface measured by X-ray photoelectron spectroscopy (XPS), Ru (zero valence) ratio R Ru (atom%) and Ru oxide ratio R RuO x (atom%) Satisfies the condition of the following formula (1).
0.50 ≦ (R Ru / R RuOx ) ≦ 4.00 (1)
０．５０≦（ＲＲｕ／ＲＲｕＯｘ）≦４．００・・・式（１） The nuclear hydrogenation reaction catalyst of the present invention includes a support and catalyst particles supported on the support, and the catalyst particles include Ru (zero-valent) and Ru oxide as constituent components. In the analysis region in the vicinity of the surface measured by X-ray photoelectron spectroscopy (XPS), Ru (zero valence) ratio R Ru (atom%) and Ru oxide ratio R RuO x (atom%) Satisfies the condition of the following formula (1).
0.50 ≦ (R Ru / R RuOx ) ≦ 4.00 (1)
本発明の核水添反応用触媒は、担体と、前記担体上に担持される触媒粒子と、を含んでいればよく、触媒粒子の担持の形態については特に制限はなく、種々の構造を採り得る。
The catalyst for nuclear hydrogenation reaction of the present invention only needs to contain a support and catalyst particles supported on the support, and there is no particular limitation on the form of support of the catalyst particles, and various structures are adopted. obtain.
（担体）
担体としては、触媒粒子を担持することができ、かつ表面積が比較的大きいものであれば特に制限されないが、触媒粒子を含んだ溶液中で良好な分散性を有し、不活性であることが好ましい。 (Carrier)
The support is not particularly limited as long as it can support catalyst particles and has a relatively large surface area, but it has good dispersibility in a solution containing catalyst particles and is inert. preferable.
担体としては、触媒粒子を担持することができ、かつ表面積が比較的大きいものであれば特に制限されないが、触媒粒子を含んだ溶液中で良好な分散性を有し、不活性であることが好ましい。 (Carrier)
The support is not particularly limited as long as it can support catalyst particles and has a relatively large surface area, but it has good dispersibility in a solution containing catalyst particles and is inert. preferable.
不活性担体としては、例えば、炭素系材料（カーボン）、シリカ、アルミナ、シリアカルミナ、マグネシア等が好ましく、アルミナ（アルミナ担体）が特に好ましい。炭素系材料としては、例えば、グラッシーカーボン（ＧＣ）、ファインカーボン、カーボンブラック、黒鉛、炭素繊維、活性炭、活性炭の粉砕物、カーボンナノファイバー、カーボンナノチューブ等が挙げられる。
As the inert carrier, for example, carbon-based material (carbon), silica, alumina, Syria carmina, magnesia and the like are preferable, and alumina (alumina carrier) is particularly preferable. Examples of the carbon-based material include glassy carbon (GC), fine carbon, carbon black, graphite, carbon fiber, activated carbon, pulverized activated carbon, carbon nanofiber, and carbon nanotube.
なお、炭素系材料としては、導電性カーボンが好ましく、特に、導電性カーボンとしては、導電性カーボンブラックが好ましい。また、導電性カーボンブラックとしては、商品名「ケッチェンブラックＥＣ３００Ｊ」、「ケッチェンブラックＥＣ６００」、「カーボンＥＰＣ」等（ライオン化学株式会社製）を例示することができる。
In addition, as the carbon-based material, conductive carbon is preferable, and as the conductive carbon, conductive carbon black is particularly preferable. Examples of the conductive carbon black include trade names “Ketjen Black EC300J”, “Ketjen Black EC600”, “Carbon EPC” and the like (manufactured by Lion Chemical Co., Ltd.).
また、上記アルミナ担体については、ＢＪＨ法により求められる細孔径ＰＳが８．００ｎｍ～１２．００ｎｍであり、ＢＪＨ法により求められる細孔容積ＰＶが０．２５０ｃｍ３／ｇ～０．４００ｃｍ３／ｇであることが好ましい。
As for the alumina support with a pore size PS obtained by BJH method is 8.00nm ~ 12.00nm, a pore volume PV obtained by BJH method 0.250cm 3 /g~0.400cm 3 / g It is preferable that
ここで、細孔径ＰＳはＢＪＨ（Barrett, Joyner, Hallender）法により吸着質（気体分子）が固体表面から脱離するときの相対圧と吸着量の関係である脱着等温線から求められる値（BJH Desorption average pore diameter）である。また、本発明において、細孔容積ＰＶも、ＢＪＨ法により求められる値（BJH Desorption cumulative volume of pores between 1.7000 nm and 300.0000 nm diameter）である。
Here, the pore diameter PS is a value obtained from a desorption isotherm (BJH) which is a relationship between a relative pressure and an adsorption amount when an adsorbate (gas molecule) desorbs from a solid surface by the BJH (Barrett, Joyner, Hallender) method. Desorption average pore diameter). In the present invention, the pore volume PV is also a value determined by the BJH method (BJH Desorption cumulative volume of pores between 1.7000 nm and 300.0000 nm diameter).
（触媒粒子）
次に、本発明において上記担体に担持される触媒粒子は、Ｒｕ（０価）とＲｕ酸化物とを構成成分として含んでおり、上記のとおり、Ｘ線光電子分光分析法（ＸＰＳ）により測定される表面近傍の分析領域における、Ｒｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）と、Ｒｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）とが、下記式（１）の条件を満たしている。
０．５０≦（ＲＲｕ／ＲＲｕＯｘ）≦４．００・・・式（１） (Catalyst particles)
Next, the catalyst particles supported on the carrier in the present invention contain Ru (zero valence) and Ru oxide as constituent components, and are measured by X-ray photoelectron spectroscopy (XPS) as described above. In the analysis region in the vicinity of the surface, the Ru (zero valence) ratio R Ru (atom%) and the Ru oxide ratio R RuOx (atom%) satisfy the condition of the following formula (1).
0.50 ≦ (R Ru / R RuOx ) ≦ 4.00 (1)
次に、本発明において上記担体に担持される触媒粒子は、Ｒｕ（０価）とＲｕ酸化物とを構成成分として含んでおり、上記のとおり、Ｘ線光電子分光分析法（ＸＰＳ）により測定される表面近傍の分析領域における、Ｒｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）と、Ｒｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）とが、下記式（１）の条件を満たしている。
０．５０≦（ＲＲｕ／ＲＲｕＯｘ）≦４．００・・・式（１） (Catalyst particles)
Next, the catalyst particles supported on the carrier in the present invention contain Ru (zero valence) and Ru oxide as constituent components, and are measured by X-ray photoelectron spectroscopy (XPS) as described above. In the analysis region in the vicinity of the surface, the Ru (zero valence) ratio R Ru (atom%) and the Ru oxide ratio R RuOx (atom%) satisfy the condition of the following formula (1).
0.50 ≦ (R Ru / R RuOx ) ≦ 4.00 (1)
上記担体への上記触媒粒子の担持量は、本発明の効果を損なわない範囲であれば特に限定されるものではなく、本発明の核水添反応用触媒が採用される反応系、反応条件、製造コストなどにより適宜設定される。通常０．５～１０質量％程度であればよい。なお、ここでいう担持量とは、式：｛触媒粒子の質量／（触媒粒子の質量＋担体の質量）｝×１００で得られる値（率）のことをいう。
The amount of the catalyst particles supported on the carrier is not particularly limited as long as the effects of the present invention are not impaired, and the reaction system, reaction conditions, and the like in which the catalyst for nuclear hydrogenation reaction of the present invention is employed. It is appropriately set depending on the manufacturing cost. Usually, it may be about 0.5 to 10% by mass. Here, the supported amount refers to a value (rate) obtained by the formula: {mass of catalyst particles / (mass of catalyst particles + mass of support)} × 100.
次に、本発明においては、上記のとおり、上記式（１）に示される（ＲＲｕ／ＲＲｕＯｘ）の値が０．５０以上で４．００以下となる構成とすることにより、本発明の核水添反応用触媒は、芳香族化合物の核水添反応において、従来のルテニウム触媒よりも優れた反応物の転化率を得ることのできる優れた触媒活性を発揮することができる。
Next, in the present invention, as described above, by setting the value of (R Ru / R RuOx ) shown in the above formula (1) to 0.50 or more and 4.00 or less, The catalyst for nuclear hydrogenation reaction can exhibit an excellent catalytic activity capable of obtaining a conversion rate of a reactant superior to that of a conventional ruthenium catalyst in the nuclear hydrogenation reaction of an aromatic compound.
この（ＲＲｕ／ＲＲｕＯｘ）の値は、Ｘ線光電子分光分析法（ＸＰＳ）により測定される核水添反応用触媒粒子の表面近傍の分析領域における、Ｒｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）と、Ｒｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）と、の比であり、Ｒｕ（０価）及びＲｕ酸化物の担持割合を示すものである。この（ＲＲｕ／ＲＲｕＯｘ）の値が大きいと、核水添反応用触媒粒子の表面近傍においてＲｕ（０価）がＲｕ酸化物に比べてより多く存在し、この（ＲＲｕ／ＲＲｕＯｘ）の値が小さいと、核水添反応用触媒粒子の表面近傍においてＲｕ（０価）がＲｕ酸化物に比べてより少なく存在することを意味する。
The value of (R Ru / R RuOx ) is the ratio R Ru (0 valence) of Ru (zero valence) in the analysis region in the vicinity of the surface of the catalyst particle for nuclear hydrogenation reaction measured by X-ray photoelectron spectroscopy (XPS). atom%) and the Ru oxide ratio R RuOx (atom%), which indicates the supported ratio of Ru (zero valence) and Ru oxide. When the value of (R Ru / R RuOx ) is large, more Ru (0 valence) is present in the vicinity of the surface of the nuclear hydrogenation reaction catalyst particles than Ru oxide, and this (R Ru / R RuOx ) When the value of is small, it means that there is less Ru (zero valence) in the vicinity of the surface of the nuclear hydrogenation reaction catalyst particles than in the Ru oxide.
そして、本発明の核水添反応用触媒粒子の表面近傍においてＲｕ（０価）がＲｕ酸化物に比べてより多く存在すると、詳細なメカニズムは解明されていないが、核水添反応に対する触媒活性が向上するという効果が得られる傾向にある。また逆に、本発明の核水添反応用触媒粒子の表面近傍においてＲｕ（０価）がＲｕ酸化物に比べてより少なく存在すると、核水添反応に対する触媒活性が低下するという効果が得られる傾向にある。本発明では、上記式（１）に示される（ＲＲｕ／ＲＲｕＯｘ）の値が０．５０以上で４．００以下となる構成にすることにより、これらの作用効果をバランス良く実現するものである。
If more Ru (zero valent) is present in the vicinity of the surface of the catalyst particle for nuclear hydrogenation reaction of the present invention than Ru oxide, the detailed mechanism has not been elucidated, but the catalytic activity for the nuclear hydrogenation reaction is not clear. There is a tendency that the effect of improvement is obtained. Conversely, if there is less Ru (zero valence) in the vicinity of the surface of the catalyst particle for nuclear hydrogenation reaction of the present invention than Ru oxide, the effect of reducing the catalytic activity for the nuclear hydrogenation reaction can be obtained. There is a tendency. In the present invention, by providing a configuration in which the value of (R Ru / R RuOx ) shown in the above formula (1) is 0.50 or more and 4.00 or less, these functions and effects are realized in a balanced manner. is there.
Ｘ線光電子分光分析法（ＸＰＳ）は、以下の分析条件（Ａ１）～（Ａ５）で実施しされるものとする。
（Ａ１）Ｘ線源：単色化ＡｌＫα
（Ａ２）光電子取出確度：θ＝７５℃
（Ａ３）帯電補正：Ｃ１ｓピークエネルギーを２８４．８ｅＶとして補正
（Ａ４）分析領域：２００μｍ、
（Ａ５）分析時チャンバ圧力：約１×１０－６Ｐａ
ここで、（Ａ２）の光電子取出確度θは、図１に示すように、エックス線源３２から放射されたＸ線が、試料ステージ３４上にセットされた試料へ照射され、当該試料から放射される光電子を分光器３６で受光するときの角度θである。すなわち、光電子取出確度θは、分光器３６の受光軸と試料ステージ３４の試料の層の面との角度に該当する。 X-ray photoelectron spectroscopy (XPS) is carried out under the following analysis conditions (A1) to (A5).
(A1) X-ray source: Monochromatic AlKα
(A2) Photoelectron extraction accuracy: θ = 75 ° C.
(A3) Charging correction: C1s peak energy is corrected to 284.8 eV (A4) Analysis area: 200 μm,
(A5) Analysis chamber pressure: about 1 × 10 −6 Pa
Here, the photoelectron extraction accuracy θ of (A2) is, as shown in FIG. 1, the X-ray emitted from the X-ray source 32 is irradiated to the sample set on the sample stage 34 and is emitted from the sample. The angle θ when the photoelectron is received by the spectroscope 36. That is, the photoelectron extraction accuracy θ corresponds to the angle between the light receiving axis of the spectrometer 36 and the surface of the sample layer of the sample stage 34.
（Ａ１）Ｘ線源：単色化ＡｌＫα
（Ａ２）光電子取出確度：θ＝７５℃
（Ａ３）帯電補正：Ｃ１ｓピークエネルギーを２８４．８ｅＶとして補正
（Ａ４）分析領域：２００μｍ、
（Ａ５）分析時チャンバ圧力：約１×１０－６Ｐａ
ここで、（Ａ２）の光電子取出確度θは、図１に示すように、エックス線源３２から放射されたＸ線が、試料ステージ３４上にセットされた試料へ照射され、当該試料から放射される光電子を分光器３６で受光するときの角度θである。すなわち、光電子取出確度θは、分光器３６の受光軸と試料ステージ３４の試料の層の面との角度に該当する。 X-ray photoelectron spectroscopy (XPS) is carried out under the following analysis conditions (A1) to (A5).
(A1) X-ray source: Monochromatic AlKα
(A2) Photoelectron extraction accuracy: θ = 75 ° C.
(A3) Charging correction: C1s peak energy is corrected to 284.8 eV (A4) Analysis area: 200 μm,
(A5) Analysis chamber pressure: about 1 × 10 −6 Pa
Here, the photoelectron extraction accuracy θ of (A2) is, as shown in FIG. 1, the X-ray emitted from the X-ray source 32 is irradiated to the sample set on the sample stage 34 and is emitted from the sample. The angle θ when the photoelectron is received by the spectroscope 36. That is, the photoelectron extraction accuracy θ corresponds to the angle between the light receiving axis of the spectrometer 36 and the surface of the sample layer of the sample stage 34.
＜核水添反応用触媒の製造方法＞
本発明の核水添反応用触媒の製造方法は、担体に上記触媒粒子を担持させることができる方法であれば、特に制限されるものではない。 <Method for producing catalyst for nuclear hydrogenation reaction>
The method for producing the catalyst for nuclear hydrogenation reaction of the present invention is not particularly limited as long as the catalyst particles can be supported on a carrier.
本発明の核水添反応用触媒の製造方法は、担体に上記触媒粒子を担持させることができる方法であれば、特に制限されるものではない。 <Method for producing catalyst for nuclear hydrogenation reaction>
The method for producing the catalyst for nuclear hydrogenation reaction of the present invention is not particularly limited as long as the catalyst particles can be supported on a carrier.
例えば、担体にＲｕ化合物を含有する溶液を接触させ、担体に触媒成分を含浸させる含浸法、触媒成分を含有する溶液に還元剤を投入して行う液相還元法、電気化学的析出法、化学還元法、吸着水素による還元析出法等を採用した製造方法を例示することができる。
For example, an impregnation method in which a solution containing a Ru compound is brought into contact with a support and a catalyst component is impregnated in the support, a liquid phase reduction method in which a reducing agent is added to a solution containing the catalyst component, an electrochemical deposition method, a chemical Examples of the production method include a reduction method, a reduction precipitation method using adsorbed hydrogen, and the like.
ただし、核水添反応用触媒の製造における製造条件は、Ｘ線光電子分光分析法（ＸＰＳ）により測定される表面近傍の分析領域における、Ｒｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）と、Ｒｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）とが、下記式（１）の条件を満たすように調節されている。
０．５０≦（ＲＲｕ／ＲＲｕＯｘ）≦４．００・・・式（１） However, the production conditions in the production of the catalyst for nuclear hydrogenation reaction are the ratio R Ru (atom%) of Ru (zero valence) in the analysis region near the surface measured by X-ray photoelectron spectroscopy (XPS), The Ru oxide ratio R RuOx (atom%) is adjusted so as to satisfy the condition of the following formula (1).
0.50 ≦ (R Ru / R RuOx ) ≦ 4.00 (1)
０．５０≦（ＲＲｕ／ＲＲｕＯｘ）≦４．００・・・式（１） However, the production conditions in the production of the catalyst for nuclear hydrogenation reaction are the ratio R Ru (atom%) of Ru (zero valence) in the analysis region near the surface measured by X-ray photoelectron spectroscopy (XPS), The Ru oxide ratio R RuOx (atom%) is adjusted so as to satisfy the condition of the following formula (1).
0.50 ≦ (R Ru / R RuOx ) ≦ 4.00 (1)
なお、本発明の核水添反応用触媒を、上述した式（１）で示した条件、及び粉末Ｘ線回折（ＸＲＤ）により測定される結晶子サイズの平均値を好ましい条件（好ましくは３～１６．０ｎｍに調節する条件など）を満たすように製造する方法は特に限定されない。このような製造方法としては、例えば、生成物（触媒）の化学組成や構造を各種の公知の分析手法を用いて分析し、得られる分析結果を製造プロセスにフィードバックし、選択する原料、その原料の配合比、選択する合成反応、その合成反応の反応条件などを調製・変更する方法が挙げられる。
Note that the catalyst for nuclear hydrogenation reaction of the present invention has the conditions indicated by the above-mentioned formula (1) and the average value of crystallite size measured by powder X-ray diffraction (XRD) (preferably 3 to There are no particular restrictions on the method for producing the film so as to satisfy the conditions for adjusting to 16.0 nm. As such a production method, for example, the chemical composition and structure of a product (catalyst) are analyzed using various known analysis techniques, and the obtained analysis results are fed back to the production process, and the raw material to be selected and the raw material are selected. And a method of preparing / changing the compounding ratio, the synthesis reaction to be selected, the reaction conditions of the synthesis reaction, and the like.
以下、実施例により本発明を更に具体的に説明するが、本発明は、以下の実施例に限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
≪実施例１≫
Ｒｕ（０価）とＲｕ酸化物とを含む触媒粒子が担体であるアルミナ（Ａｌ２Ｏ３）粒子に５質量％の担持率で担持された実施例１の核水添反応用触媒として、商品名「ＨＹＡｃ－５Ｅ Ａ－ｔｙｐｅ」、Ｎ.Ｅ.ＣＨＥＭＣＡＴ社製）を製造した。
下記のようにして求めた核水添反応用触媒１の（ＲＲｕ／ＲＲｕＯｘ）値、並びに、担体のアルミナ粒子の細孔径ＰＳ及び細孔容積ＰＶを表１に示した。 Example 1
As a catalyst for nuclear hydrogenation reaction of Example 1 in which catalyst particles containing Ru (0 valence) and Ru oxide are supported on alumina (Al 2 O 3 ) particles as a support at a support ratio of 5 mass%, The name “HYAc-5E A-type” (manufactured by NE CHEMCAT) was produced.
Table 1 shows the (R Ru / R RuOx ) value of the nuclear hydrogenation reaction catalyst 1 determined as described below, and the pore diameter PS and pore volume PV of the alumina particles of the support.
Ｒｕ（０価）とＲｕ酸化物とを含む触媒粒子が担体であるアルミナ（Ａｌ２Ｏ３）粒子に５質量％の担持率で担持された実施例１の核水添反応用触媒として、商品名「ＨＹＡｃ－５Ｅ Ａ－ｔｙｐｅ」、Ｎ.Ｅ.ＣＨＥＭＣＡＴ社製）を製造した。
下記のようにして求めた核水添反応用触媒１の（ＲＲｕ／ＲＲｕＯｘ）値、並びに、担体のアルミナ粒子の細孔径ＰＳ及び細孔容積ＰＶを表１に示した。 Example 1
As a catalyst for nuclear hydrogenation reaction of Example 1 in which catalyst particles containing Ru (0 valence) and Ru oxide are supported on alumina (Al 2 O 3 ) particles as a support at a support ratio of 5 mass%, The name “HYAc-5E A-type” (manufactured by NE CHEMCAT) was produced.
Table 1 shows the (R Ru / R RuOx ) value of the nuclear hydrogenation reaction catalyst 1 determined as described below, and the pore diameter PS and pore volume PV of the alumina particles of the support.
≪実施例２及び実施例３≫
得られた核水添反応用触媒における（ＲＲｕ／ＲＲｕＯｘ）の値を表１に示すものに変更した以外は、実施例１と同様にして、実施例２の核水添反応用触媒（商品名「ＨＹＡｃ－５Ｅ Ｂ－ｔｙｐｅ」、Ｎ.Ｅ.ＣＨＥＭＣＡＴ社製）及び実施例３の核水添反応用触媒（商品名「ＨＹＡｃ－５Ｅ Ｃ－ｔｙｐｅ」、Ｎ.Ｅ.ＣＨＥＭＣＡＴ社製）を製造した。 << Example 2 and Example 3 >>
The catalyst for nuclear hydrogenation reaction of Example 2 (Example 2) was changed in the same manner as in Example 1 except that the value of (R Ru / R RuOx ) in the obtained catalyst for nuclear hydrogenation reaction was changed to that shown in Table 1. Product name “HYAc-5E B-type” (manufactured by NE CHEMCAT) and catalyst for nuclear hydrogenation reaction of Example 3 (trade name “HYAc-5E C-type”, manufactured by NE CHEMCAT) Manufactured.
得られた核水添反応用触媒における（ＲＲｕ／ＲＲｕＯｘ）の値を表１に示すものに変更した以外は、実施例１と同様にして、実施例２の核水添反応用触媒（商品名「ＨＹＡｃ－５Ｅ Ｂ－ｔｙｐｅ」、Ｎ.Ｅ.ＣＨＥＭＣＡＴ社製）及び実施例３の核水添反応用触媒（商品名「ＨＹＡｃ－５Ｅ Ｃ－ｔｙｐｅ」、Ｎ.Ｅ.ＣＨＥＭＣＡＴ社製）を製造した。 << Example 2 and Example 3 >>
The catalyst for nuclear hydrogenation reaction of Example 2 (Example 2) was changed in the same manner as in Example 1 except that the value of (R Ru / R RuOx ) in the obtained catalyst for nuclear hydrogenation reaction was changed to that shown in Table 1. Product name “HYAc-5E B-type” (manufactured by NE CHEMCAT) and catalyst for nuclear hydrogenation reaction of Example 3 (trade name “HYAc-5E C-type”, manufactured by NE CHEMCAT) Manufactured.
≪実施例４≫
担体として表１に示した細孔径ＰＳ及び細孔容積ＰＶを有する担体を用いた以外は、実施例１と同様にして、実施例４の核水添反応用触媒（商品名「ＨＹＡｃ－５Ｅ Ｆ－ｔｙｐｅ」、Ｎ.Ｅ.ＣＨＥＭＣＡＴ社）を製造した。 Example 4
The catalyst for nuclear hydrogenation reaction of Example 4 (trade name “HYAc-5E F” was used in the same manner as in Example 1 except that the carrier having the pore diameter PS and pore volume PV shown in Table 1 was used as the carrier. -Type ", manufactured by NE CHEMCAT).
担体として表１に示した細孔径ＰＳ及び細孔容積ＰＶを有する担体を用いた以外は、実施例１と同様にして、実施例４の核水添反応用触媒（商品名「ＨＹＡｃ－５Ｅ Ｆ－ｔｙｐｅ」、Ｎ.Ｅ.ＣＨＥＭＣＡＴ社）を製造した。 Example 4
The catalyst for nuclear hydrogenation reaction of Example 4 (trade name “HYAc-5E F” was used in the same manner as in Example 1 except that the carrier having the pore diameter PS and pore volume PV shown in Table 1 was used as the carrier. -Type ", manufactured by NE CHEMCAT).
≪比較例１≫
用いた触媒粒子における（ＲＲｕ／ＲＲｕＯｘ）の値を表１に示すものに変更した以外は、実施例１と同様にして、比較例１の核水添反応用触媒を製造した。 ≪Comparative example 1≫
A nuclear hydrogenation reaction catalyst of Comparative Example 1 was produced in the same manner as in Example 1, except that the value of (R Ru / R RuOx ) in the catalyst particles used was changed to that shown in Table 1.
用いた触媒粒子における（ＲＲｕ／ＲＲｕＯｘ）の値を表１に示すものに変更した以外は、実施例１と同様にして、比較例１の核水添反応用触媒を製造した。 ≪Comparative example 1≫
A nuclear hydrogenation reaction catalyst of Comparative Example 1 was produced in the same manner as in Example 1, except that the value of (R Ru / R RuOx ) in the catalyst particles used was changed to that shown in Table 1.
≪比較例２≫
用いた触媒粒子における（ＲＲｕ／ＲＲｕＯｘ）の値を表１に示すものに変更した以外は、実施例１と同様にして、比較例２の核水添反応用触媒を製造した。 ≪Comparative example 2≫
A nuclear hydrogenation reaction catalyst of Comparative Example 2 was produced in the same manner as in Example 1 except that the value of (R Ru / R RuOx ) in the catalyst particles used was changed to that shown in Table 1.
用いた触媒粒子における（ＲＲｕ／ＲＲｕＯｘ）の値を表１に示すものに変更した以外は、実施例１と同様にして、比較例２の核水添反応用触媒を製造した。 ≪Comparative example 2≫
A nuclear hydrogenation reaction catalyst of Comparative Example 2 was produced in the same manner as in Example 1 except that the value of (R Ru / R RuOx ) in the catalyst particles used was changed to that shown in Table 1.
［評価試験］
上記の実施例１～４及び比較例１～２で得た核水添反応用触媒を用い、下記の反応式（１）にしたがって、芳香族化合物であるジフェニルメタン（反応式（１）中の化合物１）の芳香環のπ結合を水素化して、α－シクロヘキシルトルエン（反応式（１）中の化合物２）及びジシクロヘキシルメタン（反応式（１）中の化合物３）に転化する核水添反応を行った。 [Evaluation test]
Using the nuclear hydrogenation catalysts obtained in Examples 1 to 4 and Comparative Examples 1 and 2 above, diphenylmethane (a compound in reaction formula (1)) as an aromatic compound according to the following reaction formula (1) 1) Hydrogenation reaction of π bond of aromatic ring and conversion into α-cyclohexyltoluene (compound 2 in reaction formula (1)) and dicyclohexylmethane (compound 3 in reaction formula (1)). went.
上記の実施例１～４及び比較例１～２で得た核水添反応用触媒を用い、下記の反応式（１）にしたがって、芳香族化合物であるジフェニルメタン（反応式（１）中の化合物１）の芳香環のπ結合を水素化して、α－シクロヘキシルトルエン（反応式（１）中の化合物２）及びジシクロヘキシルメタン（反応式（１）中の化合物３）に転化する核水添反応を行った。 [Evaluation test]
Using the nuclear hydrogenation catalysts obtained in Examples 1 to 4 and Comparative Examples 1 and 2 above, diphenylmethane (a compound in reaction formula (1)) as an aromatic compound according to the following reaction formula (1) 1) Hydrogenation reaction of π bond of aromatic ring and conversion into α-cyclohexyltoluene (compound 2 in reaction formula (1)) and dicyclohexylmethane (compound 3 in reaction formula (1)). went.
その際、核水添反応用触媒の使用量は、原料であるジフェニルメタン（反応式（１）中の化合物１）の０．４モル％とし、圧力が０．２ＭＰａとなるように水素ガスを供給しながら、温度を５０℃に昇温し、表１に示す昇温保持時間の条件で反応させた。
At that time, the amount of the nuclear hydrogenation reaction catalyst used is 0.4 mol% of the raw material diphenylmethane (compound 1 in the reaction formula (1)), and hydrogen gas is supplied so that the pressure becomes 0.2 MPa. While raising the temperature to 50 ° C., the reaction was carried out under the conditions of the temperature rise holding time shown in Table 1.
（１）Ｘ線光電子分光分析（ＸＰＳ：Ｘ－ｒａｙ ｐｈｏｔｏｅｌｅｃｔｒｏｎ ｓｐｅｃｔｒｏｓｃｏｐｙ）による核水添反応用触媒の表面分析
(1) Surface analysis of nuclear hydrogenation catalyst by X-ray photoelectron spectroscopy (XPS: X-ray photoelectron spectroscopy)
実施例１～４及び比較例１～２の核水添反応用触媒についてＸＰＳによる表面分析を実施し、Ｒｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）と、Ｒｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）とを測定し、（ＲＲｕ／ＲＲｕＯｘ）の値を算出した。
具体的には、ＸＰＳ装置として「Ｑｕａｎｔｅｒａ ＳＸＭ」（アルバック・ファイ社製）を使用し、以下の分析条件で実施した。
（Ａ１）Ｘ線源：単色化ＡｌＫα
（Ａ２）光電子取出確度：θ＝７５℃（図１参照）
（Ａ３）帯電補正：Ｃ１ｓピークエネルギーを２８４．８ｅＶとして補正
（Ａ４）分析領域：２００μｍ
（Ａ５）分析時のチャンバ圧力：約１×１０－６Ｐａ
（Ａ６）測定深さ（脱出深さ）：約５ｎｍ以下 Surface analysis by XPS was performed on the catalysts for nuclear hydrogenation reactions of Examples 1 to 4 and Comparative Examples 1 to 2, and the Ru (zero valent) ratio R Ru (atom%) and the Ru oxide ratio R RuOx ( atom%), and the value of (R Ru / R RuOx ) was calculated.
Specifically, “Quantera SXM” (manufactured by ULVAC-PHI) was used as an XPS apparatus, and the following analysis conditions were used.
(A1) X-ray source: Monochromatic AlKα
(A2) Photoelectron extraction accuracy: θ = 75 ° C. (see FIG. 1)
(A3) Charging correction: C1s peak energy is corrected to 284.8 eV (A4) Analysis area: 200 μm
(A5) Chamber pressure during analysis: about 1 × 10 −6 Pa
(A6) Measurement depth (escape depth): about 5 nm or less
具体的には、ＸＰＳ装置として「Ｑｕａｎｔｅｒａ ＳＸＭ」（アルバック・ファイ社製）を使用し、以下の分析条件で実施した。
（Ａ１）Ｘ線源：単色化ＡｌＫα
（Ａ２）光電子取出確度：θ＝７５℃（図１参照）
（Ａ３）帯電補正：Ｃ１ｓピークエネルギーを２８４．８ｅＶとして補正
（Ａ４）分析領域：２００μｍ
（Ａ５）分析時のチャンバ圧力：約１×１０－６Ｐａ
（Ａ６）測定深さ（脱出深さ）：約５ｎｍ以下 Surface analysis by XPS was performed on the catalysts for nuclear hydrogenation reactions of Examples 1 to 4 and Comparative Examples 1 to 2, and the Ru (zero valent) ratio R Ru (atom%) and the Ru oxide ratio R RuOx ( atom%), and the value of (R Ru / R RuOx ) was calculated.
Specifically, “Quantera SXM” (manufactured by ULVAC-PHI) was used as an XPS apparatus, and the following analysis conditions were used.
(A1) X-ray source: Monochromatic AlKα
(A2) Photoelectron extraction accuracy: θ = 75 ° C. (see FIG. 1)
(A3) Charging correction: C1s peak energy is corrected to 284.8 eV (A4) Analysis area: 200 μm
(A5) Chamber pressure during analysis: about 1 × 10 −6 Pa
(A6) Measurement depth (escape depth): about 5 nm or less
分析結果を表１に示した。なお、Ｒｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）とＲｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）については、これらの２成分で１００％となるように算出した。
The analysis results are shown in Table 1. The ratio R Ru (atom%) of Ru (zero valence) and the ratio R RuOx (atom%) of Ru oxide were calculated so that these two components would be 100%.
（２）担持率の測定（ＩＣＰ分析）
実施例１～４及び比較例１～２の核水添反応用触媒について、Ｒｕ（０価）とＲｕ酸化物とを構成成分として含む触媒粒子の担持率（ｗｔ％）を以下の方法で測定した。即ち、核水添反応用触媒を王水に浸し、金属を溶解させた。次に、王水から不溶成分のアルミナを除去した。次に、アルミナを除いた王水をＩＣＰ分析した。全ての核水添反応用触媒について、触媒粒子の担持率は５％であった。 (2) Measurement of loading rate (ICP analysis)
For the catalysts for nuclear hydrogenation reaction of Examples 1 to 4 and Comparative Examples 1 to 2, the loading ratio (wt%) of catalyst particles containing Ru (zero valence) and Ru oxide as constituent components was measured by the following method. did. That is, the catalyst for nuclear hydrogenation reaction was immersed in aqua regia to dissolve the metal. Next, insoluble component alumina was removed from the aqua regia. Next, aqua regia without alumina was analyzed by ICP. For all the nuclear hydrogenation catalysts, the catalyst particle loading was 5%.
実施例１～４及び比較例１～２の核水添反応用触媒について、Ｒｕ（０価）とＲｕ酸化物とを構成成分として含む触媒粒子の担持率（ｗｔ％）を以下の方法で測定した。即ち、核水添反応用触媒を王水に浸し、金属を溶解させた。次に、王水から不溶成分のアルミナを除去した。次に、アルミナを除いた王水をＩＣＰ分析した。全ての核水添反応用触媒について、触媒粒子の担持率は５％であった。 (2) Measurement of loading rate (ICP analysis)
For the catalysts for nuclear hydrogenation reaction of Examples 1 to 4 and Comparative Examples 1 to 2, the loading ratio (wt%) of catalyst particles containing Ru (zero valence) and Ru oxide as constituent components was measured by the following method. did. That is, the catalyst for nuclear hydrogenation reaction was immersed in aqua regia to dissolve the metal. Next, insoluble component alumina was removed from the aqua regia. Next, aqua regia without alumina was analyzed by ICP. For all the nuclear hydrogenation catalysts, the catalyst particle loading was 5%.
（３）転化率の算出
反応後の混合組成物におけるジフェニルメタン、α－シクロヘキシルトルエン及びジシクロヘキシルメタンの含有比（質量）を測定することによって、ジフェニルメタンの転化率（％）を算出し、結果を表1に示した。 (3) Calculation of conversion rate The conversion rate (%) of diphenylmethane was calculated by measuring the content ratio (mass) of diphenylmethane, α-cyclohexyltoluene and dicyclohexylmethane in the mixed composition after the reaction. It was shown to.
反応後の混合組成物におけるジフェニルメタン、α－シクロヘキシルトルエン及びジシクロヘキシルメタンの含有比（質量）を測定することによって、ジフェニルメタンの転化率（％）を算出し、結果を表1に示した。 (3) Calculation of conversion rate The conversion rate (%) of diphenylmethane was calculated by measuring the content ratio (mass) of diphenylmethane, α-cyclohexyltoluene and dicyclohexylmethane in the mixed composition after the reaction. It was shown to.
表１に示す結果から、（ＲＲｕ／ＲＲｕＯｘ）の値が先に述べた式（１）を満たす実施例１～４において、従来のルテニウム触媒を用いた比較例１及び比較例２に比べて、ジフェニルメタンの転化率が高く、本発明の核水添反応用触媒の触媒活性が高く、芳香族化合物の核水添反応において優れた反応物の転化率を得ることのできる優れた触媒活性を有することが明らかとなった。
From the results shown in Table 1, in Examples 1 to 4 in which the value of (R Ru / R RuOx ) satisfies the formula (1) described above, compared to Comparative Example 1 and Comparative Example 2 using a conventional ruthenium catalyst, Thus, the conversion rate of diphenylmethane is high, the catalytic activity of the catalyst for nuclear hydrogenation reaction of the present invention is high, and the excellent catalytic activity that can obtain the excellent conversion rate of the reactant in the nuclear hydrogenation reaction of aromatic compounds. It became clear to have.
本発明の核水添反応用触媒は、優れた触媒活性を有し、芳香族化合物の核水添反応において優れた反応物の転化率を得ることができる。従って、本発明は、高機能プラスチック製品の原料となるエポキシ樹脂やポリアミドイミド樹脂等の合成に適用することができる核水添反応用触媒であり、各種産業の発達に寄与する。
The catalyst for nuclear hydrogenation reaction of the present invention has an excellent catalytic activity, and can obtain an excellent conversion rate of a reactant in the nuclear hydrogenation reaction of an aromatic compound. Accordingly, the present invention is a nuclear hydrogenation reaction catalyst that can be applied to the synthesis of epoxy resins, polyamideimide resins, and the like, which are raw materials for high-performance plastic products, and contributes to the development of various industries.
The catalyst for nuclear hydrogenation reaction of the present invention has an excellent catalytic activity, and can obtain an excellent conversion rate of a reactant in the nuclear hydrogenation reaction of an aromatic compound. Accordingly, the present invention is a nuclear hydrogenation reaction catalyst that can be applied to the synthesis of epoxy resins, polyamideimide resins, and the like, which are raw materials for high-performance plastic products, and contributes to the development of various industries.
Claims (3)
- 芳香族化合物の芳香環のπ結合の少なくとも１つを水素化する核水添反応に使用される核水添反応用触媒であって、
担体と、前記担体上に担持される触媒粒子と、を含んでおり、
前記触媒粒子が、Ｒｕ（０価）とＲｕ酸化物とを構成成分として含んでおり、
Ｘ線光電子分光分析法（ＸＰＳ）により測定される表面近傍の分析領域における、Ｒｕ（０価）の割合ＲＲｕ（ａｔｏｍ％）と、Ｒｕ酸化物の割合ＲＲｕＯｘ（ａｔｏｍ％）とが、下記式（１）の条件を満たしている、
核水添反応用触媒。
０．５０≦（ＲＲｕ／ＲＲｕＯｘ）≦４．００・・・式（１） A nuclear hydrogenation catalyst used in a nuclear hydrogenation reaction for hydrogenating at least one π bond of an aromatic ring of an aromatic compound,
A support, and catalyst particles supported on the support,
The catalyst particles contain Ru (zero valence) and Ru oxide as constituent components,
The ratio R Ru (atom%) of Ru (zero valence) and the ratio R RuOx (atom%) of Ru oxide in the analysis region near the surface measured by X-ray photoelectron spectroscopy (XPS) are as follows. Satisfies the condition of equation (1),
Catalyst for nuclear hydrogenation reaction.
0.50 ≦ (R Ru / R RuOx ) ≦ 4.00 (1) - 前記担体がアルミナ担体である、請求項１に記載の核水添反応用触媒。 The catalyst for nuclear hydrogenation reaction according to claim 1, wherein the support is an alumina support.
- 前記アルミナ担体について、ＢＪＨ法により求められる細孔径ＰＳが８．００ｎｍ～１２．００ｎｍであり、ＢＪＨ法により求められる細孔容積ＰＶが０．２５０ｃｍ３／ｇ～０．４００ｃｍ３／ｇである、
請求項１又は２に記載の核水添反応用触媒。
For the alumina carrier, the pore size PS obtained by BJH method is 8.00nm ~ 12.00nm, a pore volume PV obtained by BJH method is 0.250cm 3 /g~0.400cm 3 / g,
The catalyst for nuclear hydrogenation reaction of Claim 1 or 2.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0655073A (en) * | 1992-06-27 | 1994-03-01 | Huels Ag | Catalyst and method for selective hydrogenation of unsaturated compound and production of said catalyst |
| JP2002542210A (en) * | 1999-04-15 | 2002-12-10 | ビーエーエスエフ アクチェンゲゼルシャフト | Method for hydrogenating unsubstituted or alkyl-substituted aromatic compounds using macropore-containing catalyst |
| WO2006006277A1 (en) * | 2004-07-09 | 2006-01-19 | Asahi Kasei Chemicals Corporation | Catalyst for cycloolefin production and process for production |
| WO2006114942A1 (en) * | 2005-04-21 | 2006-11-02 | Hitachi Maxell, Ltd. | Particle containing carbon particle, platinum and ruthenium oxide, and method for producing same |
| JP2012041335A (en) * | 2010-07-21 | 2012-03-01 | Hokkaido Univ | Method of producing sugar alcohol |
| JP2012507120A (en) * | 2008-10-24 | 2012-03-22 | ナノシス・インク． | Electrochemical catalyst for fuel cell |
| JP2015504414A (en) * | 2011-10-28 | 2015-02-12 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing cis-rose oxide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1366812B1 (en) * | 2002-05-31 | 2009-02-18 | Evonik Degussa GmbH | Supported Ruthenium catalyst and process for hydrogenation of aromatic amines in presence of this catalyst |
| JP5540703B2 (en) * | 2007-08-06 | 2014-07-02 | 三菱瓦斯化学株式会社 | Method for producing nuclear hydrogenated aromatic vinyl compound / (meth) acrylate copolymer |
| KR102023260B1 (en) * | 2014-08-28 | 2019-09-19 | 엔.이. 켐캣 가부시키가이샤 | Catalyst for electrode, composition for forming gas diffusion electrode, gas diffusion electrode, membrane electrode assembly, and fuel cell stack |
-
2018
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- 2018-02-22 JP JP2019502925A patent/JP7008686B2/en active Active
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0655073A (en) * | 1992-06-27 | 1994-03-01 | Huels Ag | Catalyst and method for selective hydrogenation of unsaturated compound and production of said catalyst |
| JP2002542210A (en) * | 1999-04-15 | 2002-12-10 | ビーエーエスエフ アクチェンゲゼルシャフト | Method for hydrogenating unsubstituted or alkyl-substituted aromatic compounds using macropore-containing catalyst |
| WO2006006277A1 (en) * | 2004-07-09 | 2006-01-19 | Asahi Kasei Chemicals Corporation | Catalyst for cycloolefin production and process for production |
| WO2006114942A1 (en) * | 2005-04-21 | 2006-11-02 | Hitachi Maxell, Ltd. | Particle containing carbon particle, platinum and ruthenium oxide, and method for producing same |
| JP2012507120A (en) * | 2008-10-24 | 2012-03-22 | ナノシス・インク． | Electrochemical catalyst for fuel cell |
| JP2012041335A (en) * | 2010-07-21 | 2012-03-01 | Hokkaido Univ | Method of producing sugar alcohol |
| JP2015504414A (en) * | 2011-10-28 | 2015-02-12 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing cis-rose oxide |
Non-Patent Citations (1)
| Title |
|---|
| MAZZIERI, V. ET AL.: "XP S, FTIR and TPR characterization of Ru/A1203 catalysts", APPLIED SURFACE SCIENCE, vol. 210, no. 3 / 4, 15 April 2003 (2003-04-15), pages 222 - 230, ISSN: 0169-4332 * |
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