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WO2018159436A1 - Catalyseur pour réaction d'hydrogénation nucléaire - Google Patents

Catalyseur pour réaction d'hydrogénation nucléaire Download PDF

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Publication number
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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WIPO (PCT)
Prior art keywords
catalyst
hydrogenation reaction
nuclear hydrogenation
reaction
present
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PCT/JP2018/006392
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English (en)
Japanese (ja)
Inventor
智照 水崎
晋司 上野
晃 小松
弘康 鈴鹿
佳之 和田
Original Assignee
エヌ・イー ケムキャット株式会社
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Application filed by エヌ・イー ケムキャット株式会社 filed Critical エヌ・イー ケムキャット株式会社
Priority to CN201880014213.6A priority Critical patent/CN110366447A/zh
Priority to JP2019502925A priority patent/JP7008686B2/ja
Publication of WO2018159436A1 publication Critical patent/WO2018159436A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • 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
    • 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

Definitions

  • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Le but de la présente invention est de fournir un catalyseur pour une réaction d'hydrogénation nucléaire ayant une activité catalytique supérieure qui peut donner un taux de conversion pour des produits de réaction supérieurs aux catalyseurs de ruthénium classiques dans une réaction d'hydrogénation nucléaire pour un composé aromatique. L'invention concerne un catalyseur pour une réaction d'hydrogénation nucléaire utilisée dans une réaction d'hydrogénation nucléaire pour l'hydrogénation d'au moins une liaison π d'un cycle aromatique dans un composé aromatique, le catalyseur comprenant un support et des particules de catalyseur supportées sur ce support. Les particules de catalyseur comprennent du Ru (valence 0) et de l'oxyde de Ru en tant que composants constitutifs. Dans des zones analysées au voisinage de la surface mesurée par spectroscopie photoélectronique à rayons x (XPS), la proportion RRu (% atomique ) de Ru (valence 0) et la proportion RRuOx (% atomique) de l'oxyde de Ru satisfont les conditions dans l'équation (1). 0.50 ≤ (RRu/RRuOx) ≤ 4.00 ... Équation (1)
PCT/JP2018/006392 2017-02-28 2018-02-22 Catalyseur pour réaction d'hydrogénation nucléaire WO2018159436A1 (fr)

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CN201880014213.6A CN110366447A (zh) 2017-02-28 2018-02-22 核氢化反应用催化剂
JP2019502925A JP7008686B2 (ja) 2017-02-28 2018-02-22 核水添反応用触媒

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JP2002542210A (ja) * 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 マクロ細孔含有触媒を用いる非置換またはアルキル置換芳香族化合物の水素添加方法
WO2006006277A1 (fr) * 2004-07-09 2006-01-19 Asahi Kasei Chemicals Corporation Catalyseur pour production de cyclooléfines et procédé pour la production
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KR102023260B1 (ko) * 2014-08-28 2019-09-19 엔.이. 켐캣 가부시키가이샤 전극용 촉매, 가스확산 전극 형성용 조성물, 가스확산 전극, 막-전극 접합체, 연료전지 스택

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WO2006006277A1 (fr) * 2004-07-09 2006-01-19 Asahi Kasei Chemicals Corporation Catalyseur pour production de cyclooléfines et procédé pour la production
WO2006114942A1 (fr) * 2005-04-21 2006-11-02 Hitachi Maxell, Ltd. Particule contenant une particule de carbone, du platine et de l'oxyde de ruthenium, et son procede de fabrication
JP2012507120A (ja) * 2008-10-24 2012-03-22 ナノシス・インク． 燃料電池用電気化学的触媒
JP2012041335A (ja) * 2010-07-21 2012-03-01 Hokkaido Univ 糖アルコールの製造方法
JP2015504414A (ja) * 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 シス−ローズオキシドの生成方法

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JP7008686B2 (ja) 2022-02-10
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