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WO2022270401A1 - Procédé de fabrication de cyclopentadiène - Google Patents

Procédé de fabrication de cyclopentadiène Download PDF

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WO2022270401A1
WO2022270401A1 PCT/JP2022/024103 JP2022024103W WO2022270401A1 WO 2022270401 A1 WO2022270401 A1 WO 2022270401A1 JP 2022024103 W JP2022024103 W JP 2022024103W WO 2022270401 A1 WO2022270401 A1 WO 2022270401A1
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cyclopentadiene
zeolite
catalyst
zeolite catalyst
atoms
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PCT/JP2022/024103
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English (en)
Japanese (ja)
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裕之 今井
匡 梅田
透容 吉原
太 大内
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Ｅｎｅｏｓ株式会社
公立大学法人北九州市立大学
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Publication of WO2022270401A1 publication Critical patent/WO2022270401A1/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
    • B01J23/42—Platinum
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • 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
    • C07C13/08—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring
    • C07C13/15—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring with a cyclopentadiene 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation

Definitions

  • the present invention relates to a method for producing cyclopentadiene.
  • cyclopentadiene is widely used industrially as a raw material for synthesizing agricultural chemicals, insecticides, and various resin plasticizers.
  • Cyclopentadiene is obtained, for example, from the C5 hydrocarbon-based C5 fraction by-product in the production of ethylene by liquid feed steam cracking (e.g., naphtha and heavier feedstocks) in the dimerization process. And it can be obtained by recovering by a distillation process.
  • Non-Patent Document 1 describes a method for producing cyclopentadiene from n-pentane, n-pentene, and 1,3-pentadiene using a Pt/SiO 2 catalyst. Yields to cyclopentadiene are as high as 21%, 35%, and 53% for the conversion of n-pentane, n-pentene, and 1,3-pentadiene at 600° C., respectively, and olefin to cyclopentadiene. It can be seen that it is superior to the conversion of
  • Non-Patent Document 1 it is reported in Non-Patent Document 1 that the catalyst deteriorates in a short time (for example, within 15 minutes) in the method described in Non-Patent Document 1. This is probably because coke tends to be generated during the dehydrogenation reaction of olefins, and the generated coke accumulates on the surface of the catalyst, deactivating the catalyst. For this reason, in conventional methods for producing cyclopentadiene, sufficient studies have not been made on how to stably produce cyclopentadiene at a high yield over a long period of time in the presence of an olefin, and there is still room for improvement. was left.
  • An object of the present invention is to provide a method for stably producing cyclopentadiene at a high yield over a long period of time using a zeolite catalyst in the presence of an olefin as a novel method for producing cyclopentadiene.
  • One aspect of the present invention is the production of cyclopentadiene comprising a step of cyclizing dehydrogenation to obtain a reaction product containing cyclopentadiene by contacting a raw material composition containing an olefin having 5 carbon atoms with a zeolite catalyst having an MFI structure.
  • the zeolite catalyst contains at least one metal atom selected from transition metals and post-transition metals in the zeolite skeleton, and has Lewis acidity and strong solid basicity.
  • the raw material composition may contain a diolefin having 5 carbon atoms.
  • the content of the diolefin having 5 carbon atoms in the raw material composition may be 5% by mass or more.
  • the metal atoms are one or more selected from Zn atoms, Fe atoms, and Ni atoms, and the content of the metal atoms may be 1 to 15 atom % with respect to the Si atoms.
  • the zeolite catalyst may contain no alkali metal, or may contain 1 atom % or less of alkali metal relative to the Si atoms of the zeolite skeleton.
  • the zeolite catalyst may support Pt.
  • a gas flow rate (ml/min) ratio between the raw material composition and molecular hydrogen supplied to the reaction system may be 1:0.001 to 1:3.
  • a novel method for producing cyclopentadiene it is possible to provide a method for stably producing cyclopentadiene at a high yield over a long period of time using a zeolite catalyst in the presence of an olefin.
  • FIG. 3 shows the results of synchrotron XRD analysis of zeolite catalysts and Zn-impregnated supported catalysts according to Examples.
  • FIG. 3 is a diagram showing the results of 29 Si MAS NMR measurement of zeolite catalysts according to Examples.
  • FIG. 3 shows the results of FT-IR analysis of zeolite catalysts, ZnO crystals, and Zn-impregnated supported catalysts according to Examples.
  • FIG. 3 is a diagram showing the results of FT-IR analysis of a zeolite catalyst, ZnO crystals, and a Zn-impregnated supported catalyst according to Examples on which pyridine is adsorbed.
  • FIG. 3 shows the results of synchrotron XRD analysis of zeolite catalysts and Zn-impregnated supported catalysts according to Examples.
  • FIG. 3 is a diagram showing the results of 29 Si MAS NMR measurement of zeolite catalysts according to Examples.
  • FIG. 3 shows the results of FT-IR analysis of ze
  • FIG. 3 shows the results of CO 2 -TPD analysis of zeolite catalysts and Zn-impregnated supported catalysts according to examples.
  • FIG. 3 shows the results of NH 3 -TPD analysis of zeolite catalysts and Zn-impregnated supported catalysts according to Examples.
  • FIG. 3 shows the results of UV-vis analysis of zeolite catalysts and ZnO crystals according to Examples.
  • the method for producing cyclopentadiene according to the present embodiment includes a cyclization dehydrogenation step of contacting a raw material composition containing an olefin having 5 carbon atoms with a zeolite catalyst having an MFI structure to obtain a reaction product containing cyclopentadiene.
  • a specific zeolite catalyst by using a specific zeolite catalyst, cyclopentadiene can be stably produced at a high yield over a long period of time.
  • the zeolite catalyst according to the present embodiment contains at least one metal atom selected from transition metals and post-transition metals in the zeolite skeleton, and has Lewis acidity and strong solid basicity.
  • the zeolite catalyst according to the present embodiment almost no Bronsted acids are present in the zeolite catalyst, and only Lewis acids are present. It is generally known that the amount of by-products of the cyclization dehydrogenation reaction increases or decreases due to the presence of Bronsted acid, but the zeolite catalyst according to the present embodiment contains almost no Bronsted acid. Therefore, it is possible to control side reactions and suppress the generation of by-products.
  • the zeolite catalyst according to the present embodiment for the production of cyclopentadiene for example, side reactions are suppressed, cyclopentadiene selectivity is improved, coke generation due to polymerization of decomposition by-products is suppressed, and the like.
  • cyclopentadiene can be stably produced over a long period of time. Furthermore, since the zeolite catalyst according to the present embodiment has highly dispersed Lewis acid sites that can be active sites for cyclization dehydrogenation reaction, etc., the zeolite catalyst according to the present embodiment can be used for the production of cyclopentadiene. , cyclopentadiene can be produced in high yield.
  • zeolite is a crystalline substance in which 4 units of TO having a tetrahedral structure (T is the central atom) share O atoms and are three-dimensionally connected to form regular micropores. means.
  • a transition metal means a metal belonging to Group 3 to Group 12 elements in the periodic table of long period elements based on the IUPAC (International Union of Pure and Applied Chemistry) regulations.
  • a post-transition metal means a base metal with an atomic number after the transition metals of the 4th, 5th and 6th periods of the periodic table.
  • Containing a metal atom in the zeolite skeleton means that a metal atom is introduced into the zeolite skeleton in the same manner as silicon (Si) by a method such as mixing a compound containing the target metal atom as a raw material for hydrothermal synthesis.
  • a method such as mixing a compound containing the target metal atom as a raw material for hydrothermal synthesis.
  • the state of containing metal atoms in the zeolite skeleton is, for example, XRD (X-ray Diffraction), NMR (Nuclear Magnetic Resonance spectroscopy), FT-IR (Fourier Transform Infrared Spectroscopy), XPS (X-ray Photoelectron Spectroscopy) and It can be grasped by various measurement methods such as ESCA (Electron Spectroscopy for Chemical Analysis).
  • Lewis acidity means the property of being able to accept a lone pair of electrons. For example, when pyridine is adsorbed on a zeolite catalyst and subjected to FT-IR analysis, it means that an absorption band is detected near 1450 cm ⁇ 1 . do.
  • Solid basicity means that the surface of the zeolite catalyst exhibits basicity. Strong solid basicity means that the surface of the zeolite catalyst has strong basicity . It means that the desorption peak of CO 2 adsorbed on the catalyst is detected.
  • the zeolite catalyst according to this embodiment is a zeolite having a 10-membered ring structure and has an MFI structure.
  • the MFI structure zeolite is not particularly limited, but is preferably a crystalline metallosilicate.
  • the zeolite having an MFI structure means a zeolite corresponding to MFI with a structure code stored in the database of the International Zeolite Association. It can be confirmed by, for example, X-ray diffraction that the zeolite has a 10-membered ring structure, particularly an MFI structure.
  • the metal atoms contained in the zeolite skeleton are not particularly limited as long as they are transition metal atoms or post-transition metal atoms. Examples include titanium (Ti), vanadium (V), iron (Fe), cobalt (Co), nickel ( Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), indium (In), and the like can be used. Among these, it is preferable to use zinc (Zn), nickel (Ni), and iron (Fe) from the viewpoint of excellent reactivity in the cyclization dehydrogenation reaction.
  • the metal atoms contained in the zeolite skeleton may be of one kind alone, or two or more kinds thereof may be used.
  • the content of metal atoms contained in the zeolite skeleton is not particularly limited, but is preferably 1 to 15 atom%, more preferably 1 to 10 atom%, and still more preferably 1 to 3 atom% relative to silicon (Si) atoms.
  • the zeolite catalyst has a large number of solid base points, and tends to exhibit excellent reactivity in the cyclization dehydrogenation reaction.
  • the reaction efficiency of the cyclization dehydrogenation reaction of the starting material tends to be excellent with respect to the metal content.
  • the content of alkali metal contained in the zeolite catalyst is preferably no alkali metal or 1 atom % or less, more preferably 0.1 atom % or less, relative to Si atoms.
  • the content is equal to or less than the above upper limit, there is a tendency that the reactivity of the cyclization dehydrogenation reaction can be maintained at a high level while promoting the crystallization of the zeolite.
  • the zeolite catalyst may further contain a molding aid within the scope of the present invention.
  • the molding aid may be, for example, at least one selected from the group consisting of thickeners, surfactants, water retention agents, plasticizers, binder raw materials, and the like.
  • the molding process for molding the zeolite catalyst may be carried out at an appropriate stage of the zeolite catalyst production process in consideration of the reactivity of the molding aid.
  • the zeolite catalyst may be one in which platinum is supported on a carrier using a platinum (Pt) source.
  • Platinum sources include, for example, tetraammineplatinum(II) acid, tetraammineplatinate(II) acid salts (e.g., nitrates, etc.), tetraammineplatinum(II) acid hydroxide solutions, dinitrodiammineplatinum(II) nitric acid solutions, hexahydroxo Platinum (IV) acid nitric acid solution, hexahydroxo platinum (IV) acid ethanolamine solution, and the like.
  • the platinum source it is preferable to use a metal source containing no chlorine atoms. By using a metal source that does not contain chlorine atoms, corrosion of the device can be suppressed, and the cyclization dehydrogenation reaction can be carried out more efficiently.
  • the content of platinum in the zeolite-supported platinum catalyst is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on the total amount of the zeolite-supported platinum catalyst.
  • the content is preferably 3.0% by mass or less, more preferably 2.5% by mass or less, based on the total amount of the zeolite-supported platinum catalyst.
  • a zeolite catalyst that has been subjected to a reduction treatment as a pretreatment may be used.
  • the reduction treatment can be performed, for example, by maintaining the zeolite catalyst at 40 to 600° C. in a reducing gas atmosphere.
  • the retention time can be, for example, 0.05 to 24 hours.
  • Reducing gases may include, for example, hydrogen, carbon monoxide, and the like.
  • the zeolite catalyst according to the present embodiment can be prepared by combining a silica gel aging process, a hydrothermal synthesis process, and a calcination process. This allows zeolite catalysts to be prepared without the use of alkali metals, boron or aluminum.
  • a silica source, an organic structure directing agent (OSDA), and water are mixed, and aged (stirred) at 100° C. or less for 10 hours or more, Then, after mixing transition metal atoms or post-transition metal atoms as a metal source, hydrothermal synthesis is performed at 100° C. or higher, followed by firing at 500° C. or higher for 5 hours or more.
  • OSDA organic structure directing agent
  • the method for supporting platinum is not particularly limited, and for example, an impregnation method, a deposition method, a coprecipitation method, a kneading method, an ion exchange method, a pore filling method, or the like can be used.
  • silica sources examples include silicon alcoholates, silanes, silicon tetrachloride, hydrolyzable silicon compounds such as water glass, and the like.
  • the organic structure-directing agent is not particularly limited as long as a zeolite having an MFI structure can be obtained, and for example, quaternary alkylammonium salts, amines, and the like can be used.
  • the organic structure-directing agent may be used alone or in combination of two or more.
  • a suitable preparation example of the zeolite catalyst according to the present embodiment it is preferable to further include a step of washing the synthesized product with water before calcining the synthesized product obtained after the hydrothermal synthesis.
  • the step of washing with water the influence of alkali such as sodium on the zeolite catalyst can be reduced.
  • the above method is an example of a suitable preparation example for preparing a zeolite catalyst without using an alkali metal, boron, or aluminum.
  • alkali metals boron or aluminum.
  • an alkali metal may be mixed within the scope of the present invention. By mixing an alkali metal, promotion of zeolite crystallization is maintained, and a zeolite catalyst having an MFI structure in which transition metal atoms or post-transition metal atoms are introduced into the zeolite skeleton tends to be easily obtained.
  • alkali metals include sodium (Na), potassium (K), rubidium (Rb), and the like. Among these, sodium (Na) is preferred.
  • the amount of the alkali metal to be mixed as described above, it is preferable to mix the amount of 1 atom % or less with respect to the Si atoms in the zeolite catalyst.
  • a zeolite catalyst in which transition metal atoms or post-transition metal atoms are introduced into the zeolite skeleton and the active sites are highly dispersed can be obtained. Furthermore, it is possible to obtain a zeolite catalyst with strong solid basicity in which Bronsted acids are almost absent and only Lewis acids are present.
  • the raw material composition containing the olefin having 5 carbon atoms is brought into contact with the zeolite catalyst in the cyclization dehydrogenation step. Thereby, a cyclodehydrogenation reaction of the olefin having 5 carbon atoms takes place, and a reaction product containing cyclopentadiene is obtained.
  • the raw material composition may contain at least an olefin having 5 carbon atoms.
  • the olefin having 5 carbon atoms is an organic compound having one or more carbon-carbon double bonds in the molecule and generally having no functional group, and is a linear and/or branched carbonized carbon having 5 carbon atoms. means hydrogen.
  • the olefin having 5 carbon atoms according to the present embodiment is preferably a monoolefin and/or diolefin having 5 carbon atoms.
  • a monoolefin having 5 carbon atoms is an organic compound having only one carbon-carbon double bond in the molecule and usually having no functional group, and is a linear and/or branched chain having 5 carbon atoms. means hydrocarbons.
  • Examples of monoolefins having 5 carbon atoms according to the present embodiment include 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene. Among them, 1-pentene is preferably used.
  • the monoolefin having 5 carbon atoms may be one of the above, or may be a mixture containing two or more.
  • a diolefin having 5 carbon atoms is an organic compound having two or more carbon-carbon double bonds in the molecule and generally having no functional group. means hydrocarbons.
  • Examples of the diolefin having 5 carbon atoms according to the present embodiment include 1,3-pentadiene and 1,4-pentadiene, and among these, 1,3-pentadiene is preferably used.
  • the diolefin having 5 carbon atoms may be one of the above, or may be a mixture containing two or more.
  • the raw material composition may further contain compounds other than the olefin having 5 carbon atoms within the scope of the present invention.
  • it may contain a C5 fraction mainly composed of hydrocarbons having 5 carbon atoms obtained in a naphtha pyrolysis furnace or the like.
  • the raw material composition may be used as it is in a state in which compounds other than olefins having 5 carbon atoms due to the production method are arbitrarily mixed, or may be used after purification.
  • the content of the olefin having 5 carbon atoms in the raw material composition is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 90% by mass or more. There may be.
  • the content of the monoolefin having 5 carbon atoms in the raw material composition is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more, and 100% by mass. may be
  • the content of the diolefin having 5 carbon atoms in the raw material composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more.
  • the content is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and particularly preferably 70% by mass or less.
  • the C5 olefin may be a mixture of a C5 monoolefin and a C5 diolefin.
  • the mixing ratio (mass ratio) of the monoolefin having 5 carbon atoms and the diolefin having 5 carbon atoms is not particularly limited, and may depend on the ratio resulting from the production method.
  • the mixing ratio (mass ratio) of the monoolefin having 5 carbon atoms and the diolefin having 5 carbon atoms is preferably 20:80 to 95:5, more preferably 25:75 to 90:10, and 30:70 to 85: 15 is more preferred.
  • the cyclization dehydrogenation step may be carried out by, for example, using a reactor filled with a zeolite catalyst and passing the raw material composition through the reactor.
  • a reactor various reactors used for gas phase reactions using solid catalysts can be used. Examples of reactors include fixed bed adiabatic reactors, radial flow reactors, tubular reactors, and the like.
  • the reaction form of the cyclization dehydrogenation reaction is a continuous reaction form in which the raw material composition is continuously supplied, and may be, for example, a fixed bed system, a moving bed system, or a fluidized bed system.
  • the fixed bed type is preferable from the viewpoint of facility cost.
  • the temperature at which the raw material composition is brought into contact with the zeolite catalyst is preferably 350 to 800° C. from the viewpoint of reaction efficiency. 400 to 700°C is more preferred, and 450 to 650°C is even more preferred.
  • the reaction temperature is at least the above lower limit, the yield of cyclopentadiene tends to be further improved.
  • the reaction temperature is equal to or lower than the above upper limit, there is a tendency that the rate of coke formation is suppressed and the high cyclization dehydrogenation activity of the zeolite catalyst can be maintained for a longer period of time.
  • the pressure when the raw material composition is brought into contact with the zeolite catalyst is preferably 0.01 to 4.0 MPa, and 0.03. ⁇ 0.5 MPa is more preferred, and 0.05 to 0.3 MPa is even more preferred.
  • the reaction pressure is within the above range, the cyclization dehydrogenation reaction tends to proceed more easily, and a more excellent reaction efficiency tends to be obtained.
  • the raw material composition supplied to the reaction system is preferably gaseous.
  • the raw material composition is a gas, it can be mixed with a gas other than the raw material composition and supplied to the reaction system as a gas containing the raw material composition.
  • Gases other than the raw material composition may be gases that are substantially inert under the conditions of the cyclization dehydrogenation reaction.
  • Gases that are substantially inert under cyclization dehydrogenation reaction conditions include, for example, molecular hydrogen, nitrogen, argon, neon, carbon dioxide, helium, steam, and the like.
  • any diluent that is substantially inert under the cyclizing dehydrogenation reaction conditions may be supplied to the reaction system.
  • the mixture of the raw material composition supplied to the reaction system and a substantially inert gas under the cyclization dehydrogenation reaction conditions is The gas flow rate (ml/min) ratio is preferably 1:0.1 to 1:20, more preferably 1:0.5 to 1:10.
  • the gas flow rate (ml/min) ratio between the raw material composition and molecular hydrogen supplied to the reaction system is preferably 1:0.001 to 1:3, more preferably 1:0.001 to 1:0.5.
  • substantially not supplying molecular hydrogen to the reaction system means not intentionally supplying molecular hydrogen to the reaction system. It means that the gas flow rate (ml/min) ratio of the composition to molecular hydrogen is less than 1:0.001. This makes it possible to reduce the production cost of cyclopentadiene, which is industrially useful.
  • the mass hourly space velocity (hereinafter sometimes referred to as "WHSV") is adjusted from the viewpoint of improving the conversion rate of the raw material.
  • WHSV is preferably 0.01 h ⁇ 1 or more, more preferably 0.1 h ⁇ 1 or more.
  • WHSV is preferably 100 h ⁇ 1 or less, more preferably 20 h ⁇ 1 or less, from the viewpoint of reducing the size of the reactor.
  • WHSV is the ratio (F/W) of the feed rate (supply amount/time) F of the raw material to the mass W of the zeolite catalyst in a continuous reactor.
  • the amounts of the raw material composition and the catalyst used may be appropriately selected in a more preferable range according to the reaction conditions, the activity of the catalyst, etc., and the WHSV is not limited to the above range.
  • the method for separating and purifying cyclopentadiene from the reaction product obtained by the cyclization dehydrogenation step is not particularly limited, and purification can be performed by a known distillation operation or the like.
  • unreacted raw materials may be recovered from the reaction product after separation of cyclopentadiene, and the recovered raw materials may be mixed with new raw materials for reuse.
  • a raw material composition containing an olefin having 5 carbon atoms can be stably produced in a high yield over a long period of time. Pentadiene can be produced.
  • zeolite catalyst was pretreated at 500° C. for 1 hour while helium gas was passed through at a flow rate of 50 mL/min. After that, it was cooled to less than 40° C., and 1 vol% CO 2 /He gas was passed at a flow rate of 50 mL/min to adsorb CO 2 on the zeolite catalyst, and then helium gas was passed at a flow rate of 50 mL/min for 5 minutes. . Thereafter, the temperature was raised to 800° C. at a heating rate of 10° C./min while helium gas was circulated at 30 mL/min, and CO 2 desorption was analyzed with a TCD (Thermal Conductivity Detector) and MASS.
  • TCD Thermal Conductivity Detector
  • NH 3 -TPD analysis was performed using a TPD analyzer (BELCAT II, manufactured by Microtrack Bell Co., Ltd.). About 30 mg of the zeolite catalyst was pretreated at 500° C. for 1 hour while helium gas was passed through at a flow rate of 50 mL/min.
  • UV-vis analysis was performed with an ultraviolet-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation, V-660). The measurement method was the diffuse reflectance method, and the analysis was performed at room temperature.
  • FIG. 3 shows the results of FT-IR analysis at room temperature after pretreatment by evacuation at 450° C. for 1 hour. If Zn exists close to each other, it becomes Zn--O--Zn by pretreatment.
  • ZnO crystals and Zn-impregnated supported catalysts do not have an absorption band in the region of 3600 to 3700 cm ⁇ 1 in FT-IR analysis.
  • the [Zn]-MFI catalyst an absorption band near 3640 cm ⁇ 1 derived from the Zn—OH vibration of Zn is observed, and it is considered that Zn is isolated from each other by being incorporated into the zeolite skeleton.
  • the system was cooled to 150° C., pyridine was introduced, and the temperature was raised to 250° C. while evacuating, followed by FT-IR analysis. The results are shown in FIG.
  • the peak of ZnO crystals is assigned at 255-322 nm and the peak of ZnO clusters in zeolite pores at 240 nm.
  • the peaks of ZnO crystals and ZnO crystals in zeolite pores were not observed in the [Zn]-MFI catalyst, suggesting that Zn atoms are highly dispersed within the zeolite skeleton.
  • the [Zn]-MFI catalyst obtained was a zeolite catalyst with an MFI structure that had no Bronsted acid, only Lewis acid, and had strong solid basicity.
  • silicalite was confirmed to have an MFI structure by X-ray diffraction measurement (X-ray source: CuK ⁇ , device: RINT 2500 manufactured by Rigaku Corporation). Subsequently, zinc was impregnated and supported using an aqueous solution of 1M zinc nitrate hexahydrate so that the amount of zinc supported was 10.0% by mass, dried overnight at 130°C, and calcined at 550°C for 3 hours to form Zn. /[Si]-MFI catalyst was prepared.
  • alumina-magnesia carrier having a spinel structure was obtained.
  • a diffraction peak derived from Mg spinel was confirmed in .
  • using a dinitrodiammine platinum (II) nitric acid solution manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., [Pt(NH 3 ) 2 (NO 2 ) 2 ]/HNO 3 )
  • the platinum content was reduced to 1.0% by mass.
  • a Pt/MgAl 2 O 4 catalyst was prepared by impregnating and supporting platinum so as to obtain a Pt/MgAl 2 O 4 catalyst.
  • the product of the cyclization dehydrogenation reaction was analyzed by a gas chromatograph (FID-GC) equipped with a hydrogen flame detector. was analyzed using Based on the gas chromatogram, each component (unit: mass%) of the sampled reaction product was quantified, and the total conversion rate of the raw materials (the value obtained by adding the conversion rates of each raw material, unit: mass%) and the yield of cyclopentadiene The rate (yield with respect to the amount of olefin having 5 carbon atoms used as a raw material, mass %) was calculated. Table 1 shows the results. The total conversion rate was calculated by the following formula (1).
  • Total conversion rate (% by mass) (1-( 1-pentene produced by C + 1,3-pentadiene produced by C)/(C raw material 1-pentene + C raw material 1,3-pentadiene )) ⁇ 100
  • C raw material 1-pentene and C raw material 1,3-pentadiene are the mass % of 1-pentene and 1,3-pentadiene contained in the raw materials
  • C -generated 1-pentene and C -generated 1,3- Pentadiene is the weight percent of 1-pentene and 1,3- pentadiene contained in the product.
  • Examples 2 to 11 The yield of cyclopentadiene was calculated in the same manner as in Example 1, except that the raw material composition, catalyst, WHSV, and gas flow ratio were changed as shown in Tables 2 to 5.
  • a cyclopentadiene yield ratio (cyclopentadiene yield at a reaction time of 6.5 hours/cyclopentadiene yield at a reaction time of 2.5 hours) was calculated from the resulting cyclopentadiene yield. The results are shown in Tables 2-5.
  • Example 12 and 13 and Comparative Examples 1 to 3 In Example 1, except that the raw material composition, catalyst, WHSV, and gas flow rate ratio were changed as shown in Tables 1 and 6, the conversion rate of the raw material or the total conversion of the raw material was measured in the same manner as in Example 1. and the yield of cyclopentadiene were calculated respectively. The results are shown in Tables 1 and 6.
  • the zeolite catalyst of Example 1 in which a transition metal was introduced into the zeolite skeleton was used for the reaction using a catalyst supporting a noble metal, and the crystalline metallosilicate of Comparative Example 1 was used as a carrier.
  • the total conversion of raw materials and the yield of cyclopentadiene tended to be higher compared to supported precious metal catalysts, which were not used.
  • a high yield of cyclopentadiene was maintained even after 6.5 hours, and it was confirmed that cyclopentadiene was produced stably over the course of the reaction time.
  • the catalyst of Comparative Example 1 was deactivated due to coke deterioration immediately after the start of the reaction, and there was a tendency for the cyclopentadiene yield to remain low.
  • Table 2 shows the effect of platinum content in the zeolite catalyst on the cyclopentadiene yield ratio. As shown in Table 2, even when the platinum content in the zeolite catalyst was 0.2% by mass, stable production of cyclopentadiene was observed over the course of the reaction time.
  • Table 3 shows the effect of WHSV on the cyclopentadiene yield ratio. As shown in Table 3, stable formation of cyclopentadiene over the reaction time was observed in a wide range of WHSV from 0.5 to 5.0 h ⁇ 1 .
  • Example 1 in Table 1 and Example 8 in Table 4 show the effect of the content of the C5 diolefin in the raw material composition on the yield ratio of cyclopentadiene.
  • the yield ratio (6.5 hr/2.5 hr) of cyclopentadiene in Example 1 was 1.09.
  • Example 1 in Table 1 and Example 8 in Table 4 even if the content of the diolefin having 5 carbon atoms in the raw material composition was 33% by mass and 50% by mass, the reaction time Formation of stable cyclopentadiene was observed.
  • Example 1 in Table 1 and Examples 9 to 11 in Table 5 show the effect of the gas flow ratio supplied to the reaction system on the yield ratio of cyclopentadiene. As shown in Example 1 in Table 1 and Examples 9 to 11 in Table 5, even when molecular hydrogen was not supplied to the reaction system, stable cyclopentadiene formation was observed over the course of the reaction time. was taken.

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Abstract

L'invention fournit un nouveau procédé de fabrication de cyclopentadiène, selon lequel un cyclopentadiène est fabriqué selon un haut rendement et de manière stable sur le long terme, à l'aide d'un catalyseur de zéolite et en présence d'une oléfine. Plus précisément, l'invention concerne un procédé de fabrication de cyclopentadiène qui comporte une étape de cyclisation et déshydrogénation au cours de laquelle une composition de matière de départ contenant une oléfine de 5 atomes de carbone, est mise en contact avec le catalyseur de zéolite de structure MFI, et un produit de réaction contenant un cyclopentadiène est obtenu. Le catalyseur de zéolite contient au moins une sorte d'atome de métal choisie parmi des métaux de transition ou des métaux de post-transition, et présente une acidité de Lewis ainsi qu'une forte basicité solide.
PCT/JP2022/024103 2021-06-21 2022-06-16 Procédé de fabrication de cyclopentadiène WO2022270401A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011073913A (ja) * 2009-09-30 2011-04-14 Asahi Kasei Chemicals Corp Ｚｓｍ−５型ゼオライトの製造方法
JP2018533587A (ja) * 2015-11-04 2018-11-15 エクソンモービル ケミカル パテンツ インコーポレイテッド 非環式ｃ５化合物の環式ｃ５化合物への変換プロセス及びそのプロセスに用いる触媒組成物
WO2020091968A1 (fr) * 2018-10-30 2020-05-07 Exxonmobil Chemical Patents Inc. Calcination de catalyseurs à tamis moléculaire microporeux
JP2021514831A (ja) * 2018-03-02 2021-06-17 サウジ アラビアン オイル カンパニーＳａｕｄｉ Ａｒａｂｉａｎ Ｏｉｌ Ｃｏｍｐａｎｙ 脱水素反応に有用な触媒系

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011073913A (ja) * 2009-09-30 2011-04-14 Asahi Kasei Chemicals Corp Ｚｓｍ−５型ゼオライトの製造方法
JP2018533587A (ja) * 2015-11-04 2018-11-15 エクソンモービル ケミカル パテンツ インコーポレイテッド 非環式ｃ５化合物の環式ｃ５化合物への変換プロセス及びそのプロセスに用いる触媒組成物
JP2021514831A (ja) * 2018-03-02 2021-06-17 サウジ アラビアン オイル カンパニーＳａｕｄｉ Ａｒａｂｉａｎ Ｏｉｌ Ｃｏｍｐａｎｙ 脱水素反応に有用な触媒系
WO2020091968A1 (fr) * 2018-10-30 2020-05-07 Exxonmobil Chemical Patents Inc. Calcination de catalyseurs à tamis moléculaire microporeux

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