WO2021132239A1 - Procédé de production d'indène - Google Patents

Procédé de production d'indène Download PDF

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WO2021132239A1
WO2021132239A1 PCT/JP2020/047943 JP2020047943W WO2021132239A1 WO 2021132239 A1 WO2021132239 A1 WO 2021132239A1 JP 2020047943 W JP2020047943 W JP 2020047943W WO 2021132239 A1 WO2021132239 A1 WO 2021132239A1
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catalyst
indene
zeolite
zeolite catalyst
atom
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PCT/JP2020/047943
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English (en)
Japanese (ja)
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裕之 今井
瀬川　敦司
泰博 荒木
匡 梅田
泰之 岩佐
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公立大学法人北九州市立大学
Ｅｎｅｏｓ株式会社
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    • 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
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/45—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing nine carbon atoms
    • C07C13/465—Indenes; Completely or partially hydrogenated indenes
    • 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

Definitions

  • the present invention relates to a method for producing indene.
  • Inden is an industrially useful substance as a raw material for kumaron-indene resin and optical resin.
  • a method for producing indene a method of recovering indene from a coal tar fraction is known, but the coal tar fraction contains many impurities such as benzonitrile and benzofuran, and the separation and recovery method by distillation is used. In particular, it is difficult to separate benzofurans with similar boiling points to obtain high-purity indene.
  • a method for producing high-purity indene a method by a direct dehydrogenation reaction of tetrahydroindene is known (Patent Documents 1 to 3).
  • a zeolite catalyst and the like are known (Patent Document 4).
  • An object of the present invention is to provide a method for stably producing indene in a high yield for a long period of time using a zeolite catalyst as a new method for producing indene.
  • indene can be stably produced from a raw material composition containing indane in a high yield for a long period of time by using a specific zeolite catalyst. We have found that we can do this, and have completed the present invention.
  • One aspect of the present invention relates to a method for producing indene, which comprises a dehydrogenation step of bringing a raw material composition containing indane into contact with a zeolite catalyst having an MFI structure to obtain a reaction product containing indene.
  • the zeolite catalyst contains at least one metal atom selected from a transition metal or a post-transition metal in the zeolite skeleton, and has Lewis acidity and strong solid basicity.
  • the metal atom is one or more selected from Zn atom, Fe atom, and Ni atom, and the content of the metal atom may be 1 to 15 atom% with respect to the Si atom.
  • the zeolite catalyst may not contain an alkali metal or may contain 1 atom% or less of an alkali metal with respect to the Si atom of the zeolite skeleton.
  • the zeolite catalyst may be a catalyst on which a Pt atom is supported.
  • the raw material composition may further contain at least one or more of octahydroindene and hexahydroindene.
  • the raw material composition may further contain molecular hydrogen.
  • the production method according to one embodiment may further include a raw material synthesis step for obtaining indane by a dehydrogenation reaction of tetrahydroindene.
  • the present invention as a new method for producing inden, it is possible to provide a method for stably producing inden in a high yield for a long period of time using a zeolite catalyst.
  • the method for producing indene according to the present embodiment includes a dehydrogenation step of bringing a raw material composition containing indane into contact with a zeolite catalyst having an MFI structure to obtain a reaction product containing indene. According to the production method according to the present embodiment, by adopting a specific zeolite catalyst, indene can be stably produced in a high yield for a long period of time.
  • the zeolite catalyst according to the present embodiment contains at least one metal atom selected from a transition metal or a post-transition metal in the zeolite skeleton, and has Lewis acidity and strong solid basicity.
  • the zeolite catalyst according to the present embodiment Bronsted acid is hardly present in the zeolite catalyst, and only Lewis acid is present. In general, it is known that the amount of by-products of the dehydrogenation reaction increases or decreases depending on the presence of Bronsted acid, but since the zeolite catalyst according to the present embodiment contains almost no Bronsted acid. , Side reactions can be controlled, and the generation of by-products can be suppressed.
  • the zeolite catalyst according to the present embodiment for the production of inden for example, it is conceivable that side reactions are suppressed and the inden selectivity is improved, coke generation due to polymerization of decomposition by-products is suppressed, and the like.
  • inden can be stably produced over a long period of time. Further, since the zeolite catalyst according to the present embodiment has the active sites of the dehydrogenation reaction arranged in a high dispersion, the zeolite catalyst according to the present embodiment is used for the production of indene, so that the indene can be produced in a high yield. Can be manufactured.
  • zeolite is a crystal in which TO 4 units (T is the central atom) having a tetrahedral structure share an O atom and are three-dimensionally connected to form open regular micropores. It means a sex substance.
  • the transition metal means a metal belonging to the Group 3 to Group 12 elements of the periodic table in the periodic table of long-periodic elements based on the provisions of the IUPAC (International Union of Pure and Applied Chemistry).
  • the post-transition metal means a base metal having an atomic number after the transition metal of the 4th, 5th, and 6th periods of the periodic table in the periodic table.
  • the inclusion of metal atoms in the zeolite skeleton means that the metal atoms are introduced into the zeolite skeleton in the same manner as silicon (Si) by a method of mixing the metal atoms as a raw material for hydrothermal synthesis.
  • the states containing metal atoms in the zeolite skeleton include, 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 unshared electron pairs, and means that, for example, when pyridine is adsorbed on a zeolite catalyst and FT-IR analysis is performed, an absorption band is detected in the vicinity of 1450 cm -1. To do.
  • Solid basicity means that the surface of the zeolite catalyst is basic.
  • strong solid basic means that strong basicity of the surface of the zeolite catalyst, for example, TPD (Temperature Programmed Desorption) upon CO 2 -TPD analyzed by the analyzer, the zeolite to a high temperature range of not lower than 500 ° C. It means that the peak derived from 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.
  • Zeolites having an MFI structure are not particularly limited, but are preferably crystalline metallosilicates.
  • the zeolite having an MFI structure means a zeolite corresponding to MFI in the structure code stored in the database by the International Zeolite Association. It can be confirmed by, for example, X-ray diffraction that the zeolite is a zeolite having a 10-membered ring structure, particularly an MFI structure.
  • the metal atom contained in the zeolite skeleton is not particularly limited as long as it is a transition metal atom or a post-transition metal atom, and for example, 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.
  • 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.
  • zinc (Zn), nickel (Ni), and iron (Fe) are preferably used from the viewpoint of excellent reactivity in the dehydrogenation reaction.
  • the metal atom contained in the zeolite skeleton one kind may be used alone, or two or more kinds may be used.
  • the content of the metal atom contained in the zeolite skeleton is not particularly limited, but is preferably 1 to 15 atom% and more preferably 2 to 10 atom% with respect to the silicon (Si) atom.
  • the content of the metal atom contained in the zeolite skeleton is at least the lower limit of the above range, the solid basicity of the zeolite catalyst becomes strong, and the reactivity of the dehydration reaction of indane is excellent.
  • the content of the metal atom contained in the zeolite skeleton is not more than the upper limit of the above range, the reaction efficiency of the dehydrogenation reaction of indane with respect to the metal content is excellent, which is preferable.
  • the content of the alkali metal contained in the zeolite catalyst is preferably not containing the alkali metal or is preferably 1 atom% or less, and more preferably 0.1 atom% or less with respect to the Si atom.
  • it is not more than the above upper limit value it is preferable because the reactivity of the dehydrogenation reaction of indene can be maintained high while promoting the crystallization of zeolite.
  • the zeolite catalyst may further contain a molding aid as long as it does not deviate from the gist 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 step of molding the zeolite catalyst may be performed at an appropriate stage in the manufacturing process of the zeolite catalyst in consideration of the reactivity of the molding aid.
  • the zeolite catalyst may be a catalyst in which platinum is supported on a carrier using a platinum (Pt) source.
  • platinum platinum
  • the platinum source include tetraammine platinum (II) acid, tetraammine platinum (II) acid salt (for example, nitrate), tetraammine platinum (II) acid hydroxide solution, dinitrodiammine platinum (II) nitric acid solution, and hexahydroxo.
  • platinum it is preferable to use a metal source containing no chlorine atom. By using a metal source that does not contain chlorine atoms, corrosion of the device can be suppressed and indane can be dehydrogenated more efficiently.
  • the content of platinum in the zeolite catalyst is usually 0.05 to 2.5 wt% based on the total amount of the zeolite catalyst.
  • the amount of platinum carried is preferably 0.1 wt% or more based on the total amount of the zeolite catalyst.
  • the amount of platinum supported is preferably 2.0 wt% or less based on the total amount of the zeolite catalyst. With such a loading amount, the platinum surface area per unit platinum weight becomes large, so that a more efficient reaction system can be realized.
  • a catalyst that has been reduced as a pretreatment may be used as the zeolite catalyst.
  • the reduction treatment can be carried out, for example, by holding the zeolite catalyst at 40 to 600 ° C. in an atmosphere of a reducing gas.
  • the holding time may be, for example, 0.05 to 24 hours.
  • the reducing gas may be, for example, a gas containing hydrogen, carbon monoxide, or the like.
  • the zeolite catalyst in the present embodiment can be prepared by treating a combination of a silica gel aging step, a hydrothermal synthesis step, and a firing step. This allows the zeolite catalyst to be prepared without the use of alkali metals, boron or aluminum.
  • a silica source, an organic structure defining agent (OSDA), and water are mixed and aged (stirred) at 100 ° C. or lower for 10 hours or more. Then, after mixing the transition metal atom or the post-transition metal atom as a metal source, hydrothermal synthesis is performed at 100 ° C. or higher, and then firing is performed at 500 ° C. or higher for 5 hours or longer.
  • OSDA organic structure defining 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 and the like can be used.
  • a hydrolyzable silicon compound such as silicon alcoholate, silane, silicon tetrachloride, or water glass
  • the organic structure defining agent is not particularly limited as long as a zeolite having an MFI structure can be obtained, and for example, a quaternary alkylammonium salt, an amine or the like can be used.
  • the organic structure defining agent one kind may be used alone, or two or more kinds may be mixed and used.
  • a step of washing the synthetic reaction product with water before firing the synthetic reaction product obtained after hydrothermal synthesis at 500 ° C. or higher for 5 hours or more is further performed. It is preferable to include it. By including the step of washing with water, the influence of alkali such as sodium on the zeolite catalyst can be reduced.
  • the above-mentioned method is an example of a suitable production example for preparing a zeolite catalyst without using alkali metal, boron or aluminum, but the production method of the present embodiment does not deviate from the gist of the present invention.
  • the production method of the present embodiment does not deviate from the gist of the present invention.
  • it does not limit the use of alkali metals, boron or aluminum.
  • an alkali metal may be mixed as long as it does not deviate from the gist of the present invention.
  • the alkali metal By mixing the alkali metal, crystallization of the zeolite is promoted, and there is a tendency that a zeolite catalyst having an MFI structure in which a transition metal atom or a post-transition metal atom is introduced into the zeolite skeleton can be easily obtained.
  • the alkali metal include sodium (Na), potassium (K), rubidium (Rb) and the like. Of these, sodium (Na) is preferred.
  • the mixing amount of the alkali metal as described above, it is preferable to mix an amount of 1 atom% or less with respect to the Si atom in the zeolite catalyst.
  • a transition metal atom or a post-transition metal atom is introduced into the skeleton of zeolite, and a zeolite catalyst in which active sites are highly dispersed can be obtained. Furthermore, it is possible to obtain a zeolite catalyst having a strong solid basicity in which Bronsted acid is almost absent and only Lewis acid is present.
  • the raw material composition containing indane is brought into contact with the above-mentioned zeolite catalyst. As a result, a dehydrogenation reaction of indane occurs, and a reaction product containing indene is obtained.
  • the raw material composition may contain at least indane, but it is preferable that at least one of octahydroindene and hexahydroindene is further contained. Since the zeolite catalyst according to the present embodiment has excellent reactivity in the dehydrogenation reaction, indene can be efficiently produced by containing at least one of octahydroindene and hexahydroindene.
  • Octahydroindene has two isomers, a cis form and a trans form, and hexahydroindene has a plurality of isomers having different double bond positions.
  • Hexahydroindene has a structure in which one molecule of hydrogen is dehydrogenated from octahydroindene, so that it is easily dehydrogenated and indene is likely to occur.
  • the origin of production of indane, octahydroindene and hexahydroindene (hereinafter, may be referred to as "indane mixture”) is not particularly limited.
  • tetrahydroindene may be obtained by a dehydrogenation reaction.
  • a mixture in which compounds other than the indane mixture resulting from the production method are arbitrarily mixed may be used as it is, or a purified product may be used.
  • the mixing ratio of indane, octahydroindene, and hexahydroindene is not particularly limited, and for example, the mixing ratio depends on the ratio due to the production method. May be.
  • the mixing ratio (wt%) of indane and hexahydroindene is preferably 40 to 90: 1 to 60.
  • the mixing ratio of indane, octahydroindene, and hexahydroindene can be measured using a gas chromatograph analyzer.
  • the raw material composition may further contain an indane or a compound other than the indane mixture.
  • the raw material composition may further contain, for example, an inert gas such as nitrogen or argon, steam, molecular hydrogen, oxygen, carbon monoxide, carbon dioxide, alkanes, olefins and the like.
  • the raw material composition preferably contains molecular hydrogen from the viewpoint of improving the reaction efficiency in the dehydrogenation reaction of indane.
  • an inert gas such as nitrogen or argon, steam, molecular hydrogen, oxygen, carbon monoxide, carbon dioxide, alkanes, olefins and the like.
  • the raw material composition preferably contains molecular hydrogen from the viewpoint of improving the reaction efficiency in the dehydrogenation reaction of indane.
  • the coexistence of molecular hydrogen reduces the yield from the viewpoint of thermodynamic equilibrium constraint.
  • the present inventors have found that when the zeolite catalyst of the present embodiment is used, the reaction efficiency in the dehydrogenation reaction of indane or an indane mixture can be improved by intentionally coexisting with molecular hydrogen. It was. Therefore, the raw material composition preferably contains molecular hydrogen.
  • the mole fraction of the indane or the indane mixture in the raw material composition is preferably 0.1 or more, and more preferably 0.2 or more.
  • the upper limit of the molar fraction of indane or the indane mixture in the raw material composition is not particularly limited, but may be, for example, 0.95 or less, preferably 0.9 or less.
  • the molar ratio of molecular hydrogen to the indan or indan mixture is preferably 10.0 or less in the raw material composition. It is more preferable that it is 7.0 or less. As a result, the influence of the thermodynamic equilibrium constraint is reduced, and the dehydrogenation reaction tends to proceed more efficiently.
  • the molar ratio of molecular hydrogen to the indane or indane mixture in the raw material composition is preferably 0.01 or more, more preferably 0.05 or more. As a result, the presence of molecular hydrogen can suppress the formation of cork on the catalyst, improve the durability of the catalyst, and obtain indene in a high yield.
  • the total content of the indane or the indane mixture and other compounds other than the molecular hydrogen is, for example, 10.0 times mol or less with respect to the indane or the indane mixture. It is preferably 5.0 times or less the molar amount of indane or an indane mixture, and may be 0.
  • a reactor filled with a zeolite catalyst may be used, and the dehydrogenation reaction may be carried out by flowing a raw material gas through the reactor.
  • the reactor various reactors used for the gas phase reaction using a solid catalyst can be used. Examples of the reactor include a fixed bed adiabatic reactor, a radial flow reactor, a tubular reactor and the like.
  • the reaction type of the dehydrogenation reaction may be, for example, a fixed bed type, a moving bed type or a fluidized bed type. Of these, the fixed floor type is preferable from the viewpoint of equipment cost.
  • the temperature at which the raw material composition is brought into contact with the zeolite catalyst (which may also be the reaction temperature of the dehydrogenation reaction or the temperature inside the reactor) may be, for example, 350 to 800 ° C. from the viewpoint of reaction efficiency. , 400 to 700 ° C., and may be 450 ° C. to 650 ° C.
  • the reaction temperature is 350 ° C. or higher, the equilibrium conversion rate of indane or an indane mixture does not become too low, so that the yield of indene tends to be further improved.
  • the reaction temperature is 800 ° C. or lower, the rate of cork formation is suppressed, and the high activity of the zeolite catalyst can be maintained for a longer period of time.
  • the pressure at which the raw material composition is brought into contact with the zeolite catalyst (which can also be referred to as the reaction pressure of the dehydrogenation reaction or the pressure inside the reactor) may be, for example, 0.01 to 4.0 MPa, and may be 0. It may be 03 to 0.5 MPa, and may be 0.05 to 0.3 MPa. If the reaction pressure is within the above range, the dehydrogenation reaction tends to proceed easily, and a more excellent reaction efficiency tends to be obtained.
  • the mass space velocity (hereinafter, may be referred to as “WHSV”) may be 0.01 h -1 or more. It may be 0.1h -1 or more. When the WHSV is equal to or higher than the above lower limit value, the conversion rate of indane can be further increased. Further, the WHSV may be 100h -1 or less, and may be 20h -1 or less. When the WHSV is equal to or less than the above upper limit value, the reactor size can be further reduced.
  • WHSV is the ratio (F / W) of the supply rate (supply amount / hour) F of the raw material to the mass W of the zeolite catalyst in the continuous reactor.
  • the amount of the raw material and the catalyst used may be appropriately selected in a more preferable range depending on the reaction conditions, the activity of the catalyst, and the like, and WHSV is not limited to the above range.
  • the production method according to the present embodiment may further include a raw material synthesis step of obtaining indane or an indane mixture by a dehydrogenation reaction of tetrahydroindene. It has a production method having a first dehydrogenation step of obtaining an indane mixture by dehydrogenating tetrahydroindene and a second dehydrogenation step of obtaining indene from the obtained indane mixture by a dehydrogenation reaction, that is, having tetrahydroindene.
  • a production method for producing indene from a raw material is mentioned as a preferable production example according to the present embodiment.
  • the production conditions (conditions such as temperature and pressure) in the first and second dehydrogenation steps are not particularly limited and can be appropriately adjusted according to the purpose.
  • the production conditions are not particularly limited, but for example, the production conditions in the first dehydrogenation step are relatively mild conditions, and the production conditions in the second dehydrogenation step are the first dehydrogenation step. It is preferable to manufacture under harsher conditions. Under the above production conditions, an indane mixture in which indane, octahydroindene and hexahydroindene are mixed in a suitable ratio is obtained in the first dehydrogenation step, and the indane mixture is used in the second dehydrogenation step. Indane tends to be produced efficiently and in high yield.
  • the temperature at which the raw material having tetrahydroindene is brought into contact with the dehydrogenation catalyst is not particularly limited, but may be, for example, 150 to 300 ° C.
  • the pressure at which the raw material having tetrahydroindene is brought into contact with the dehydrogenation catalyst is not particularly limited, but may be, for example, 0.01 to 5.0 MPa.
  • the WHSV is not particularly limited, but may be, for example, 0.1 to 10 h- 1 .
  • a solid catalyst that catalyzes the dehydrogenation reaction of tetrahydroindene can be used without particular limitation.
  • the dehydrogenation catalyst chromium / Al 2 O 3 catalyst used as a catalyst for the dehydrogenation reaction, platinum / Al 2 O 3 catalyst, Fe-K catalyst, platinum / SnO 2 -Al 2 O 3 catalyst , Platinum-tin / magnesia alumina catalyst, Bi-Mo catalyst often used as a catalyst for oxidative dehydrogenation reaction, etc.
  • the dehydrogenation catalyst chromium / Al 2 O 3 catalyst used as a catalyst for the dehydrogenation reaction
  • platinum / Al 2 O 3 catalyst Fe-K catalyst
  • platinum / SnO 2 -Al 2 O 3 catalyst platinum / SnO 2 -Al 2 O 3 catalyst
  • Platinum-tin / magnesia alumina catalyst platinum-tin / magnesia alumina catalyst
  • Bi-Mo catalyst often used as a catalyst
  • indene can be produced using an indane mixture in which indane, octahydroindene and hexahydroindene are mixed, and therefore indene can be produced from tetrahydroindene. Can be produced with high efficiency and high yield.
  • the downstream side of the reactor is filled with the above-mentioned zeolite catalyst, and the upstream side of the reactor is filled with a dehydrogenation catalyst for converting tetrahydroindene into indane or an indane mixture.
  • a dehydrogenation catalyst for converting tetrahydroindene into indane or an indane mixture.
  • indene can be stably produced from a raw material composition containing indane in a high yield for a long period of time by using a specific zeolite catalyst. Can be done. As a result, the number of times of catalyst regeneration required for producing inden can be reduced and the production efficiency can be improved, which is very useful industrially.
  • the zeolite catalyst was pretreated at 500 ° C. for 1 hour while flowing helium gas at a flow rate of 50 mL / min. Then, it was cooled to less than 40 ° C., 1 vol% CO 2 / He gas was circulated at a flow rate of 50 mL / min to adsorb CO 2 on the zeolite catalyst, and then helium gas was circulated at a flow rate of 50 mL / min for 5 minutes. .. Then, while helium gas was circulated at 30 mL / min, the temperature was raised to 800 ° C.
  • the mixture was cooled to 100 ° C., 1 vol% NH 3 / He gas was circulated at a flow rate of 50 mL / min to adsorb NH 3 on a zeolite catalyst, and then helium gas was circulated at a flow rate of 50 mL / min for 15 minutes. Then, while helium gas was circulated at 30 mL / min, the temperature was raised to 700 ° C. at a heating rate of 10 ° C./min, and the withdrawal of NH 3 was analyzed by TCD and MASS. As MASS, BELMass manufactured by Microtrack Bell Co., Ltd. was used. Measurement of the Lewis acid amount was calculated from the peak area by NH 3 -TPD.
  • (C) FT-IR analysis The result of FT-IR analysis at room temperature is shown in FIG. 3 after performing pretreatment by vacuum exhausting at 450 ° C. for 1 hour. If Zns are close to each other, they become 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. However, in the zeolite catalyst of this example, an absorption band around 3640 cm -1 derived from the Zn-OH vibration of Zn is observed, and it is considered that the Zns are isolated from each other by being incorporated into the zeolite skeleton.
  • the obtained zeolite catalyst is a zeolite catalyst having an MFI structure, which does not have Bronsted acid but has only Lewis acid and has strong solid basicity.
  • HZSM-5 commercially available MFI-type zeolite
  • silica light was confirmed to have an MFI structure by X-ray diffraction measurement (X-ray source: CuK ⁇ , apparatus: manufactured by Rigaku, RINT 2500).
  • X-ray source CuK ⁇ , apparatus: manufactured by Rigaku, RINT 2500.
  • platinum was supported so that the amount of platinum supported was 1.0 wt%.
  • Catalyst synthesis example 5 ⁇ Preparation of catalyst E> To silicalite 1.25g obtained by the process of Catalyst Preparation Example 4, zinc nitrate hexahydrate (Kishida Chemical Ltd., Zn (NO 3) 2 ⁇ 6H 2 O) and 0.57g of water 0.71mL The dissolved aqueous solution was mixed, and zinc was impregnated and supported so that the final zinc content after the catalyst was prepared was 9.0 wt%. Then, it was dried overnight at 130 ° C. and calcined at 550 ° C. for 3 hours.
  • II dinitrodiammine platinum
  • FIG. 9 is a graph showing the indene yield at the time when 2, 4 and 6 hours have passed from the start of the reaction in the indene production of Examples and Comparative Examples.
  • the indene yield is defined by the following formula (1).
  • rY (m 1 / m 0 ) x 100 (1)
  • RY in the formula (1) is the indene yield (wt%).
  • m 0 is the total mass of the indane mixture present in the raw material.
  • m 1 is the mass of indene contained in the product.
  • Example 2 When 2, 4 and 6 hours have passed from the start of the reaction, the product of the dehydrogenation reaction was collected from the tubular reactor, and from the start of the reaction to 24 hours, every 2 hours. The same procedure as in Example 1 was carried out except that the product of the dehydrogenation reaction was collected from a tubular reactor. The results are shown in FIG. FIG. 10 is a graph showing the indene yield from the start of the reaction to 24 hours in the indene production of Examples and Comparative Examples.
  • Examples 1 and 2 are experimental examples showing the indene yield using a zeolite catalyst in which a transition metal is introduced into the zeolite skeleton.
  • a transition metal is not introduced in the zeolite skeleton and the aluminum content is small (Comparative Example 1), and a transition metal is not introduced in the zeolite skeleton and the aluminum content is high.
  • a large zeolite catalyst (Comparative Example 2), a catalyst using silicalite as a carrier (Comparative Example 3), a catalyst using a silicalite as a carrier impregnated with a transition metal (Comparative Example 4), and an alumina having a spinel-type structure.
  • the inden yield was determined by a method similar to that of Examples.
  • Tetrahydroindene (3a, 4,7,7a-tetrahydroindene; manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a raw material and supplied at 3.0 g / h from the first stage entrance.
  • the reaction temperature of the first stage was 180 ° C.
  • the reaction pressure was 0.9 MPa
  • no diluting gas such as hydrogen or nitrogen was used, and only the raw materials were supplied (first dehydrogenation step).
  • the product oil of the first stage is supplied as it is to the second stage, the reaction temperature of the second stage is set to 500 ° C., the reaction pressure is set to normal pressure, and molecular hydrogen is added from the inlet of the second stage in an amount three times as much as that of tetrahydroinden.
  • the reaction was carried out to produce an inden (second dehydrogenation step).
  • the reaction was carried out for 12 hours, and the first-stage outlet composition and the second-stage outlet composition were measured every 2 to 3 hours.
  • the first-stage outlet composition was stable at 52 wt% for indene, 1 wt% for indene, 6 wt% for octahydroindene, 40 wt% for hexahydroindene, and 1 wt% for unidentified material.
  • the raw material tetrahydroindene was not detected at the exit of the first stage, and the conversion rate was 100%.
  • the time course of indene and hexahydroindene at the exit of the second stage is shown in FIG.
  • the composition of the first-stage outlet was stable, and the indene yield of the second-stage outlet was also stable. Since hexahydroindene was significantly reduced and indene was generated at the second stage reaction outlet, it is considered that hexahydroindene is easily dehydrogenated and contributes to the improvement of indene yield.

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Il est prévu un procédé de production stable d'indène sur une longue durée avec un rendement élevé en utilisant un catalyseur de zéolite, comme nouveau procédé de production d'indène.　Ce procédé de production d'indène comprend une étape de déshydrogénation consistant à amener une composition de matière première comprenant de l'indène en contact avec un catalyseur de zéolite ayant une structure MFI pour obtenir un produit de réaction comprenant de l'indène, le catalyseur de zéolite comprenant, à l'intérieur du squelette de zéolite, au moins un type d'atomes métalliques choisi parmi des métaux de transition ou des métaux de post-transition et ayant une acidité de Lewis et une basicité solide forte.
PCT/JP2020/047943 2019-12-24 2020-12-22 Procédé de production d'indène WO2021132239A1 (fr)

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JPS61291528A (ja) * 1985-06-17 1986-12-22 ザ　スタンダ−ド　オイル　カンパニ− インデン類の製法
JP2000063298A (ja) * 1998-08-18 2000-02-29 Nippon Petrochem Co Ltd インデンの製造方法
JP2003327551A (ja) * 2002-05-10 2003-11-19 San Petrochemical:Kk インダンの製造方法
JP2018202396A (ja) * 2017-05-31 2018-12-27 古河電気工業株式会社 アルカンの脱水素化触媒構造体及びその製造方法、並びに該脱水素化触媒構造体を有するアルケン製造装置
JP2018202395A (ja) * 2017-05-31 2018-12-27 古河電気工業株式会社 アルカンの脱水素化触媒構造体及びその製造方法、並びに該脱水素化触媒構造体を有するアルケン製造装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61291528A (ja) * 1985-06-17 1986-12-22 ザ　スタンダ−ド　オイル　カンパニ− インデン類の製法
JP2000063298A (ja) * 1998-08-18 2000-02-29 Nippon Petrochem Co Ltd インデンの製造方法
JP2003327551A (ja) * 2002-05-10 2003-11-19 San Petrochemical:Kk インダンの製造方法
JP2018202396A (ja) * 2017-05-31 2018-12-27 古河電気工業株式会社 アルカンの脱水素化触媒構造体及びその製造方法、並びに該脱水素化触媒構造体を有するアルケン製造装置
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