WO2018038169A1 - Composition de catalyseur pour la production d'hydrocarbure aromatique monocyclique de c6-8 et procédé de production d'hydrocarbure aromatique monocyclique de c6-8 - Google Patents

Composition de catalyseur pour la production d'hydrocarbure aromatique monocyclique de c6-8 et procédé de production d'hydrocarbure aromatique monocyclique de c6-8 Download PDF

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WO2018038169A1
WO2018038169A1 PCT/JP2017/030162 JP2017030162W WO2018038169A1 WO 2018038169 A1 WO2018038169 A1 WO 2018038169A1 JP 2017030162 W JP2017030162 W JP 2017030162W WO 2018038169 A1 WO2018038169 A1 WO 2018038169A1
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catalyst composition
gallium
carbon atoms
monocyclic aromatic
crystalline aluminosilicate
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PCT/JP2017/030162
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English (en)
Japanese (ja)
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泰之 岩佐
小林　正英
賢 小倉
和 奥村
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Ｊｘｔｇエネルギー株式会社
国立大学法人東京大学
学校法人工学院大学
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Publication of WO2018038169A1 publication Critical patent/WO2018038169A1/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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • the present invention relates to a catalyst composition for producing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms and a method for producing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms.
  • catalytic reforming of straight run naphtha using a platinum / alumina catalyst has been widely used commercially as a method for obtaining gasoline and aromatic hydrocarbons having a high octane number.
  • a fraction having a boiling point of 70 to 180 ° C. is mainly used for the purpose of producing gasoline for automobiles.
  • aromatic fractions such as benzene, toluene and xylene, so-called BTX
  • BTX a fraction of 60 to 150 ° C. is used.
  • the carbon number of the raw material hydrocarbons decreases, the conversion ratio to aromatics decreases, and the octane number of the product also decreases.
  • Patent Documents 1 to 3 describe an aromatic hydrocarbon production method using a gallium-containing crystalline aluminosilicate catalyst composition and a hydrocarbon having 2 to 7 carbon atoms as a main raw material.
  • a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms with high added value can be produced in a high yield. Since the monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms with high yield and high added value is produced, the catalyst composition for producing monocyclic aromatic hydrocarbons as described in Patent Documents 1 to 3 has not been improved. There was room.
  • the present invention has been made in view of the above circumstances, and is a catalyst composition for producing monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms that can produce monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms with high yield. The issue is to provide goods. It is another object of the present invention to provide a method for producing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms using the catalyst composition for producing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms.
  • the present inventors have obtained high yields of monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms by using crystalline aluminosilicates containing specific gallium atoms as catalyst compositions. We found that it can be obtained at a rate.
  • a first aspect of the present invention is a catalyst composition used for producing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms, comprising a crystalline aluminosilicate containing gallium, and the catalyst composition
  • the catalyst composition In the radial distribution function obtained from the wide-area X-ray absorption fine structure (EXAFS) spectrum at the K absorption edge of gallium, the ratio of the peak intensity I due to Ga—O to the peak intensity II due to Ga—Ga
  • a single carbon atom having 6 to 8 carbon atoms which is brought into contact with the catalyst composition for producing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms according to the first aspect of the present invention.
  • This is a method for producing a ring aromatic hydrocarbon.
  • a catalyst composition for producing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms that can produce a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms with a high yield.
  • a method for producing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms using the catalyst composition for producing a monocyclic aromatic hydrocarbon having 6 to 8 carbon atoms is possible to provide.
  • EXAFS extended X-ray absorption fine structure
  • the present invention is a catalyst composition used for the production of monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms such as benzene, toluene, xylene and the like (hereinafter referred to as “BTX”).
  • the catalyst composition of the present invention is a catalyst composition containing a crystalline aluminosilicate containing gallium, and is determined from a broad X-ray absorption fine structure (EXAFS) spectrum of the K absorption edge of gallium for the catalyst composition.
  • EXAFS broad X-ray absorption fine structure
  • EXAFS means Extended X-ray Absorption Fine Structure, “extended X-ray absorption fine structure”.
  • X-ray energy is plotted on the horizontal axis and the X-ray absorption intensity is plotted on the vertical axis, a steep rise (characteristic absorption edge) appears at a specific energy, but EXAFS is the characteristic absorption edge.
  • EXAFS reflects a structure in the range of several tens of kilometers as viewed from the absorbing atoms (see Non-Patent Document: PETROTECH Vol. 30 No. 10 (2007)).
  • the catalyst composition of the present invention when performing EXAFS measurement on the catalyst composition of the present invention, when the catalyst composition of the present invention consists only of crystalline aluminosilicate containing gallium, the catalyst composition itself may be measured. In addition, when the catalyst composition of the present invention contains other components other than the crystalline aluminosilicate containing gallium, EXAFS is measured for the crystalline aluminosilicate containing gallium before being mixed with the other components. It is preferable.
  • FIG. 1 schematically shows a crystalline aluminosilicate or gallium oxide containing gallium.
  • X-ray 1 When this is irradiated with X-ray 1, if the energy of X-ray 1 exceeds the binding energy of electrons of gallium atom 3, X-ray absorption occurs, and the electrons are excited to become free electrons (photoelectrons). Since electrons have wave properties as well as particle properties, the emitted photoelectron electron wave (w1) is scattered by surrounding atoms, the scattered photoelectron waves (w2, w3, w4) and the original photoelectron wave (w1). ) causes interference.
  • the X-ray absorption intensity is slightly high, but when this interference weakens each other, the X-ray absorption intensity is low.
  • the way in which interference occurs depends on the number and distance of surrounding atoms (gallium atoms 5, oxygen atoms 2 and 4 existing around gallium atom 3 in FIG. 1). Surrounding information can be obtained. Specifically, the distance to the surrounding atoms (inter-atomic distance), the type of surrounding atoms, and the number of surrounding atoms (coordination number) are known. This is the principle of EXAFS.
  • oxygen atoms 2 and 4 and a gallium atom 5 exist around the gallium atom 3.
  • the electron wave (w1) of the emitted photoelectrons is scattered by the oxygen atoms 2 and 4 and the gallium atom 5, and the scattered photoelectron waves (w2, w3, w4).
  • the original photoelectron wave (w1) cause interference.
  • a peak corresponding to the interatomic distance between the gallium atom 3 and the oxygen atoms 2 and 4, and an atom between the gallium atom 3 and the gallium atom 5 Peaks according to the distance can be measured.
  • FIG. 2 shows a radial distribution obtained from EXAFS at the K absorption edge of a gallium atom for a catalyst composition containing a crystalline aluminosilicate containing gallium (Example 4 described later) and gallium oxide (Ga 2 O 3 ). Indicates a function.
  • the radial distribution function obtained from EXAFS at the K absorption edge of a gallium atom has a Ga—O peak at an interatomic distance of about 1.5 ⁇ and a Ga—Ga peak at an interatomic distance of about 2.8 ⁇ .
  • the catalyst composition of the present invention has a peak intensity I due to Ga—O (interatomic distance of about 1.5 mm shown in FIG. 2) and a peak intensity II attributable to Ga—Ga (interatomic distance 2 shown in FIG. 2).
  • the ratio (I / II) to the vicinity of .8 cm is greater than 0.25.
  • a small peak intensity II due to Ga—Ga means that the proportion of galliums close to each other is small, and a large peak intensity II means that a large proportion of galliums are close to each other.
  • the gallium present in the crystalline aluminosilicate containing gallium is considered the former, and the compound such as gallium oxide represented by Ga 2 O 3 is considered the latter. That is, the catalyst composition of the present invention means that the proportion of gallium present in the crystalline aluminosilicate is relatively high.
  • the ratio (I / II) between the peak intensity I and the peak intensity II is preferably 0.26 or more, and more preferably 0.28 or more. Moreover, although an upper limit is not specifically limited, For example, 2.0 or less is preferable and 1.0 is more preferable.
  • the present inventors paid attention to the principle of EXAFS, and used a catalyst composition comprising a crystalline aluminosilicate in which the intensity of a peak due to Ga—Ga is relatively small, in other words, a small proportion of gallium present in the vicinity of gallium. It has been found that monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms can be produced with a high yield when used in the above.
  • the gallium-containing crystalline aluminosilicate catalyst composition described in Patent Document 3 focuses on aluminum atoms in the gallium-containing crystalline aluminosilicate catalyst composition by MASNMR analysis.
  • the present application focuses on gallium atoms and is an invention based on a new idea different from Patent Document 3.
  • the structure of the crystalline aluminosilicate containing gallium (hereinafter referred to as "gallium-containing crystalline aluminosilicate") contained in the catalyst composition of the present invention is not particularly limited, but is a pentasil-type zeolite.
  • Zeolite having an MFI type and / or MEL type crystal structure is more preferable (a crystalline aluminosilicate having a three-dimensionally connected structure is called a zeolite).
  • MFI-type and MEL-type zeolites belong to a known zeolite structure type of the kind published by “The Structure Commission of the International Zeolite Association” (Atlas of Zeolite Structure. 1978) Distributed by Polycrystalline Book Service, Pittsburgh, PA, USA).
  • An example of an MFI type zeolite is ZSM-5, and an example of an MEL type zeolite is ZSM-11.
  • gallium-containing crystalline aluminosilicate contained in the catalyst composition of the present invention examples include those in which gallium is present in the crystalline aluminosilicate, and those in which gallium is supported on the crystalline aluminosilicate (hereinafter referred to as “gallium-supporting crystalline aluminosilicate”). Silicate ”) or a material containing both of them is used, but at least a crystalline aluminosilicate containing gallium is preferred. Further, it is more preferable that the crystalline aluminosilicate contains a gallium cation.
  • the gallium-containing crystalline aluminosilicate contained in the catalyst composition of the present invention is preferably produced by inserting gallium into the crystalline aluminosilicate by an ion exchange method.
  • an ion exchange method a method in which a gallium source is used as a solution and a crystalline aluminosilicate is immersed (in many cases, an aqueous solution), or a crystalline aluminosilicate and a gallium source are physically mixed in a solid state.
  • gallium salts such as gallium nitrate and gallium chloride, gallium oxide and the like can be preferably used.
  • a method of performing ion exchange by physically mixing crystalline aluminosilicate and a gallium source in a solid state is preferable.
  • a method of heating in an atmosphere of a reducing gas, an inert gas, or a mixed gas containing them is preferable.
  • the particle diameter of the gallium-containing crystalline aluminosilicate contained in the catalyst composition of the present invention is preferably 0.05 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, particularly preferably 0.5 to 5 ⁇ m, and 1 to 3 ⁇ m. Highly preferred. Moreover, it is preferable that the content rate of the particle
  • the diffusion rate of the molecule tends to be slow in the crystalline aluminosilicate pore.
  • the particle diameter is 20 ⁇ m or less, the reactive molecule easily approaches the active site in the deep pores, and the active site is easily used effectively during the reaction.
  • factors affecting the size of the generated particles include the type of silica source, the amount of organic additives such as quaternary ammonium salts, and inorganic salts as mineralizers. And the amount of base, the amount of base in the gel, the pH of the gel, the heating rate during the crystallization operation, the temperature and the stirring rate, and the like. By appropriately adjusting these conditions, a crystalline aluminosilicate having the above-mentioned particle size range can be obtained.
  • the catalytic activity for the aromatization reaction of the gallium-containing crystalline aluminosilicate contained in the catalyst composition of the present invention is affected by the composition.
  • the gallium atom is preferably contained in an amount of 0.1 to 5.0% by mass, more preferably 0.1 to 3.0% by mass.
  • the molar ratio of gallium to aluminum is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.9, and from 0.3 to 1 .8 or less is particularly preferable.
  • the content of gallium in the catalyst composition is preferably 0.02 parts by mass or more and 3.0 parts by mass or less.
  • the molar ratio of gallium to aluminum is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.9, and from 0.3 to 1 .8 or less is particularly preferable.
  • the gallium-containing crystalline aluminosilicate contained in the catalyst composition of the present invention is various activation treatments that are generally performed when crystalline aluminosilicate is used as a catalyst component, as desired. Can be applied. That is, the gallium-containing crystalline aluminosilicate contained in the catalyst composition of the present invention includes not only those produced by the method such as hydrothermal synthesis but also those obtained by modification or activation treatment thereof. It is.
  • a metal ion other than alkali metal or alkaline earth metal is used.
  • a desired metal other than an alkali metal or an alkaline earth metal can be introduced by ion exchange in an aqueous solution containing or impregnating the aqueous solution.
  • the ammonium-type gallium-containing crystalline aluminosilicate is heated in an atmosphere of air, nitrogen or hydrogen at a temperature of 200 to 800 ° C., preferably 350 to 700 ° C. for 3 to 24 hours to remove ammonia, thereby removing the acid type.
  • the structure can be activated.
  • the acid catalyst may be treated with hydrogen or a mixed gas of hydrogen and nitrogen under the above conditions. Furthermore, you may give the ammonia modification
  • the catalyst composition of the present invention is preferably used after being subjected to the activation treatment before contacting with the hydrocarbon feedstock.
  • the active component of the catalyst composition of the present invention is the gallium-containing crystalline aluminosilicate, but for the purpose of facilitating molding or improving the mechanical strength of the catalyst, the catalyst composition is supported or molded.
  • An auxiliary agent or the like may be included.
  • the content of the gallium-containing crystalline aluminosilicate in the total mass of the catalyst composition is not particularly limited, but the gallium-containing crystalline aluminosilicate is based on the total mass of the catalyst composition. 40 to 95% by mass is preferable, 50 to 90% by mass is more preferable, and 60 to 80% by mass is further preferable.
  • compositions containing gallium-containing crystalline aluminosilicate are various molded products such as granules, spheres, plates, pellets, etc. by methods such as extrusion, spray drying, tableting, rolling granulation, and granulation in oil. It can be. In molding, it is desirable to use an organic compound lubricant to improve moldability.
  • composition of a gallium-containing crystalline aluminosilicate can be formed prior to the ion-exchange step of the gallium-containing crystalline aluminosilicate with ammonium ions or the like, or after the gallium-containing crystalline aluminosilicate is ion-exchanged. It can also be done.
  • the catalyst composition of the present invention may contain an additive in addition to the gallium-containing crystalline aluminosilicate described above.
  • the additive is not particularly limited, and examples thereof include inorganic oxides such as alumina boria, silica, silica alumina, and aluminum phosphate, clay minerals such as kaolin and montmorillonite, inorganic phosphorus compounds, and organic phosphorus compounds.
  • the addition amount is not particularly limited, but is added to the catalyst composition so as to be 50% by mass or less, more preferably 30% by mass or less, and further preferably 15% by mass or less.
  • the catalyst composition of the present invention can be used with a metal component supported as an auxiliary component.
  • the metal component as an auxiliary component may be supported on gallium-containing crystalline aluminosilicate, or may be supported on other additives, or both.
  • auxiliary metal components include metals having dehydrogenation ability and metals having an effect of suppressing carbon deposition.
  • Specific examples of the auxiliary metal component include those that improve catalytic activity, such as magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium.
  • Ytterbium lutetium, titanium, vanadium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, aluminum, indium, germanium, tin, lead , Phosphorus, antimony, bismuth, selenium and the like.
  • These metals can be used alone or in combination of two or more, and the supported amount is 0.1 to 10% by mass in terms of metal.
  • known techniques such as an ion exchange method, an impregnation method, and physical mixing can be used.
  • an auxiliary component metal can be contained by adding the metal component as an auxiliary component during the synthesis of the pentasil-type zeolite.
  • an auxiliary metal component having an effect of suppressing the deposition of coke during the reaction magnesium, calcium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium,
  • One or more metals selected from ruthenium and iridium can be supported, and the supported amount is 0.01 to 5% by mass in terms of metal.
  • the above-described catalyst composition of the present invention is brought into contact with a raw material oil containing a hydrocarbon having 2 to 7 carbon atoms to produce an aromatic hydrocarbon.
  • the raw material used in the present invention contains a light hydrocarbon having 2 to 7 carbon atoms, and the content of the light hydrocarbon having 2 to 7 carbon atoms in the raw material is not particularly limited, but is preferably 20% by mass. Above, more preferably 40% by mass or more, particularly preferably 60 to 100% by mass.
  • the light hydrocarbon having 2 to 7 carbon atoms is not particularly limited, and may be linear, branched or cyclic, and may be paraffin or olefin. Furthermore, a mixture thereof may be used. Specific examples of such hydrocarbons include linear aliphatic saturated hydrocarbons having 2 to 7 carbon atoms (ethane, propane, normal butane, normal pentane, normal hexane, normal heptane), branched aliphatic saturated hydrocarbons.
  • cycloaliphatic saturated hydrocarbon cyclopropane, cyclobutane, cyclopentane, 1-methylcyclopentane, 1,1-dimethylcyclopentane 1,2-dimethylcyclopentane, 1,3-dimethylcyclopentane, cyclohexa , Methylcyclohexane, etc.
  • linear aliphatic unsaturated hydrocarbons ethylene, propylene, normal butene, normal pentene, normal hexene, normal heptene, etc.
  • branched aliphatic unsaturated hydrocarbons branched aliphatic unsaturated hydrocarbons
  • reaction process In this step, at least n reaction layers holding the above-described catalyst composition are arranged in series, and a heating furnace or the like is provided between the reaction layers as means for heating the effluent from the reaction layer.
  • a mixture of a light hydrocarbon as a raw material and a recycle gas which will be described later, is passed through a reaction layer to convert the mixture into an aromatic hydrocarbon.
  • Preferred reaction conditions in this step are a reaction layer inlet temperature of 350 to 650 ° C., a hydrogen partial pressure of 0.5 MPa or less, and a raw material gas space velocity of 100 to 2000 hr ⁇ 1 .
  • the reaction layer inlet temperature in the conversion reaction step according to the present invention is generally in the preferred range of 350 to 650 ° C., but 450 to 650 ° C. when the light hydrocarbon as the main component is normal paraffin.
  • isoparaffin is the main component
  • olefin is the main component
  • 350 to 550 ° C. are more preferable temperature ranges.
  • the reactor used in the conversion reaction step is not particularly limited, and examples thereof include a fixed bed reactor, a CCR reactor, and a fluidized bed reactor.
  • a fixed bed or a CCR type reactor at least n reaction layers holding the catalyst composition described above (n is an integer of 2 or more) are arranged in series, and further between the reaction layers or in the reaction layer, A heating device such as a heating furnace is preferably provided as means for heating the effluent from the previous reaction layer.
  • the catalyst amount in the first-stage reaction layer is 30% by volume or less, preferably 1-30% by volume, more preferably 2-30% by volume of the total catalyst amount. %, More preferably 2 to 28% by volume.
  • the amount of catalyst in the first-stage reaction layer is preferably 60 / n volume% or less of the total amount of catalyst.
  • the number n of the reaction layers is not particularly limited as long as it is 2 or more. However, if the number is too large, the effect is not changed and the economical efficiency is deteriorated. Accordingly, n is preferably 2 or more and 8 or less, more preferably 3 or more and 6 or less.
  • the conversion reaction step it is possible to operate at a constant reaction layer inlet temperature, and to increase the reaction layer inlet temperature continuously or stepwise so as to obtain a predetermined aromatic yield. You can also drive.
  • the reactor is switched to a reactor filled with new catalyst or a reactor filled with regenerated catalyst.
  • the regeneration of the catalyst can be performed by heat treatment at 200 to 800 ° C., preferably 350 to 700 in an air stream such as air, nitrogen, hydrogen, or a nitrogen / hydrogen mixed gas.
  • the method for producing aromatic hydrocarbons of the present invention is preferably carried out using two series of fixed bed reactors including a reaction layer holding the catalyst composition.
  • each series of reaction apparatuses is composed of a plurality of reaction layers arranged in series. While the raw material containing light hydrocarbons is introduced into one series of reactors and the reaction proceeds, the catalyst in the other series of reactors is subjected to a regeneration treatment. By performing the reaction / regeneration alternately at intervals of 1 to 10 days in these two series of reactors, for example, continuous operation for one year can be performed. Further, like the cyclic operation, it is possible to continuously perform the reaction by switching a part or all of the series of reactors used for the reaction to another series. It is preferable to keep the aromatic yield within a predetermined range of 40 to 75% by weight by continuously or stepwise increasing the reaction temperature for each cycle of the reaction for 1 to 10 days.
  • the aromatic yield R is represented by the following formula (1).
  • R A / B ⁇ 100 (%) (1)
  • a reaction involving dehydrogenation proceeds. Therefore, under the reaction conditions, a hydrogen partial pressure suitable for the reaction is set without adding hydrogen. Will have. Intentional addition of hydrogen has the advantage of suppressing coke deposition and reducing the frequency of regeneration, but the yield of aromatics is not necessarily advantageous because it decreases rapidly with increasing hydrogen partial pressure. Therefore, the hydrogen partial pressure is preferably suppressed to 0.5 MPa or less.
  • the total amount of light gas (recycle gas) circulated to the reaction system is desirably 0.1 to 10 parts by mass, preferably 0.5 to 3 parts by mass, per 1 part by mass of the hydrocarbon feedstock.
  • the effluent from the conversion reaction step is introduced into a gas-liquid separation zone composed of one or more gas-liquid separators, and gas-liquid separation is performed under relatively high pressure, and aromatic hydrocarbons are removed.
  • This is a step of separation into a liquid component (high pressure separation liquid) contained as a main component and a light gas (high pressure separation gas) such as hydrogen, methane, ethane, propane, or butane.
  • the temperature is usually 10 to 50 ° C., preferably 20 to 40 ° C.
  • the pressure is usually 0.5 to 8 MPa, preferably 1 to 3 MPa.
  • reaction bed effluent is cooled by indirect heat exchange with low-temperature raw hydrocarbons before being introduced into the gas-liquid separation process, and, if necessary, hydrogen from the gas-liquid separation process and light gas is separated. In order to reduce the process load, a part of the light gas can be separated.
  • This step is a step of selectively separating hydrogen from the high-pressure separation gas separated in the gas-liquid separation step to obtain a recycle gas containing methane and / or ethane.
  • a hydrogen separation method in this case, a conventionally known method such as a membrane separation method or a cryogenic separation method is used. From the viewpoint of selective hydrogen separation efficiency, it is preferable to use a membrane separation method.
  • unreacted propane is maximized compared to off gas from the membrane separation method. Therefore, there is an advantage that the aromatic hydrocarbon yield can be increased by 1 to 3% by mass. Which method to use is judged from an economic point of view.
  • the membrane separation device for example, a device using polyimide, polysulfone, a blend of polysulfone and polydimethylsiloxane as a separation membrane is commercially available. Part of the recycled gas obtained in this step is discharged out of the system in order to keep the total amount of circulating gas within a certain range.
  • a membrane separation device or a PSA absorption / desorption separation device
  • the selection of the latter device is determined from an economic point of view.
  • This step is a step of separating aromatic hydrocarbon and low boiling point hydrocarbon gas from the high-pressure separation liquid obtained in the gas-liquid separation step, and a stabilizer (distillation tower) is used as the apparatus.
  • the low-boiling point hydrocarbon gas separated as the top fraction is composed of C3 to C4 hydrocarbons and is used as a recycle gas.
  • the raw material light hydrocarbon is mixed with the recycle gas containing methane and / or ethane obtained in the hydrogen gas separation step and the low boiling point hydrocarbon gas separated in the aromatic hydrocarbon separation step. It is a process, and this mixing can be performed in a pipe. This mixture is introduced into the conversion reaction step.
  • the mixing ratio of the recycle gas and the low boiling point hydrocarbon gas per 1 part by mass of the raw light hydrocarbon is 0.1 to 10 parts by mass, preferably 0.5 to 3 parts by mass.
  • the aromatization reaction by dehydrocyclization is an endothermic reaction, and therefore the catalyst layer temperature is lowered, which is disadvantageous for the aromatization reaction.
  • Methane and / or ethane is considered an inert gas because it does not aromatize under the reaction conditions.
  • this acts as a heat supply medium, suppresses the temperature drop of the catalyst layer, favorably advances the aromatization reaction, and improves the aromatic hydrocarbon yield.
  • generated by the conversion reaction of a raw material can be reduced by recycling, and an aromatization reaction can be advanced advantageously, As a result, an aromatic hydrocarbon yield can be improved.
  • the gas velocity in the reaction layer is increased (GHSV is increased), the contact time between the reaction substrate and the catalyst active site is shortened, and the excessive reaction that gives the coke-like substance can be suppressed. As a result, it is possible to suppress the decrease in activity that occurs with the elapsed time of the reaction and maintain the aromatic hydrocarbon yield at a high level.
  • the recycle gas ratio must be determined from an economic point of view.
  • Tableting was performed by applying a pressure of 39.2 MPa (400 kgf), coarsely pulverized to a size of 20 to 28 mesh, and granulated to obtain crystalline aluminosilicate 1 containing gallium.
  • This crystalline aluminosilicate 1 was used as the catalyst composition for producing monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms of Example 1.
  • Example 2 3. 0.12 g of gallium chloride and the above ZSM-5 (proton type) so that 1.0% by mass (value with the total mass of crystalline aluminosilicate being 100% by mass) is ion-exchanged (or impregnated).
  • a crystalline aluminosilicate 2 containing gallium was prepared in the same manner as in Example 1 except that the amount was 8 g. This crystalline aluminosilicate 2 was used as the catalyst composition for producing monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms of Example 2.
  • This crystalline aluminosilicate 4 was used as the catalyst composition for producing monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms of Example 4.
  • Example 5 3. 0.25 g of gallium chloride and ZSM-5 (proton type) so that 2.0% by mass (a value obtained when the total mass of crystalline aluminosilicate is 100% by mass) is ion-exchanged (or impregnated).
  • a crystalline aluminosilicate 5 containing gallium was prepared in the same manner as in Example 3 except that the amount was 8 g. This crystalline aluminosilicate 5 was used as the catalyst composition for producing monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms of Example 5.
  • Tableting was performed by applying a pressure of 39.2 MPa (400 kgf), coarsely pulverized to a size of 20 to 28 mesh, and granulated to obtain crystalline aluminosilicate 8 containing gallium.
  • This crystalline aluminosilicate 8 was used as the catalyst composition for producing monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms of Comparative Example 1.
  • X-ray source Continuous X-ray spectroscopic crystal: Si (111) Beam size: 1mm x 5mm Detector: Ionization chamber Measurement atmosphere: Atmospheric measurement time: 5 minutes Dwell time: 1 sec Measurement range: Ga K absorption edge (10000 to 10500 eV)
  • Examples 1 to 7 using the catalyst composition to which the present invention was applied had higher BTX yield than the case of using the catalyst composition of Comparative Example 1 to which the present invention was not applied. .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne une composition de catalyseur utilisée pour produire un hydrocarbure aromatique monocyclique de C6-8 caractérisée en ce qu'elle comprend : un aluminosilicate cristallin contenant du gallium; et le rapport (I /II) supérieur à 0,25, I représentant l'intensité de pic due à Ga-O et II l'intensité de pic due à Ga-Ga dans une fonction de distribution radiale déterminée à partir d'une structure fine d'absorption de rayons X étendue (EXAFS) du spectre d'un bord d'absorption Ga-K.
PCT/JP2017/030162 2016-08-26 2017-08-23 Composition de catalyseur pour la production d'hydrocarbure aromatique monocyclique de c6-8 et procédé de production d'hydrocarbure aromatique monocyclique de c6-8 WO2018038169A1 (fr)

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WO2020050199A1 (fr) * 2018-09-03 2020-03-12 Ｊｘｔｇエネルギー株式会社 Procédé de production d'hydrocarbure aromatique monocyclique ayant de 6 à 8 atomes de carbone

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WO2020050092A1 (fr) * 2018-09-03 2020-03-12 Ｊｘｔｇエネルギー株式会社 Procédé de production de xylène

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JP2009233601A (ja) * 2008-03-27 2009-10-15 Nippon Oil Corp 触媒組成物及び芳香族炭化水素の製造方法
WO2014129585A1 (fr) * 2013-02-21 2014-08-28 Ｊｘ日鉱日石エネルギー株式会社 Procédé de production d'hydrocarbures aromatiques monocycliques

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JP2001062305A (ja) * 1999-06-24 2001-03-13 Eni Spa 炭化水素の芳香族化用触媒組成物
JP2009233601A (ja) * 2008-03-27 2009-10-15 Nippon Oil Corp 触媒組成物及び芳香族炭化水素の製造方法
WO2014129585A1 (fr) * 2013-02-21 2014-08-28 Ｊｘ日鉱日石エネルギー株式会社 Procédé de production d'hydrocarbures aromatiques monocycliques

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020050199A1 (fr) * 2018-09-03 2020-03-12 Ｊｘｔｇエネルギー株式会社 Procédé de production d'hydrocarbure aromatique monocyclique ayant de 6 à 8 atomes de carbone
JP2020037521A (ja) * 2018-09-03 2020-03-12 Ｊｘｔｇエネルギー株式会社 炭素数６〜８の単環芳香族炭化水素の製造方法
US11420913B2 (en) 2018-09-03 2022-08-23 Eneos Corporation Method for producing monocyclic aromatic hydrocarbon having 6-8 carbon atoms
JP7239100B2 (ja) 2018-09-03 2023-03-14 Ｅｎｅｏｓ株式会社 炭素数６～８の単環芳香族炭化水素の製造方法

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