WO2015152160A1 - Procédé de production d'un hydrocarbure insaturé - Google Patents

Procédé de production d'un hydrocarbure insaturé Download PDF

Info

Publication number
WO2015152160A1
WO2015152160A1 PCT/JP2015/059947 JP2015059947W WO2015152160A1 WO 2015152160 A1 WO2015152160 A1 WO 2015152160A1 JP 2015059947 W JP2015059947 W JP 2015059947W WO 2015152160 A1 WO2015152160 A1 WO 2015152160A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
producing
unsaturated hydrocarbon
catalyst
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/059947
Other languages
English (en)
Japanese (ja)
Inventor
裕一 池永
智 宮添
スーペイ ン
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
Original Assignee
Mitsui Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Priority to JP2016511886A priority Critical patent/JP6426711B2/ja
Publication of WO2015152160A1 publication Critical patent/WO2015152160A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • 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
    • 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
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • C07C5/3335—Catalytic processes with metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/60—Platinum group metals with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
    • C07C2529/035—Crystalline silica polymorphs, e.g. silicalites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/86—Borosilicates; Aluminoborosilicates
    • 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

Definitions

  • the present invention relates to a method for producing an unsaturated hydrocarbon by performing a hydrocarbon dehydrogenation reaction.
  • Unsaturated hydrocarbons are very useful as basic raw materials for various derivatives in the petrochemical industry.
  • Representative lower olefins and dienes include propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene and the like. These lower olefins and dienes are also known to be produced by dehydrogenating the corresponding paraffins and / or olefins.
  • a catalyst having chromium oxide supported on an alumina support, an alumina support or zinc aluminate It is known that such a catalyst having platinum supported on a spinel carrier is suitable for its production (Non-patent Document 1).
  • Patent Documents 1 to 9 disclose that a catalyst in which platinum and zinc are supported on a zeolite carrier exhibits high activity over a long period of time as compared with other catalyst systems.
  • metallic zinc is used under typical dehydrogenation reaction conditions that require high temperature and low pressure. Continues to evaporate from the catalyst, resulting in irreversible degradation of the catalyst.
  • Patent Document 7 describes that the addition of a Group IVB element such as zirconium is effective.
  • Patent Document 10 discloses a method of adding gallium to a zeolite carrying zinc as a propane aromatization catalyst.
  • Patent Document 11 uses a zeolite containing zinc as a lower hydrocarbon aromatization catalyst.
  • a method of supplying carbon dioxide, steam, thiophene and the like together with the raw material gas is disclosed.
  • Patent Document 12 discloses that the formation of zinc aluminate by the reaction of the zinc component contained in the aromatization catalyst and alumina greatly contributes to the stabilization of zinc.
  • the present invention provides a method for producing an unsaturated hydrocarbon by dehydrogenating a hydrocarbon using a dehydrogenation catalyst, and effectively suppressing the volatilization of zinc from the dehydrogenation catalyst. It is an object of the present invention to provide a method for stably producing unsaturated hydrocarbons, that is, olefins or dienes.
  • the present inventors made contact with the catalyst after bringing the raw material-containing gas into contact with metallic zinc and / or a zinc compound, or made the raw material-containing gas containing zinc vapor into the catalyst. It has been found that, by contacting, volatilization of zinc from the catalyst can be effectively suppressed, and as a result, unsaturated hydrocarbons, that is, olefins and dienes can be produced stably over a long period of time.
  • the raw material-containing gas (1) containing hydrocarbon is brought into contact with zinc metal or zinc compound or both, and then brought into contact with a dehydrogenation catalyst containing zinc as one of the active components.
  • a method for producing an unsaturated hydrocarbon (hereinafter also referred to as “production method (1)”), which comprises a step of producing an unsaturated hydrocarbon by dehydrogenating the hydrocarbon.
  • the raw material-containing gas (2) containing hydrocarbon and zinc vapor is brought into contact with a dehydrogenation catalyst containing zinc as one of the active components, and the hydrocarbon is dehydrogenated.
  • This is a method for producing an unsaturated hydrocarbon including a step of producing unsaturated hydrocarbon (hereinafter also referred to as “production method (2)”).
  • production method (2) The said raw material containing gas (2) can be obtained by making the said raw material containing gas (1) contact metal zinc or a zinc compound, or both.
  • the reaction temperature of the dehydrogenation reaction is 300 to 800 ° C. and the reaction pressure is 0.01 to 1 MPa.
  • the partial pressure of zinc vapor contained in the raw material-containing gas (2) is not more than the vapor pressure of zinc at the reaction temperature of the dehydrogenation reaction.
  • the zinc vapor source is preferably metallic zinc or zinc oxide or both.
  • the hydrocarbon as the raw material is preferably at least one selected from propane, n-butane and isobutane, or n-butene.
  • the raw material-containing gas (1) preferably further contains water vapor and / or hydrogen.
  • the raw material-containing gas (2) preferably further contains water vapor and / or hydrogen.
  • a preferred form as the dehydrogenation catalyst is a catalyst in which zeolite is used as a carrier and zinc and a Group VIIIA metal are supported as active components.
  • the amount of zinc contained in such a catalyst is preferably 0.01 to 15% by weight, with the total weight of the catalyst being 100% by weight, and the amount of the Group VIIIA metal is the total weight of the catalyst. When it is 100% by weight, it is preferably 0.01 to 5% by weight.
  • the Group VIIIA metal is preferably platinum.
  • silicalite or borosilicate is preferable, and one having an MFI structure is more preferable.
  • a more preferable zeolite carrier is a silicate obtained by removing at least a part of boron atoms from MFI-type borosilicate, and the boron atom remaining rate in the silicate is 80% or less of the total amount of boron atoms in MFI-type borosilicate. Some are particularly preferred.
  • the volatilization of zinc from the dehydrogenation catalyst can be effectively suppressed by a very simple method, and as a result, the high activity of the dehydrogenation catalyst can be obtained over a long period of time. It is possible to produce predominantly unsaturated hydrocarbons, ie olefins or dienes.
  • production method (1) a raw material-containing gas (1) containing hydrocarbons is brought into contact with metal zinc and / or a zinc compound, and then one of the active ingredients. And a step of producing an unsaturated hydrocarbon by bringing the hydrocarbon into contact with a dehydrogenation catalyst containing zinc.
  • an unsaturated hydrocarbon production method uses a raw material-containing gas (2) containing hydrocarbon and zinc vapor as one of the active components. It includes a step of producing an unsaturated hydrocarbon by contacting with a dehydrogenation catalyst containing zinc to perform a dehydrogenation reaction of the hydrocarbon.
  • production method (2) uses a raw material-containing gas (2) containing hydrocarbon and zinc vapor as one of the active components. It includes a step of producing an unsaturated hydrocarbon by contacting with a dehydrogenation catalyst containing zinc to perform a dehydrogenation reaction of the hydrocarbon.
  • the reaction temperature range during the dehydrogenation reaction is preferably 300 to 800 ° C., more preferably 400 to 700 ° C., and particularly preferably 450 to 650 ° C.
  • the reaction temperature is equal to or higher than the lower limit, the hydrocarbon as a raw material is converted to an unsaturated hydrocarbon at a high equilibrium conversion rate, so that the unsaturated hydrocarbon is produced in a high yield with a single pass.
  • the reaction temperature is not more than the above upper limit value, the coking speed is not increased, and the activity deterioration of the catalyst can be suppressed.
  • the range of the reaction pressure is preferably 0.01 to 1 MPa, more preferably 0.01 to 0.5 MPa. The lower the reaction pressure, the higher the equilibrium conversion rate of the raw material hydrocarbon, and the higher the yield of unsaturated hydrocarbon in one pass.
  • the reaction is preferably carried out in a continuous reaction apparatus.
  • the amount of catalyst used is simply and appropriately expressed by the weight hourly space velocity WHSV (the weight of the feedstock hydrocarbon per unit weight of catalyst and unit time).
  • Range of WHSV in the present invention is not particularly limited, preferably 0.01 ⁇ 50h -1, more preferably from 0.1 ⁇ 20h -1.
  • the present invention is characterized in that a raw material-containing gas containing zinc vapor is brought into contact with a catalyst containing zinc as one of active components.
  • a catalyst containing zinc as one of active components.
  • the partial pressure of the zinc vapor contained in the raw material-containing gas in contact with the catalyst is equal to or lower than the vapor pressure of zinc at the reaction temperature, and the concentration (based on volume) of the zinc vapor contained in the raw material-containing gas exceeds 0%.
  • it is 0.01% or more, More preferably, it is 0.05% or more.
  • Examples of the source of zinc vapor include metal zinc, zinc oxide, zinc nitrate, zinc chloride, zinc acetate, zinc aluminate and the like, and since zinc vapor is easily generated, metal zinc and / or zinc oxide is used. preferable.
  • the source of zinc vapor is heated to generate zinc vapor having a predetermined partial pressure, but the temperature range is preferably 300 ° C. or higher and the reaction temperature or lower, more preferably 400 ° C. or higher and the reaction temperature or lower. Particularly preferably, it is 450 ° C. or higher and the reaction temperature or lower.
  • the method for supplying zinc vapor to the raw material-containing gas there is no particular limitation on the method for supplying zinc vapor to the raw material-containing gas.
  • the metallic zinc and / or zinc compound is heated to a predetermined temperature in a chamber separate from the reactor (that is, the vessel for performing the hydrocarbon dehydrogenation reaction).
  • a mixed gas consisting of a hydrocarbon gas as a raw material and an inert gas optionally used, zinc vapor corresponding to the maximum vapor pressure and a hydrocarbon gas as a raw material and an inert gas You may include in the mixed gas which consists of.
  • a catalyst layer containing the catalyst is formed in the reaction tube, and a layer of zinc oxide or zinc aluminate is provided on the upstream side of the gas flow in the reaction tube with respect to the catalyst layer, and this layer is formed as a reducing gas (for example, , Hydrogen gas) is heated in the presence of this gas to generate zinc vapor from this layer, including the raw material hydrocarbon gas, optionally used inert gas, and optionally unreacted reducing gas.
  • a reducing gas for example, Hydrogen gas
  • the supply of zinc vapor may be continuous or intermittent, but in the case of intermittent supply, it is necessary to provide a chamber separate from the reactor.
  • hydrocarbons that are converted to unsaturated hydrocarbons by dehydrogenation are fed to the reactor.
  • the unsaturated hydrocarbon produced in the present invention is preferably an olefin (unsaturated hydrocarbon in which one double bond exists in one molecule) and a diene (one double bond in one molecule) from the viewpoint of industrial usefulness. Unsaturated hydrocarbons present in the two). That is, the method for producing unsaturated hydrocarbons of the present invention is preferably a method for producing olefins or dienes.
  • Particularly preferred compounds as the hydrocarbon as the raw material are propane, n-butane, isobutane, 1-butene, 2-butene and mixtures thereof, and particularly preferred compounds as the unsaturated hydrocarbon are propylene, 1-butene, 2 -Butene, isobutene, 1,3-butadiene and mixtures thereof.
  • a mixture of 1-butene and 2-butene is usually referred to as n-butene.
  • the raw material hydrocarbon gas may be supplied to the reactor together with other gases that do not impair the effects of the present invention.
  • the other gases include water vapor, nitrogen gas, carbon dioxide gas, hydrogen gas, and methane gas. Can be mentioned. Among these, water vapor is particularly preferable from the viewpoint of extending the life of the dehydrogenation catalyst.
  • steam from zinc oxide may be supplied as other gas.
  • the mixing method and mixing ratio of the hydrocarbon gas and the other gas are not particularly limited.
  • the reaction format used in the present invention is not particularly limited, and a known method can be employed, and examples thereof include a fixed bed, a moving bed, and a fluidized bed. From the viewpoint of ease of process design, a fixed bed type is particularly preferable.
  • a dehydrogenation catalyst containing zinc is used as one of the active components, preferably a catalyst using zeolite as a carrier and carrying zinc and a Group VIIIA metal as the active components.
  • Zinc and Group VIIIA metals can be supported on the zeolite using, for example, metal compounds such as the corresponding metal nitrates, metal chlorides or metal complexes.
  • the loading on zeolite can be carried out by a known method such as an ion exchange method or an impregnation method, and the order of loading is not particularly limited.
  • Examples of the zinc compound include zinc nitrate, zinc chloride, and zinc acetate.
  • Examples of the Group VIIIA metal compound include chloroplatinic acid, tetraammineplatinum chloride, tetraammineplatinum hydroxide, and tetraammineplatinum nitrate.
  • the range of the amount of zinc contained in the dehydrogenation catalyst is preferably from 0.01 to 15% by weight, more preferably from 0.05 to 15% by weight as the ratio of the weight of zinc metal atoms to the weight of the whole catalyst (100% by weight). 5% by weight, particularly preferably 0.1 to 3% by weight.
  • the range of the amount of the Group VIIIA metal contained in the dehydrogenation catalyst is preferably 0.01 to 5% by weight, more preferably as a ratio of the weight of the Group VIIIA metal atom to the total weight (100% by weight) of the catalyst. Is 0.05 to 3% by weight, particularly preferably 0.1 to 1.5% by weight.
  • the ratio of zinc to the Group VIIIA metal is usually 0.5 or more, preferably 0.5 to 50, more preferably 1 to 30, in terms of molar ratio (number of moles of Zn / number of moles of Group VIIIA metal). Preferably it is 1-20.
  • the Group VIIIA metal is an old IUPAC system notation, which is a Group 8-10 metal in the IUPAC system.
  • Examples of the Group VIIIA metal include platinum, palladium, ruthenium, iridium, rhodium, and nickel. Among these, platinum is preferable from the viewpoint of catalytic activity.
  • the zinc compound and optionally the Group VIIIA metal compound are supported on zeolite, followed by drying and calcination.
  • the drying conditions are not particularly limited, but the drying is usually performed at 80 to 150 ° C. for a predetermined time.
  • the firing conditions are not particularly limited, but the firing is usually performed at 400 to 600 ° C. for a predetermined time.
  • the atmosphere during firing is not particularly limited, but usually drying and firing are carried out under air circulation.
  • zeolite is a name used as a general term for crystalline porous aluminosilicate, and is classified by a structure code according to the topology. For each structure code, information about structure, composition, crystallographic data is known (for example, Atlas of Zeolite Structure Types, 4th Ed., Elsevier 1996, and Collection of Simulated XRD Powder Pattern 19). ).
  • silicalite not containing aluminum, metallosilicate containing iron, gallium, titanium, etc. instead of aluminum are also included in zeolite (for example, the science of zeolite And engineering, Kodansha Scientific).
  • silicalite containing no aluminum or borosilicate which is a metallosilicate containing boron instead of aluminum is preferably used as a catalyst carrier.
  • the aluminum content in the silicalite or borosilicate used in the present invention is not particularly limited, but the silica / alumina molar ratio (number of moles of SiO 2 / number of moles of Al 2 O 3 ) in these zeolites is 100 or more. Is more preferably 500 or more, particularly preferably 1000 or more, and most preferably 2000 or more.
  • the silica / alumina molar ratio is 100 or more, side reactions such as oligomerization that proceeds on acid sites caused by aluminum are suppressed. If the silica / alumina molar ratio is 2000 or more, such side reactions can be more effectively suppressed.
  • the boron content in the borosilicate is not particularly limited, but is preferably 100 to 30000 ppm, more preferably 500 to 10000 ppm, and particularly preferably 1000 to 80000 ppm.
  • the content of alkali metal and alkaline earth metal in silicalite or borosilicate is not particularly limited, but it is preferable that these metals are not substantially present. “Substantially absent” means that the content of alkali metal and alkaline earth metal in silicalite or borosilicate is 300 ppm or less, respectively.
  • the silicalite and the borosilicate have an MFI structure.
  • a borosilicate having an MFI structure (hereinafter also referred to as “MFI-type borosilicate”) may be used as a carrier as it is, but a silicate obtained by removing at least a part of boron atoms from the MFI-type borosilicate is used as a carrier. It is preferable to use it.
  • the boron atom remaining rate in the silicate after removing at least a part of boron atoms from the MFI-type borosilicate is preferably 80% or less of the total amount of boron atoms in the borosilicate, and is 50% or less. Is more preferably 30% or less, and most preferably 20% or less.
  • the boron atom residual ratio is calculated by comparing the boron atom content in the borosilicate before removing the boron atom and the boron atom content in the silicate after removing the boron atom.
  • the method for removing at least a part of boron atoms from the borosilicate is not limited, and a known method such as a method of treating with an aqueous solution of an inorganic acid or an organic acid is employed.
  • the catalyst charged in the reactor may be in the form of a powder or a molded body.
  • molding method Well-known methods, such as extrusion molding, tableting shaping
  • a pretreatment for activating the catalyst may be performed after the catalyst is charged into the reactor and before the start of the reaction.
  • the catalyst is usually a reducing gas such as hydrogen or carbon monoxide. Contact. These reducing gases may be used without being diluted, or may be appropriately diluted with the above-described inert gas.
  • the reaction may be stopped and the catalyst may be reactivated by a method called regeneration treatment.
  • the method is not particularly limited, but usually a method of burning and removing heavy hydrocarbons called coke deposited on the catalyst surface by bringing a gas containing oxygen into contact with the catalyst at a predetermined temperature.
  • the washed cake was dried for 3 hours in a static electric furnace in which air was circulated and maintained at 120 ° C., and then calcined at 500 ° C. for 4 hours.
  • a silicate from which part was removed was obtained.
  • the amount of boron atoms in the obtained silicate was 260 ppm, and the residual ratio of boron atoms at this time was 8%.
  • Catalyst preparation 2 To 2 g of the silicate obtained in Catalyst Preparation 1, 0.66 g of an aqueous solution containing 0.058 g of zinc nitrate hexahydrate was added and impregnated with zinc ions by the incipient-wetness method. The silicate impregnated with zinc ions was dried for 3 hours in a static electric furnace maintained at 120 ° C. through which air was circulated, and then baked at 500 ° C. for 4 hours to form a silicate on which zinc was supported. Prepared.
  • Catalyst preparation 3 Add 0.375 g of an aqueous solution containing 0.0127 g of chloroplatinic acid hexahydrate to 1.5 g of the zinc-supported silicate obtained in Catalyst Preparation 2, and impregnate it with platinum ions by the incipient-wetness method. It was. The silicate impregnated with platinum ions was dried for 3 hours in a static electric furnace in which air was circulated and maintained at 120 ° C., followed by firing at 500 ° C. for 4 hours to support platinum and zinc. Silicate catalyst powder was obtained. This silicate catalyst had a platinum loading of 0.32 wt% and a zinc loading of 0.64 wt%.
  • Example 1 An SUS tube equipped with an inner tube of alumina with an inner diameter of 6 mm was filled with 0.2 g of the silicate catalyst carrying platinum and zinc obtained in Catalyst Preparation 3, and then oxidized upstream of the catalyst with silica wool in between.
  • a reaction tube was manufactured by charging 0.1 g of zinc (manufactured by Sigma-Aldrich), filling alumina balls before and after them, and fixing the catalyst and zinc oxide.
  • the catalyst was pretreated by flowing a mixed gas consisting of 20 sccm of hydrogen and 0.064 g / min of water vapor at 600 ° C.
  • reaction tube was pretreated with 2.1 sccm of hydrogen, 13.55 sccm of propane, and 0.
  • the propane dehydrogenation reaction was started by feeding 022 g / min.
  • reaction temperature was raised to 650 degreeC with the start of reaction.
  • the catalyst showed stable activity over a long period of time, with a propylene yield of 60% over about 120 hours.
  • Example 1 A reaction tube was produced in the same manner as in Example 1 except that zinc oxide was not charged, and propane dehydrogenation reaction was started under the same pretreatment conditions and reaction conditions as in Example 1.
  • the catalyst showed a propylene yield of 60% over about 60 hours.
  • Example 2 A reaction tube was manufactured in the same manner as in Example 1 except that the silicate catalyst was not charged. As in Example 1, the reaction tube was charged with 20 sccm of hydrogen and 0.064 g / min of water vapor at 600 ° C. and normal pressure. After flowing the mixed gas for 2 hours, 2.1 sccm of hydrogen, 13.55 sccm of propane, and 0.022 g / min of water vapor were supplied at 650 ° C. Zinc oxide did not show any catalytic activity in the propane dehydrogenation reaction. From the above results, it is clear that the zinc oxide itself charged upstream of the catalyst has no catalytic activity, while the presence of zinc oxide exhibits a high activity over a long period of time.
  • a reaction tube was manufactured in the same manner as in Comparative Example 2 except that a quartz tube that had been processed to fix the catalyst was used instead of the SUS tube that was fitted with an alumina intubation tube, and the alumina balls were not filled.
  • a mixed gas composed of hydrogen at 20 ° C. and water vapor at 0.064 g / min at 600 ° C. and normal pressure for 2 hours, 650 ° C. at 2.1 sccm of hydrogen and propane 13.55 sccm and water vapor 0.022 g / min were fed.

Landscapes

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

Abstract

L'invention vise à procurer un procédé de production d'un hydrocarbure insaturé par la déshydrogénation d'un hydrocarbure au moyen d'un catalyseur de déshydrogénation, qui produit de manière stable un hydrocarbure insaturé, c'est-à-dire une oléfine et/ou un diène pendant une longue période en supprimant de façon efficace la volatilisation du zinc du catalyseur de déshydrogénation. L'invention concerne un procédé de production d'un hydrocarbure insaturé qui comprend une étape dans laquelle un gaz contenant une matière de départ (1), qui contient un hydrocarbure, est mis en contact avec du zinc métallique et/ou un composé de zinc, puis le gaz contenant une matière de départ (1) est mis en contact avec un catalyseur de déshydrogénation qui contient du zinc comme constituant actif, ce qui permet d'effectuer une réaction de déshydrogénation de l'hydrocarbure de manière à produire un hydrocarbure insaturé.
PCT/JP2015/059947 2014-03-31 2015-03-30 Procédé de production d'un hydrocarbure insaturé Ceased WO2015152160A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016511886A JP6426711B2 (ja) 2014-03-31 2015-03-30 不飽和炭化水素の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-073071 2014-03-31
JP2014073071 2014-03-31

Publications (1)

Publication Number Publication Date
WO2015152160A1 true WO2015152160A1 (fr) 2015-10-08

Family

ID=54240483

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/059947 Ceased WO2015152160A1 (fr) 2014-03-31 2015-03-30 Procédé de production d'un hydrocarbure insaturé

Country Status (3)

Country Link
JP (1) JP6426711B2 (fr)
TW (1) TW201542512A (fr)
WO (1) WO2015152160A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017177056A (ja) * 2016-03-31 2017-10-05 三菱ケミカル株式会社 アルカン脱水素用触媒及びこれを用いたアルケンの製造方法
EP4036073A4 (fr) * 2019-12-18 2022-11-09 Rezel Catalysts Corporation Procédé, dispositif et système de réaction de déshydrogénation d'alcanes à faible teneur en carbone
WO2023218140A1 (fr) * 2022-05-10 2023-11-16 Arkema France Procede ameliore de deshydrogenation d'hydrocarbures

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0649460A (ja) * 1991-06-12 1994-02-22 Sekiyu Shigen Kaihatsu Kk エタンから液状炭化水素混合物の製造方法
JPH0975732A (ja) * 1995-09-08 1997-03-25 Chiyoda Corp 脱水素触媒
JP2000037629A (ja) * 1998-07-24 2000-02-08 Chiyoda Corp 脱水素触媒
JP2005008575A (ja) * 2003-06-19 2005-01-13 Japan Science & Technology Agency アルケンの製造方法、硫化水素の製造方法、アルカンの脱水素方法、および触媒
JP2011529781A (ja) * 2008-08-07 2011-12-15 ウーデ ゲゼルシャフト ミット ベシュレンクテル ハフツング アルカンの脱水素化用触媒担体としての高空隙率セラミックス発泡体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0649460A (ja) * 1991-06-12 1994-02-22 Sekiyu Shigen Kaihatsu Kk エタンから液状炭化水素混合物の製造方法
JPH0975732A (ja) * 1995-09-08 1997-03-25 Chiyoda Corp 脱水素触媒
JP2000037629A (ja) * 1998-07-24 2000-02-08 Chiyoda Corp 脱水素触媒
JP2005008575A (ja) * 2003-06-19 2005-01-13 Japan Science & Technology Agency アルケンの製造方法、硫化水素の製造方法、アルカンの脱水素方法、および触媒
JP2011529781A (ja) * 2008-08-07 2011-12-15 ウーデ ゲゼルシャフト ミット ベシュレンクテル ハフツング アルカンの脱水素化用触媒担体としての高空隙率セラミックス発泡体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALMUTAIRI, SAMI M. T. ET AL.: "Structure and Reactivity of Zn-Modified ZSM-5 Zeolites: The Importance of Clustered Cationic Zn Complexes", ACS CATALYSIS, vol. 2, no. 1, 2012, pages 71 - 83 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017177056A (ja) * 2016-03-31 2017-10-05 三菱ケミカル株式会社 アルカン脱水素用触媒及びこれを用いたアルケンの製造方法
EP4036073A4 (fr) * 2019-12-18 2022-11-09 Rezel Catalysts Corporation Procédé, dispositif et système de réaction de déshydrogénation d'alcanes à faible teneur en carbone
WO2023218140A1 (fr) * 2022-05-10 2023-11-16 Arkema France Procede ameliore de deshydrogenation d'hydrocarbures
FR3135458A1 (fr) * 2022-05-10 2023-11-17 Arkema France Procede ameliore de deshydrogenation d’hydrocarbures

Also Published As

Publication number Publication date
TW201542512A (zh) 2015-11-16
JP6426711B2 (ja) 2018-11-21
JPWO2015152160A1 (ja) 2017-04-13

Similar Documents

Publication Publication Date Title
RU2614977C2 (ru) Каталитическая композиция и способ дегидрирования бутенов или смесей бутанов и бутенов с получением 1,3-бутадиена
CN103068774B (zh) 不饱和烃的制造方法和用于该方法的脱氢用催化剂
JP4523947B2 (ja) 金属触媒を用いたジメチルナフタレンの製造方法
JP6595606B2 (ja) オレフィンを製造するための触媒及びプロセス
JP2008537944A (ja) アセチレンのエチレンへの選択的水素化方法
JPH0729058B2 (ja) 化学方法および触媒
JP2018177750A (ja) 不飽和炭化水素の製造方法及び脱水素触媒の再生方法
JP5345058B2 (ja) メタセシス触媒の再活性化方法およびその再活性化工程を含むオレフィン類の製造方法
JP4706945B2 (ja) 優れたアクセシビリティーを有する、第８、９または１０族の元素を含む触媒、およびパラフィン脱水素方法におけるその使用
TW201821159A (zh) 烴轉化製程
CN109926087B (zh) 轻质烷烃脱氢用沸石负载型催化剂和其制备方法
JP6426711B2 (ja) 不飽和炭化水素の製造方法
CA2747085A1 (fr) Variation de l'impregnation en etain d'un catalyseur pour la deshydrogenation d'alcanes
RU2127242C1 (ru) Способ получения олефиновых углеводородов
TW201822879A (zh) 烴轉化催化劑系統
CN101965323B (zh) 乙苯的转化方法和对二甲苯制造方法
JP6446033B2 (ja) 不飽和炭化水素の製造方法
KR101440695B1 (ko) 노말-부텐 및 부타디엔 선택성이 향상된 노말-부탄의 탈수소화 및 탈수소 이성화 반응용 촉매 및 이를 이용해 노말부텐, 1,3-부타디엔 및 이소부텐의 혼합물을 고수율로 제조하는 방법
TW201822880A (zh) 催化劑系統與使用催化劑系統的烴進料轉化製程
KR101485697B1 (ko) 알칼리금속으로 개질된 노말-부탄의 탈수소화 및 탈수소 이성화 반응용 촉매 및 이를 이용하여 노말-부탄으로부터 노말-부텐 대 이소부텐 생성비가 조절된 노말-부텐, 1,3-부타디엔 및 이소부텐의 혼합물을 제조하는 방법
JP6037849B2 (ja) 酸化脱水素触媒の製造方法およびアルケンの製造方法
RU2627667C1 (ru) Катализатор с низким содержанием оксида хрома для дегидрирования изобутана и способ дегидрирования изобутана с его использованием
KR102234498B1 (ko) 티타니아 내에 금속 클러스터가 함유된 탈수소화 촉매 및 이의 제조방법
JP7064897B2 (ja) 不飽和炭化水素の製造方法
WO2017138667A1 (fr) Procédé de fabrication d'hydrocarbure insaturé, et procédé de fabrication de diène conjugué

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15772555

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016511886

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase
122 Ep: pct application non-entry in european phase

Ref document number: 15772555

Country of ref document: EP

Kind code of ref document: A1