[go: up one dir, main page]

WO2015152159A1 - Procédé de production d'hydrocarbure insaturé - Google Patents

Procédé de production d'hydrocarbure insaturé Download PDF

Info

Publication number
WO2015152159A1
WO2015152159A1 PCT/JP2015/059946 JP2015059946W WO2015152159A1 WO 2015152159 A1 WO2015152159 A1 WO 2015152159A1 JP 2015059946 W JP2015059946 W JP 2015059946W WO 2015152159 A1 WO2015152159 A1 WO 2015152159A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
producing
unsaturated hydrocarbon
ethylene
dehydrogenation
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/JP2015/059946
Other languages
English (en)
Japanese (ja)
Inventor
智 宮添
裕一 池永
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 JP2016511885A priority Critical patent/JP6446033B2/ja
Publication of WO2015152159A1 publication Critical patent/WO2015152159A1/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
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/50—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with an organic compound as an acceptor
    • C07C5/52—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with an organic compound as an acceptor with a hydrocarbon as an acceptor, e.g. hydrocarbon disproportionation, i.e. 2CnHp -> CnHp+q + CnHp-q
    • 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
    • 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
    • C07C2529/86—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 7 also 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.
  • hydrocarbon dehydrogenation is subject to equilibrium constraints. Higher temperature and / or lower pressure conditions are advantageous for the product, but at higher temperatures, the catalytic activity is largely degraded due to coking, and special equipment is required to lower or reduce the pressure. It becomes a difficult point.
  • Patent Document 8 discloses a method for removing hydrogen by introducing oxygen.
  • Patent Document 9 discloses a hydrocarbon conversion method using ethylene as a hydrogen acceptor. Unlike the case of oxygen, mixing of olefins such as ethylene is preferable in that the amount of mixing is not limited from the viewpoint of ensuring safety.
  • Patent Document 10 It has already been reported that when a hydrogen acceptor is actually used, a yield exceeding the equilibrium limit value when not used is obtained (Patent Document 10). However, it is already known that reaction inhibition occurs when an olefin is used as a hydrogen acceptor, as described in Patent Document 11.
  • a method of supplying ethylene in the same reactor in a divided manner is also conceivable, but in this case, the catalyst and high-concentration ethylene are locally in contact with each other, and as a result, the local catalytic activity is significantly reduced. After all, it is hard to say that it is effective. Against this background, it is desirable to establish a new ethylene supply method that effectively shifts the equilibrium to the product side, enables a significant increase in product yield, and minimizes the loss of expensive ethylene. It is.
  • the present invention relates to a method for producing an unsaturated hydrocarbon by dehydrogenating a hydrocarbon, wherein the unsaturated hydrocarbon is produced while supplying ethylene as an acceptor of hydrogen produced by the dehydrogenation reaction.
  • An object of the present invention is to provide a method for producing unsaturated hydrocarbons, that is, olefins and dienes, with a minimum loss of ethylene and with good yield over a long period of time.
  • the present inventors have started investigations to solve the above-mentioned problems, and have found that when a hydrocarbon gas containing hydrogen and ethylene are mixed and then brought into contact with the catalyst, deterioration of the catalyst performance may be suppressed. Then, by mixing ethylene with the dehydrogenation product gas using a specific reactor and controlling the rate of conversion of ethylene to ethane by the acceptance of hydrogen, the equilibrium in the hydrocarbon dehydrogenation reaction is effectively increased. It has been found that the product can be shifted to the product side and the loss of ethylene is minimized, and as a result, the target product, an unsaturated hydrocarbon, that is, olefin or diene, can be produced with higher efficiency than before.
  • the present invention A method for producing an unsaturated hydrocarbon by dehydrogenating a hydrocarbon in a reactor,
  • the reactor has a first reaction region, a second reaction region provided on the downstream side thereof, and a connection region that connects the first reaction region and the second reaction region,
  • the method supplies a raw material-containing gas containing hydrocarbons (excluding ethylene) to the first reaction region, and performs hydrocarbon dehydrogenation to contain hydrocarbons, unsaturated hydrocarbons, and hydrogen.
  • a process for producing an unsaturated hydrocarbon comprising a step of performing a dehydrogenation reaction of the above and a reaction of adding the hydrogen to the ethylene to produce ethane.
  • the conversion rate of ethylene to ethane is preferably 50% or more, more preferably 70% or more, particularly preferably 90% or more, and preferably 95% or more. Most preferred.
  • ethylene When ethylene is contained in the gas recovered from the reactor on the downstream side of the second reaction zone, at least a part of the ethylene may be treated as off-gas without being separated from ethane, You may use as at least one part of ethylene supplied to a connection area.
  • the reaction temperature in the dehydrogenation reaction is preferably in the range of 300 to 700 ° C., more preferably in the range of 400 to 650 ° C., and particularly preferably in the range of 450 to 600 ° C.
  • the reaction pressure during the dehydrogenation reaction is preferably in the range of 0.01 to 3 MPa.
  • 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 preferably further contains water vapor.
  • a preferred form as a 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 equilibrium in hydrocarbon dehydrogenation can be greatly shifted to the product side, and the loss of expensive ethylene for accepting hydrogen generated in the dehydrogenation can be minimized.
  • This makes it possible to produce unsaturated hydrocarbons, that is, olefins or dienes, with a significant economic advantage.
  • FIG. 1 shows the transition of the conversion rate of ethylene and propane in the propane dehydrogenation reaction in Example 1, Comparative Example 1 and Comparative Example 2.
  • the method for producing an unsaturated hydrocarbon according to the present invention is a method for producing an unsaturated hydrocarbon by carrying out a hydrocarbon dehydrogenation reaction in a reactor, wherein the reactor comprises a first reaction region, downstream thereof. A second reaction region provided on the side, and a connection region that connects the first reaction region and the second reaction region, and the method contains a raw material containing a hydrocarbon (excluding ethylene).
  • the “reactor” is a reaction system including the first reaction region, the connection region, and the second reaction region (hereinafter collectively referred to as “reaction region connected in series”). Means the whole.
  • the “first reaction region” means a region where a hydrocarbon dehydrogenation reaction is performed, and the “second reaction region” is a region where a hydrocarbon dehydrogenation reaction and a hydrogen addition reaction to ethylene are performed. Means.
  • the number of series of “reaction zones connected in series” may be single or plural. Also, each reaction region may be provided in a separate container, and a plurality of containers may be connected to constitute one reactor, or a plurality of reaction regions may be provided in one container to constitute a reactor. You may do it. Alternatively, these configurations may be combined.
  • the first reaction zone and the second reaction zone are usually filled with a dehydrogenation catalyst.
  • a dehydrogenation catalyst Any known catalyst bed system may be applied as the catalyst bed system, and examples of the catalyst bed include a fixed bed, a moving bed, and a fluidized bed.
  • the dehydrogenation catalyst is present in the connection region, the catalyst and high-concentration ethylene are locally in contact with each other, and as a result, the local catalyst activity may be significantly reduced.
  • hydrocarbons that are converted to unsaturated hydrocarbons by dehydrogenation are supplied to the reactor.
  • the hydrocarbon is preferably an aliphatic hydrocarbon having 3 to 6 carbon atoms.
  • Particularly preferred compounds as the hydrocarbon are propane, normal butane, isobutane, 1-butene, 2-butene and mixtures thereof.
  • the unsaturated hydrocarbon produced in the present invention is a hydrocarbon having the same carbon number as the raw material hydrocarbon and having at least one more carbon-carbon unsaturated bond than the raw material hydrocarbon, From the viewpoint of industrial utility, olefins (unsaturated hydrocarbons having one double bond in one molecule) and dienes (unsaturated hydrocarbons having two double bonds in one molecule) are preferable. is there. 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 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 hydrocarbon gas as the raw material may be supplied to the reactor together with other gas (inert gas) that does not impair the effects of the present invention.
  • the inert gas include water vapor, nitrogen gas, carbon dioxide gas, hydrogen Examples thereof include gas and methane gas. Among these, water vapor is particularly preferable.
  • the mixing method and mixing ratio of hydrocarbon gas and these inert gases are not particularly limited.
  • the raw material-containing gas may contain a trace amount of ethylene that does not hinder the effects of the present invention, but preferably does not contain ethylene.
  • the primary product gas supplied from the upstream first reaction region in this gas, unsaturated hydrocarbons and hydrogen generated in the dehydrogenation reaction, and hydrocarbons as raw materials
  • ethylene is mixed, and the obtained mixed gas is supplied to the second reaction zone on the downstream side.
  • the “second reaction zone” On the downstream side of the “second reaction zone”, the “second reaction zone” is further connected via a connection zone for mixing the gas generated in the “second reaction zone” and ethylene supplied from outside the system. May be provided.
  • Ethylene is converted to ethane by hydrogen addition reaction in the second reaction zone.
  • the conversion of ethylene to ethane is preferably 50% or more from the viewpoint of minimizing ethylene loss, more preferably 70% or more, particularly preferably 90% or more, and 95 % Or more is most preferable.
  • the conversion ratio of ethylene to ethane is calculated from the total amount of ethylene supplied and the ratio of ethane contained in the product gas obtained from the reactor.
  • the conversion rate of ethylene to ethane is adjusted by the ethylene supply rate, and the lower the ethylene supply rate (B) relative to the hydrogen supply rate (A) from the first reaction zone, the higher the conversion rate can be.
  • the ethylene supply rate in each connecting portion may be unified or different, and the ethylene supplying rate to the connecting portion may be adjusted while measuring the ethylene concentration in the product gas from the upstream reaction region. .
  • ethylene When ethylene is contained in the product gas obtained from the reactor on the downstream side of the second reaction zone, at least a part of this ethylene may be treated as off-gas together with ethane, or continuously or batchwise. When the production method of the present invention is carried out a plurality of times, it may be recycled to the reactor together with ethane.
  • the off gas may be used as a fuel gas or may be supplied to a pyrolysis furnace and used as an ethylene production raw material.
  • the reaction temperature range during the dehydrogenation reaction is preferably 300 to 700 ° C., more preferably 400 to 650 ° C., and particularly preferably 450 to 600 ° 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 rate is not increased, the catalyst activity deterioration is suppressed, and the equilibrium between ethane and ethylene is advantageous to the ethane side.
  • the range of the partial pressure of the raw material hydrocarbon supplied to the reactor is preferably 0.001 to 1 MPa, and more preferably 0.005 to 0.5 MPa.
  • the lower the partial pressure the higher the equilibrium conversion rate of the hydrocarbon as a raw material, and the higher the yield of unsaturated hydrocarbons in one pass.
  • the partial pressure of the hydrocarbon can be lowered.
  • the range of the reaction pressure is preferably 0.01 to 3 MPa, more preferably 0.1 to 1.5 MPa.
  • the lower the reaction pressure the higher the equilibrium conversion rate of the hydrocarbon as a raw material, and the higher the yield of unsaturated hydrocarbons in a single operation.
  • a special design and equipment for keeping the pressure low may be used.
  • 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).
  • the feed weight of the hydrocarbon as a raw material does not include the feed weight of ethylene.
  • Range of WHSV in the present invention is not particularly limited, preferably 0.01 ⁇ 50h -1, more preferably from 0.1 ⁇ 20h -1.
  • a catalyst carrying a Group VIIIA metal as an active component is preferably used as the dehydrogenation catalyst.
  • the catalyst carrier an alumina carrier, a spinel carrier such as zinc aluminate or magnesium aluminate, a calcined hydrotalcite, a silica carrier, a zeolite carrier and the like can be used.
  • the zeolite carrier those with or without acid properties are preferred.
  • 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 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.
  • a dehydrogenation catalyst containing zinc in addition to the Group VIIIA metal is preferably used as one of the active components.
  • the amount of zinc contained in the dehydrogenation catalyst is preferably in the range of 0.01 to 15% by weight, and more preferably in the range of 0.01 to 15% by weight as the ratio of the weight of zinc metal atoms to the weight of the whole catalyst (100% by weight). 05 to 5% by weight, particularly preferably 0.1 to 3% 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.
  • 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). ). Further, as a compound other than an aluminosilicate having a similar crystal structure, silicalite not containing aluminum, metallosilicate containing iron, gallium, titanium and the like instead of aluminum are also included in zeolite (for example, “zeolite of Science 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 of the produced unsaturated hydrocarbon on the 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. More preferably, it is used.
  • 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.
  • a dehydrogenation catalyst suitable for the present invention can be produced by supporting a Group VIIIA metal compound or zinc compound on a catalyst carrier, followed by drying and firing.
  • 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 firing is usually performed under air circulation.
  • the Group VIIIA metal and zinc can be supported on a catalyst using, for example, a metal compound such as a corresponding metal nitrate, metal chloride or metal complex.
  • a metal compound such as a corresponding metal nitrate, metal chloride or metal complex.
  • Support on the catalyst carrier can be carried out by a known method such as an ion exchange method or an impregnation method, and the order of support is not particularly limited.
  • the Group VIIIA metal compound include chloroplatinic acid, tetraammineplatinum chloride, tetraammineplatinum hydroxide, and tetraammineplatinum nitrate.
  • the zinc compound include zinc nitrate, zinc chloride, and zinc acetate.
  • the dehydrogenation catalyst can be used in any form suitable for the catalyst bed system employed when filling the reaction region, and may be a powder, a granule, or a molded one such as a pellet, a sphere, or a cylinder. .
  • molding method Well-known methods, such as extrusion molding, tableting shaping
  • a pretreatment for activating the catalyst may be performed in advance, and the pretreatment usually involves adding hydrogen or monoxide to the catalyst.
  • a reducing gas such as carbon.
  • These reducing gases may be used without being diluted, or may be appropriately diluted with the above-described inert gas.
  • the production of unsaturated hydrocarbons is stopped and the catalyst can 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 contacting a gas containing oxygen at a predetermined temperature with the catalyst is adopted. .
  • the regeneration of the dehydrogenation catalyst is not particularly limited as long as it is a known method suitable for the catalyst bed system in the reaction zone.
  • a method may be used in which the catalyst is separated from the series, the catalyst is regenerated while being filled in the container, and then the catalyst is reconnected to the series.
  • a part of the packed catalyst may be extracted and returned to the reaction region after being subjected to a regeneration process, whereby the regeneration process may be continuously performed while circulating the catalyst.
  • 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. From the MFI-type borosilicate, at least boron atoms were baked. A silicate with a part removed was obtained.
  • 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 is dried for 3 hours in a static electric furnace maintained at 120 ° C. through which air is circulated, and then baked at 500 ° C. for 4 hours to silicate on which zinc is supported Was 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 is dried for 3 hours in a static electric furnace maintained at 120 ° C. through which air is circulated, and then baked at 500 ° C. for 4 hours to support platinum and zinc.
  • Silicate powder was obtained. This silicate had a platinum loading of 0.32 wt% and a zinc loading of 0.64 wt%.
  • the obtained powder was compression-molded into a disk shape and then crushed, and the particle size was adjusted to 250 to 500 micrometers with a sieve to obtain Catalyst A.
  • reaction tube 1 Two small fixed bed reaction tubes (reaction tube 1, reaction tube 2) were filled with 0.1 g of catalyst A, and each catalyst A was pretreated (heated at 600 ° C. for 2 hours). Subsequently, the two reaction tubes were connected in series in the order of reaction tubes 1 and 2 from the upstream side to the downstream side of the gas flow in the reaction tube, and 3.2 g / hour of propane was added to the reaction tube 1 as a hydrocarbon. Nitrogen was started to be supplied at a rate of 3.0 g / h, and ethylene was started to be supplied to a pipe (connecting portion) connecting the reaction tube 1 and the reaction tube 2 at a rate of 0.97 g / h. The connecting portion was not filled with catalyst A.
  • Example 2 A propane dehydrogenation reaction was carried out in the same manner as in Example 1 except that ethylene was supplied to the reaction tube 1 instead of from each connecting portion at a rate of 0.97 g per hour together with propane and nitrogen. The results are shown in Table 3. Moreover, transition of the conversion rate of Example 1, Comparative Example 1, and Comparative Example 2 is shown in FIG. From the comparison with Example 1, it can be seen that when ethylene is supplied all at once, the ethylene conversion rate and the propane conversion rate tend to decrease with time.
  • Example 2 In the same manner as in Example 1, two small fixed bed reaction tubes (reaction tube 1 and reaction tube 2) were filled with catalyst A, and then each catalyst A was pretreated (heated at 600 ° C. for 2 hours). Subsequently, the two reaction tubes were connected in series in the order of reaction tubes 1 and 2 from the upstream side to the downstream side of the gas flow in the reaction tube, and 1-butene as a hydrocarbon was connected to the reaction tube 1 at 0 hour per hour. .64 g, nitrogen was supplied at a rate of 1.68 g / h, and water vapor was supplied at a rate of 0.51 g / h, and the temperature setting of each reaction tube was changed to 500 ° C.
  • Example 4 A 1-butene dehydrogenation reaction was carried out in the same manner as in Example 2 except that ethylene was supplied to the reaction tube 1 instead of from each connecting portion at a rate of 0.08 g per hour together with 1-butene, nitrogen and water vapor. It was. The results are shown in Table 6.

Landscapes

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

Abstract

L'invention vise à procurer un procédé de production d'un hydrocarbure insaturé par la réalisation d'une réaction de déshydrogénation d'un hydrocarbure, tout en alimentant de l'éthylène comme récepteur pour l'hydrogène produit, grâce auquel un hydrocarbure insaturé est produit à un rendement élevé pendant une longue période, tout en minimisant la perte de l'éthylène. L'invention concerne un procédé de production d'un hydrocarbure insaturé par la réalisation d'une réaction de déshydrogénation d'un hydrocarbure dans un réacteur qui a une première zone de réaction, une deuxième zone de réaction qui est ménagée en aval de la première zone de réaction, et une zone de connexion qui relie la première zone de réaction et la deuxième zone de réaction l'une avec l'autre. Ce procédé de production d'un hydrocarbure insaturé comprend : une étape dans laquelle un gaz contenant une matière de départ qui contient un hydrocarbure, est alimenté à la première zone de réaction et une réaction de déshydrogénation de l'hydrocarbure est effectuée, ce qui permet d'obtenir un produit primaire gazeux ; et une étape dans laquelle de l'éthylène est mélangé au produit primaire gazeux dans la zone de connexion et le gaz mixte ainsi obtenu est alimenté à la deuxième zone de réaction, ce qui permet de réaliser une réaction de déshydrogénation de l'hydrocarbure et une réaction de production d'éthane par l'ajout d'hydrogène à l'éthylène.
PCT/JP2015/059946 2014-03-31 2015-03-30 Procédé de production d'hydrocarbure insaturé Ceased WO2015152159A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016511885A JP6446033B2 (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
JP2014073070 2014-03-31
JP2014-073070 2014-03-31

Publications (1)

Publication Number Publication Date
WO2015152159A1 true WO2015152159A1 (fr) 2015-10-08

Family

ID=54240482

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/059946 Ceased WO2015152159A1 (fr) 2014-03-31 2015-03-30 Procédé de production d'hydrocarbure insaturé

Country Status (3)

Country Link
JP (1) JP6446033B2 (fr)
TW (1) TW201542513A (fr)
WO (1) WO2015152159A1 (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
KR20180065938A (ko) * 2016-12-08 2018-06-18 에보니크 데구사 게엠베하 올레핀-풍부 탄화수소 혼합물의 탈수소화
EP3197852B1 (fr) * 2014-09-23 2023-11-22 Borealis AG Processus de déshydrogénation catalytique de phase de gaz endothermique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008523013A (ja) * 2004-12-09 2008-07-03 ビーエーエスエフ ソシエタス・ヨーロピア プロパンからプロペンを製造する方法
JP2009531368A (ja) * 2006-03-29 2009-09-03 ビーエーエスエフ ソシエタス・ヨーロピア プロパンからプロペンを製造する方法
JP2009544746A (ja) * 2006-07-28 2009-12-17 ビーエーエスエフ ソシエタス・ヨーロピア 脱水素化される炭化水素の連続実施型不均一系触媒部分脱水素化の長期実施方法
JP2012512015A (ja) * 2008-12-18 2012-05-31 ティッセンクルップ 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 アルカン脱水素化用触媒のスズ含浸の変形
JP2012519685A (ja) * 2009-03-05 2012-08-30 ユーオーピー エルエルシー 炭化水素脱水素方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008523013A (ja) * 2004-12-09 2008-07-03 ビーエーエスエフ ソシエタス・ヨーロピア プロパンからプロペンを製造する方法
JP2009531368A (ja) * 2006-03-29 2009-09-03 ビーエーエスエフ ソシエタス・ヨーロピア プロパンからプロペンを製造する方法
JP2009544746A (ja) * 2006-07-28 2009-12-17 ビーエーエスエフ ソシエタス・ヨーロピア 脱水素化される炭化水素の連続実施型不均一系触媒部分脱水素化の長期実施方法
JP2012512015A (ja) * 2008-12-18 2012-05-31 ティッセンクルップ 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 アルカン脱水素化用触媒のスズ含浸の変形
JP2012519685A (ja) * 2009-03-05 2012-08-30 ユーオーピー エルエルシー 炭化水素脱水素方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3197852B1 (fr) * 2014-09-23 2023-11-22 Borealis AG Processus de déshydrogénation catalytique de phase de gaz endothermique
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
KR20180065938A (ko) * 2016-12-08 2018-06-18 에보니크 데구사 게엠베하 올레핀-풍부 탄화수소 혼합물의 탈수소화
JP2018095642A (ja) * 2016-12-08 2018-06-21 エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ オレフィン系炭化水素混合物の脱水素
KR102393017B1 (ko) 2016-12-08 2022-05-02 에보니크 오퍼레이션즈 게엠베하 올레핀-풍부 탄화수소 혼합물의 탈수소화

Also Published As

Publication number Publication date
JPWO2015152159A1 (ja) 2017-04-13
TW201542513A (zh) 2015-11-16
JP6446033B2 (ja) 2018-12-26

Similar Documents

Publication Publication Date Title
JP5828975B2 (ja) 触媒の再生
US7582805B2 (en) Supported catalyst for the selective hydrogenation of alkynes and dienes
JP6595606B2 (ja) オレフィンを製造するための触媒及びプロセス
JPS6238241A (ja) 化学方法および触媒
CN102123790A (zh) 用于烃的脱氢的催化剂
EP1874713A2 (fr) Procede d'hydrogenation selective d'acetylene en ethylene
CN107428635B (zh) 二烯的制造方法
TW201821159A (zh) 烴轉化製程
JP4335144B2 (ja) 低級オレフィンの製造方法
KR20230071120A (ko) 개질된 usy-제올라이트 탈수소화 촉매를 사용하는 파라핀계 나프타의 가공
JP6446033B2 (ja) 不飽和炭化水素の製造方法
EP3554688A1 (fr) Système de catalyseur pour conversion d'hydrocarbures
JP2018520858A (ja) 触媒及び当該触媒を利用した炭化水素転換プロセス
JP2018153769A (ja) 金属含有ゼオライト
CN1170632C (zh) 烃脱氢的催化剂和方法
JP6426711B2 (ja) 不飽和炭化水素の製造方法
KR102464447B1 (ko) 촉매 시스템 및 상기 촉매 시스템을 이용한 탄화수소 공급물의 전환 공정
JP6527364B2 (ja) ブタジエンを含む生成物の製造方法
CN110072616A (zh) 烃转化催化剂
JPH1033987A (ja) 芳香族炭化水素製造用触媒
JP2018521050A (ja) 炭化水素供給原料の転換方法
JP2022127708A (ja) ベンゼンの製造方法

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: 15772541

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016511885

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: 15772541

Country of ref document: EP

Kind code of ref document: A1