WO2021095782A1 - 触媒及びその製造方法、並びに不飽和炭化水素の製造方法 - Google Patents

触媒及びその製造方法、並びに不飽和炭化水素の製造方法 Download PDF

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WO2021095782A1
WO2021095782A1 PCT/JP2020/042127 JP2020042127W WO2021095782A1 WO 2021095782 A1 WO2021095782 A1 WO 2021095782A1 JP 2020042127 W JP2020042127 W JP 2020042127W WO 2021095782 A1 WO2021095782 A1 WO 2021095782A1
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catalyst
carbon
producing
alkane
transition metal
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English (en)
French (fr)
Japanese (ja)
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加藤　裕樹
二宮　航
杉山　茂
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Mitsubishi Chemical Corp
University of Tokushima NUC
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Mitsubishi Chemical Corp
University of Tokushima NUC
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Priority to CN202080079057.9A priority Critical patent/CN114728272B/zh
Priority to KR1020227015941A priority patent/KR102801354B1/ko
Priority to JP2021556132A priority patent/JP7582623B2/ja
Publication of WO2021095782A1 publication Critical patent/WO2021095782A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • 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
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • C07C11/09—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor

Definitions

  • the present invention relates to a catalyst, a method for producing the same, and a method for producing an unsaturated hydrocarbon.
  • a method for producing an alkene by dehydrogenating an alkane is generally known, and various catalysts for this dehydrogenation are being studied.
  • Patent Document 1 describes a dehydrogenation catalyst in which nickel and tin are supported on a composite carrier in which a specific amount of zinc oxide is supported on a specific ⁇ -alumina carrier. Then, an example is described in which isobutane is dehydrogenated to produce isobutylene (isobutene) using this dehydrogenation catalyst.
  • Patent Document 2 describes a catalyst in which zinc and a metal belonging to the VIIIA of the Periodic Table are supported on a specific zeolite carrier. A method for producing unsaturated hydrocarbons by dehydrogenating hydrocarbons in the presence of this catalyst is described. As an example, an example is described in which n-butane is dehydrogenated to produce butene (1-butene, 2-butene, isobutene) using this catalyst.
  • a surfactant is added after the step (a) of dispersing the silicate in water, the step (b) of adding the chromium element, and the step (a) or the step (b).
  • a method for producing an oxidative dehydrogenating catalyst which comprises a step (c) of heat-treating at a temperature of 50 to 150 ° C. for 1 to 20 hours and a step (d) of heat-treating at a temperature of 200 to 700 ° C. for 1 to 10 hours.
  • a method for producing an alkene from an alkane by contacting the obtained catalyst with a mixed gas containing an alkane and oxygen at a specific mixing ratio is described.
  • an example of producing isobutylene (isobutene) from isobutane using this catalyst is described.
  • Patent Document 4 describes that in the hydrocarbon conversion process, a pretreatment is performed on a catalyst in which a transition metal is supported on a carrier, but the pretreatment time is 30 to 90 minutes. It was short and could not suppress the aggregation of transition metals, and could not achieve a high selectivity.
  • an object of the present invention is to solve the problem in view of the above circumstances, that is, a catalyst capable of producing unsaturated hydrocarbons with a high selectivity in dehydrogenation of alkanes, a method for producing the same, and non-compliance.
  • the purpose is to provide a method for producing a saturated hydrocarbon.
  • a catalyst characterized in that a transition metal and carbon are supported on a carrier and the carbon contains fibrous carbon.
  • a method for producing a catalyst including Provided is a method for producing a catalyst, which forms and supports fibrous carbon by bringing a carbon-containing gas into contact with the catalyst precursor in the step of forming the catalyst.
  • a method for producing an unsaturated hydrocarbon in which the above catalyst is brought into contact with a mixed gas containing an alkane and carbon dioxide to produce an unsaturated hydrocarbon from the alkane.
  • a carbon-containing gas was brought into contact with the catalyst precursor on which the transition metal compound was supported on the carrier, carbon containing fibrous carbon was supported on the catalyst precursor, and the transition metal and carbon containing fibrous carbon were supported.
  • the present invention it is possible to provide a catalyst capable of producing an unsaturated hydrocarbon with a high selectivity in dehydrogenation of an alkane, a method for producing the same, and a method for producing an unsaturated hydrocarbon.
  • the catalyst according to the embodiment of the present invention is a catalyst in which carbon is supported on a carrier on which a transition metal is supported.
  • This catalyst is a solid catalyst that has catalytic activity in the reaction of forming unsaturated hydrocarbons by dehydrogenation of alkanes.
  • it is suitable as a catalyst for a reaction for forming an unsaturated hydrocarbon (preferably an alkene) by dehydrogenation of the alkane.
  • the carrier on which the transition metal and carbon are supported is not particularly limited, and for example, at least one selected from the group consisting of silica, alumina, zirconia, and titania can be used. One of these may be used alone or two or more thereof may be used in combination. Among these, alumina is preferable, and ⁇ -alumina is particularly preferable.
  • the particle size of the carrier can be appropriately selected, but it is preferable to adjust the particle size so that the pressure loss in the catalyst layer of the reactor (for example, the reaction tube) filled with the obtained catalyst does not become excessively large.
  • the particle size of the carrier is preferably as small as possible from the viewpoint of securing the surface area of the catalyst while suppressing the pressure loss in the catalyst layer, and when a mesh according to the Japanese Industrial Standards (JIS) is used, 3.5 mesh (opening). It is preferably 5.6 mm) or more, and particularly preferably 8.6 mesh (opening 2.0 mm) or more.
  • the fine particles are difficult to handle, and from the viewpoint of the influence on the reactivity due to the increase in pressure loss when filled in the reactor, it is preferably 635 mesh (opening 20 ⁇ m) or less, and 280 mesh (opening 20 ⁇ m). It is particularly preferably 53 ⁇ m) or less.
  • the catalyst according to the embodiment of the present invention can be filled in a reactor (for example, a reaction tube) in a powder state. At that time, it is preferable to adjust the particle size so that the pressure loss in the catalyst layer does not become excessively large.
  • the particle size of the catalyst is preferably as small as possible from the viewpoint of securing the surface area of the catalyst while suppressing the pressure loss in the catalyst layer.
  • the catalyst may be mixed with other materials or may be filled after molding from the viewpoint of suppressing the pressure loss in the catalyst layer.
  • a filler sica ball, alumina ball
  • alumina ball that is inert to the catalyst and does not deteriorate the catalyst performance can be used.
  • a binder that does not deteriorate the catalytic performance can be added to the obtained catalyst, kneaded, heated and fired.
  • the binder include silica-based, alumina-based, zirconia-based, and diatomaceous earth-based.
  • the shape after molding includes tablets, pellets, spheres, and extruded shapes. By molding, strength and handleability can be improved.
  • the transition metal carried on the carrier is at least selected from the group consisting of molybdenum, tungsten, chromium, nickel, iron, noble metals (Au, Ag, Pt, Pd, Rh, Ir, Ru, Os), vanadium, manganese, and zinc.
  • One type can be used, and a plurality of types may be used.
  • nickel (Ni) is preferable from the viewpoint of cost and catalytic performance.
  • the amount of the transition metal carried on the carrier is preferably 1.0% by mass or more and 30.0% by mass or less with respect to the carrier from the viewpoint of exhibiting good activity as a catalyst.
  • the amount of the transition metal carried on the carrier is preferably 1.0% by mass or more and 30.0% by mass or less with respect to the carrier from the viewpoint of exhibiting good activity as a catalyst.
  • the amount of the transition metal carried on the carrier is more preferably 3.0% by mass or more, further preferably 5.0% by mass or more, and 10.0% by mass or more. Is particularly preferable, and it is most preferably 15.0% by mass or more, while it is more preferably 28.0% by mass or less, further preferably 25.0% by mass or less, and 23.0% by mass. The following is particularly preferable.
  • the amount of the transition metal supported on the carrier can be measured by fluorescent X-ray analysis measurement.
  • the catalyst of this embodiment carries carbon including fibrous carbon in addition to the transition metal.
  • the conversion rate of alkanes and the selectivity of alkenes corresponding to the alkanes can be improved in the dehydrogenation reaction of alkanes. The reason for this is not clear, but the following reasons can be considered.
  • a normal metal-supported catalyst in general, as the reaction progresses, the metal particles on the carrier aggregate to become coarse particles, so that the reactivity decreases due to the decrease in the surface area of the active site, and the selectivity decreases due to the structural change of the active site. Is caused.
  • the presence of carbon containing fibrous carbon suppresses aggregation of transition metals due to heat or vibration during the reaction. Therefore, it is considered that a good active site can be maintained, and the selectivity of the alkane, the selectivity of the alkene corresponding to the alkane, and the selectivity of the unsaturated hydrocarbon are improved.
  • fibrous carbon carbon that extends in a fibrous form (carbon that exists in a so-called elongated shape) when observed with a scanning electron microscope (SEM) is referred to as fibrous carbon.
  • the cross-sectional shape of the fibrous carbon (the shape of the cross section perpendicular to the longitudinal direction) may be any of a circle, an ellipse, a triangle, a quadrangle, a polygon, etc. It may be. Further, the ratio of the length of fibrous carbon to the average diameter of the cross section is not particularly limited. Further, the fibrous carbon may be bent, linearly extended, or branched.
  • the amount of carbon containing fibrous carbon supported on the carrier is preferably 510% by mass or more and preferably 2500% by mass or less with respect to the supported transition metal. If the amount of carbon including fibrous carbon supported on the carrier is 550% by mass or more with respect to the supported transition metal, the effect of immobilizing the transition metal particles can be easily obtained, so that the transition metal during the reaction can be easily obtained. It becomes easier to suppress the aggregation of particles. As a result, the conversion rate of alkanes and the selectivity of alkenes corresponding to the alkanes can be increased.
  • the carbon supported on the carrier may contain fibrous carbon, and if the amount of carbon containing fibrous carbon is in such a range, the above-mentioned effect can be more sufficiently obtained.
  • the carbon supported on the carrier contains fibrous carbon (the presence of the fibrous carbon supported on the carrier). It is preferable that the observation image obtained by SEM is divided into 12 by a uniform lattice, and fibrous carbon is formed on the carrier to the extent that the presence of fibrous carbon can be confirmed in each lattice.
  • the amount of carbon including fibrous carbon supported on the carrier is 2500% by mass or less with respect to the supported transition metal, the transition metal particles are coated with an excess amount of carbon and hinder the catalytic activity. This can be further prevented, and the conversion rate of alkanes and the selectivity of alkenes corresponding to the alkanes can be increased.
  • the amount of carbon containing fibrous carbon supported on the carrier is more preferably 700% by mass or more, particularly preferably 1000% by mass or more, based on the supported transition metal. On the other hand, it is more preferably 2300% by mass or less, and particularly preferably 2000% by mass or less.
  • the amount of carbon including fibrous carbon supported on the carrier is raised to 1000 ° C. using simultaneous measurement of thermal weight and differential thermal (TG-DTA), and is supported from the weight reduction at that time. It is possible to measure the amount of carbon used. In the examples described later, since the weight loss when heated to 200 ° C. is due to the desorption of adsorbed water, the fiber carrying the weight loss amount in the heating process from 200 ° C. to 1000 ° C. Calculated as due to carbon containing carbon.
  • the fibrous carbon supported on the carrier on which the transition metal is supported preferably has an average diameter of 20 nm or more and 100 nm or less.
  • the average diameter of the fibrous carbon is 20 nm or more, the agglomeration of transition metal particles can be further prevented during the reaction, and the conversion rate of alkanes and the selectivity of alkenes corresponding to the alkanes can be further improved.
  • the average diameter of the fibrous carbon is 100 nm or less, the coating of the transition metal particles by the fibrous carbon can be further suppressed, and the decrease in catalytic activity tends to be easily prevented.
  • the average diameter of the fibrous carbon is more preferably 25 nm or more, particularly preferably 30 nm or more, while further preferably 95 nm or less, and particularly preferably 90 nm or less.
  • the average diameter of the fibrous carbon is defined as the portion where the observation image obtained by the scanning electron microscope (SEM) is divided into 12 by a uniform grid, and the diameter of the fibrous carbon is the largest in each grid. Then, the part having the smallest diameter is selected and used as the representative diameter value, and the average value of the representative diameter values of the fibrous carbon is used as the average diameter of the fibrous carbon.
  • the method for producing a catalyst according to the embodiment of the present invention includes a step of mixing a solution containing a transition metal compound and a carrier and heating to remove the catalyst to obtain a catalyst precursor, and a carbon-containing gas in the catalyst precursor. It has a step of contacting the catalyst to form a catalyst in which a transition metal and a carbon are supported. By contacting the catalyst precursor with a carbon-containing gas, fibrous carbon can be formed and supported.
  • the steps of obtaining the catalyst precursor include a step of mixing a solution in which a transition metal compound is dissolved and a carrier and heating to evaporate the solvent to obtain a solid, and a step of crushing the solid to obtain a powdery catalyst precursor.
  • the step of obtaining can be included.
  • a transition metal compound containing a transition metal to be supported is dissolved in a solution to prepare a solution, and a carrier is added to the solution to obtain a mixed solution containing the transition metal compound and the carrier.
  • a carrier is added to the solution to obtain a mixed solution containing the transition metal compound and the carrier.
  • the addition is a kind of mixing, but it means that it may be further mixed after the addition.
  • the carrier used in the step of obtaining the catalyst precursor at least one selected from the above-mentioned group consisting of silica, alumina, zirconia, and titania can be used.
  • alumina is preferable, and ⁇ -alumina is particularly preferable.
  • the mixed solution containing the transition metal compound and the carrier can be heated to evaporate the solvent to obtain a catalyst precursor in which the transition metal is supported on the carrier as a solid.
  • a powdery catalyst precursor By pulverizing the obtained catalyst precursor (solid), a powdery catalyst precursor can be obtained.
  • the obtained catalyst precursor can be dried, for example, at 20 ° C. or higher and 200 ° C. or lower, for example, for 1 hour or longer and 20 hours or shorter.
  • the temperature of this drying treatment is more preferably 60 ° C. or higher, further preferably 100 ° C. or higher, and more preferably 120 ° C. or lower.
  • the drying treatment time is more preferably 5 hours or more, while more preferably 15 hours or less.
  • the obtained catalyst precursor may be heat-treated (calcined) for, for example, 2 hours or more and 30 hours or less at a high temperature of 300 ° C. or higher and 1000 ° C. or lower.
  • the temperature of this heat treatment (calcination) is more preferably 400 ° C. or higher, while more preferably 800 ° C. or lower.
  • the heat treatment (calcination) time is more preferably 3 hours or more, while more preferably 12 hours or less.
  • the obtained powdery catalyst precursor can be filled into a reactor (for example, a reaction tube) in a powder state. At that time, it is preferable to adjust the particle size so that the pressure loss in the catalyst precursor phase does not become excessively large.
  • the particle size of the catalyst precursor is preferably as small as possible from the viewpoint of securing the surface area of the catalyst precursor while suppressing the pressure loss in the catalyst precursor phase.
  • the catalyst precursor may be mixed with other materials or may be filled after molding from the viewpoint of suppressing the pressure loss in the catalyst precursor phase.
  • a filler sica ball, alumina ball
  • alumina ball that is inert to the catalyst and does not deteriorate the catalyst performance can be used.
  • a binder that does not deteriorate the performance of the finally obtained catalyst can be added to the catalyst precursor, kneaded, heated and sintered.
  • the binder include silica-based, alumina-based, zirconia-based, and diatomaceous earth-based.
  • the shape after molding includes tablets, pellets, spheres, and extruded shapes. By molding, strength and handleability can be improved.
  • the carbon-containing gas is brought into contact with the obtained catalyst precursor. As a result, it is carbonized by the oxidation reaction of the carbon-containing gas.
  • the transition metal transition metal oxide
  • carbon was supported at the same time as the reduction of the transition metal oxide, and the transition metal and carbon were supported.
  • a catalyst catalyst for alcan dehydrogenation
  • carbon is generated between the transition metal oxides during the reduction of the transition metal oxide, and aggregation of the transition metal crystallites can be suppressed. ..
  • the crystallite diameter of the transition metal supported on (the carrier) of the catalyst is the ratio of the crystallite diameter of the transition metal after contact with the carbon-containing gas to the crystallite diameter when the carbon-containing gas is not brought into contact, or on the carrier.
  • the ratio of the crystallite diameter of the transition metal when it contains fibrous carbon to the crystal particle size of the transition metal supported on the carrier when the supported carbon does not contain fibrous carbon is 0. It is preferably .80 or less, more preferably more than 0.00, preferably 0.60 or less, and further preferably 0.20 or more and 0.50 or less. The conditions shown below can be adjusted as appropriate so as to fall within this range.
  • the powder X-ray analysis measurement of the catalyst is performed, and the peak attributable to the transition metal crystallite is calculated from the obtained result from Scherrer's equation. It is possible.
  • SmartLab / R / INP / DX manufactured by Rigaku Co., Ltd.
  • the measurement conditions were Cu-K ⁇ ray as an X-ray source, a tube voltage of 45 kV, and a tube current of 150 mA.
  • the standard for the ratio of the crystallite diameter of the transition metal supported on the catalyst (carrier) is the crystallite diameter of the transition metal when the carbon-containing gas is not brought into contact with the catalyst precursor, or the supported carbon. It can be the crystal particle size of the transition metal supported on the carrier when it does not contain fibrous carbon.
  • the crystallite diameter as such a reference is preferably the crystallite diameter of the transition metal when the catalyst precursor is subjected to hydrogen reduction treatment (contact with a pretreatment gas containing hydrogen that does not contain carbon-containing gas). ..
  • hydrogen reduction treatment contact with a pretreatment gas containing hydrogen that does not contain carbon-containing gas.
  • This carbon-containing gas preferably contains a hydrocarbon as a carbon source (carbon source) to be supported on the catalyst precursor.
  • a hydrocarbon as a carbon source (carbon source) to be supported on the catalyst precursor.
  • a hydrocarbon an alkane having 2 to 5 carbon atoms is preferable.
  • alkanes having 2 to 5 carbon atoms include ethane, propane, n-butane, isobutane, n-pentane, and isopentane. These may be used alone or in admixture of two or more.
  • the raw materials may be different hydrocarbons or the same hydrocarbons, but the same hydrocarbons are preferable from the viewpoint of simplifying the process.
  • the carbon source and the alkane raw material the above-mentioned alkane having 2 to 5 carbon atoms (for example, ethane, propane, n-butane, isobutane, n-pentane, isopentane) is preferable, and isobutane is more preferable.
  • This carbon-containing gas may contain an inert gas such as helium or nitrogen in addition to the carbon source.
  • the concentration of the carbon source (preferably hydrocarbon) contained in the carbon-containing gas is preferably 1% by volume or more and 30% by volume or less, and 5% by volume in particular. The above is particularly preferable, while 20% by volume or less is particularly preferable.
  • concentration of the carbon source is 1% by volume or more, a sufficient amount of carbon can be supported better, and the selectivity of unsaturated hydrocarbons can be further increased.
  • concentration of the carbon source is 30% by volume or less, the support of excess carbon can be more easily controlled, and the decrease in the alkane conversion rate and the selectivity of unsaturated hydrocarbons can be more sufficiently suppressed. ..
  • the temperature in the step of supporting carbon on the catalyst precursor is preferably 300 ° C. or higher and 1000 ° C. or lower, and above all, 400 ° C. or higher. On the other hand, it is more preferably 700 ° C. or lower, and particularly preferably 600 ° C. or lower.
  • the temperature of this carbon supporting step is 300 ° C. or higher, a more sufficient carbon supporting amount can be obtained.
  • the temperature of this carbon supporting step is 1000 ° C. or lower, it is possible to more sufficiently suppress a decrease in the amount of carbon supported and a decrease in catalytic activity due to the thermal decomposition reaction of the carbon source alkane.
  • the pressure in the step of supporting carbon on the catalyst precursor can be appropriately selected depending on the type of carbon-containing gas used, but is 0.01 MPa or more and 1 MPa or more. The following is preferable.
  • By setting the pressure to 0.01 MPa or more it is possible to easily suppress the desorption of components on the carrier under reduced pressure.
  • Further, by setting the pressure to 1 MPa or less an increase in reactivity due to pressurization can be more sufficiently prevented, and an excessive amount of carbon supported on the carrier can be prevented.
  • it is more preferably 0.8 MPa or less, particularly preferably 0.5 MPa or less, and further preferably 0.05 MPa or more.
  • the pressure may be atmospheric pressure (0.101 MPa).
  • a fixed-bed flow type reaction method in which the carbon-containing gas is circulated in a reactor (for example, a reaction tube) filled with the catalyst precursor can be used.
  • the W / F when the carbon-containing gas is brought into contact with the catalyst precursor is preferably 0.03 g ⁇ min / ml or more and 0.5 g ⁇ min / ml or less.
  • W is the mass (g) of the catalyst precursor filled in the reaction tube
  • F is the flow rate (ml / min) of the carbon-containing gas to be circulated in the reaction tube filled with the catalyst precursor. That is, W / F is the mass of the catalyst precursor filled in the reaction tube with respect to the flow rate of the carbon-containing gas flowing in the reactor, and is represented by the following formula.
  • W / F (Amount of catalyst precursor filled in the reaction tube [g]) / (Flow rate of carbon-containing gas flowing in the reaction tube [ml / min])
  • the W / F is particularly preferably 0.05 g ⁇ min / ml or more, while it is particularly preferably 0.2 g ⁇ min / ml or less.
  • the catalyst according to the present invention is brought into contact with a mixed gas containing alkane and carbon dioxide (hereinafter, also appropriately referred to as “reaction gas”), and the unsaturated hydrocarbon is derived from the alkane.
  • reaction gas a mixed gas containing alkane and carbon dioxide
  • the alkane raw material used for the dehydrogenation reaction of alkane is not particularly limited, but an alkane having 2 to 5 carbon atoms is preferable. When the number of carbon atoms is 5 or less, it is possible to suppress the generation of low carbon number by-products due to the decomposition reaction.
  • alkanes having 2 to 5 carbon atoms include ethane, propane, n-butane, isobutane, n-pentane, and isopentane. These may be used alone or in admixture of two or more.
  • the dehydrogenation reaction mainly produces ethylene from ethane, propylene from propane, butadiene from n-butane, isobutene from isobutane, pentene from n-pentane, and isoprene from isopentane.
  • the above-mentioned dehydrogenation reaction of alkane is performed to produce the corresponding unsaturated hydrocarbon.
  • This dehydrogenation reaction is carried out by bringing a mixed gas (reaction gas) containing alkane and carbon dioxide into contact with the catalyst according to the present invention.
  • the molar ratio of carbon dioxide to alkane contained in this mixed gas (reaction gas) is preferably 0.1 or more and 1.9 or less, and more preferably 0.25 or more, while 1. It is more preferably 6 or less.
  • this molar ratio is less than 0.1, the concentration of carbon dioxide is low, so that the reactivity tends to decrease.
  • this molar ratio is larger than 1.9, the concentration of carbon dioxide is high, so that the selectivity tends to decrease.
  • This mixed gas may contain an inert gas such as helium or nitrogen, water vapor (water), methane, hydrogen or the like as long as the effect of the present invention is not impaired, in addition to alkane and carbon dioxide.
  • an inert gas such as helium or nitrogen, water vapor (water), methane, hydrogen or the like as long as the effect of the present invention is not impaired, in addition to alkane and carbon dioxide.
  • the concentration of alkane in this mixed gas is preferably 1% by volume or more and 30% by volume or less, more preferably 1% by volume or more, further preferably 5% by volume or more, and 20% by volume. % Or less is more preferable.
  • concentration of alkane is 1% by volume or more, it is possible to further suppress the decrease in selectivity of unsaturated hydrocarbon due to the improvement of the conversion rate of alkane. Further, when the concentration of alkane is 30% by volume or less, the decrease in the conversion rate of alkane can be further suppressed.
  • the temperature of the dehydrogenation reaction of the alkane (the temperature at which the mixed gas is brought into contact with the catalyst) is preferably 300 ° C. or higher and 1000 ° C. or lower, more preferably 400 ° C. or higher, and more preferably 700 ° C. or lower. 600 ° C. or lower is more preferable.
  • the temperature of this dehydrogenation reaction is 300 ° C. or higher, more sufficient catalytic activity can be obtained.
  • the temperature of this dehydrogenation reaction is 1000 ° C. or lower, it is possible to further suppress a decrease in selectivity of unsaturated hydrocarbon and a decrease in catalytic activity due to a thermal decomposition reaction of alkane.
  • the pressure in the dehydrogenation reaction of alkanes can be appropriately selected depending on the type of alkane used in the reaction, but it can usually be set to 1 MPa or less, preferably 0.01 MPa or more and 1 MPa or less. Among these, the pressure is more preferably 0.8 MPa or less, further preferably 0.5 MPa or less, while more preferably 0.05 MPa or more, further preferably 0.1 MPa or more.
  • the pressure may be atmospheric pressure (0.101 MPa). By setting the pressure to 0.01 MPa or more, the active site on the catalyst and the alkane are more appropriately contacted during the reaction, and the selectivity of the alkane is likely to be improved.
  • the runaway reaction caused by the excessive contact of the alkane in the reaction gas and the generated unsaturated hydrocarbon with the active site on the catalyst can be further suppressed, and the corresponding alkene can be further suppressed. Can increase the selectivity of.
  • the reaction form used in the method for producing unsaturated hydrocarbons according to the embodiment of the present invention is not particularly limited, and the usual form used for the catalytic reaction can be adopted.
  • reaction types such as fixed beds, moving beds, and fluidized beds can be mentioned.
  • the fixed floor method can be preferably adopted because the apparatus is relatively simple and the process design is easy. That is, in the method for producing an unsaturated hydrocarbon according to the embodiment of the present invention, the dehydrogenation reaction of alkanes is carried out by mixing a reactor (for example, a reaction tube) filled with a catalyst according to the present invention containing raw materials such as alkanes and carbon dioxide. It can be carried out by a fixed bed flow type reaction method in which gas (reaction gas) is circulated.
  • the W / F in the dehydrogenation reaction of alkanes is preferably 0.001 g ⁇ min / ml or more and 1000 g ⁇ min / ml or less.
  • the W / F is more preferably 0.01 g ⁇ min / ml or more, and more preferably 100 g ⁇ min / ml or less.
  • W is the mass (g) of the catalyst filled in the reaction tube
  • F is the flow rate (ml / min) of the mixed gas (reaction gas) containing alcan and carbon dioxide to be distributed in the reaction tube filled with the catalyst.
  • W / F is the mass of the catalyst filled in the reaction tube with respect to the flow rate of the mixed gas (reaction gas) flowing in the reaction tube, and is represented by the following formula.
  • W / F (Amount of catalyst filled in the reaction tube [g]) / (Flow rate of mixed gas flowing in the reaction tube [ml / min])
  • the reaction time of the alkane with the catalyst can be further secured, and the conversion rate of the alkane can be improved.
  • the W / F is 1000 g ⁇ min / ml or less, it is possible to further prevent the reaction time of the alkane with the catalyst from becoming excessive, and the produced alkene reacts on the catalyst to carbon dioxide. It is possible to prevent a decrease in the selectivity due to the above.
  • a catalyst Ni—C / ⁇ -Al 2 O 3 catalyst
  • Nickel nitrate hexahydrate (Wako Pure Chemical Industries, Ltd.) was added in an amount of 3.89 parts by mass and dissolved in 15 parts by mass of water so that the amount of Ni charged with respect to ⁇ -Al 2 O 3 was 20% by mass.
  • ⁇ -Al 2 O 3 (Nippon Light Metal Co., Ltd.) was added to this aqueous solution and mixed. The mixture was then heated to evaporate the water to give a solid.
  • the obtained solid was pulverized and vacuum dried at 110 ° C. for 12 hours.
  • the pulverized solid was further calcined at 550 ° C. for 1 hour (heating rate 1 ° C./min).
  • the obtained solid was pulverized again to obtain a powdery catalyst precursor 1 (nickel-supported ⁇ -Al 2 O 3 ).
  • the obtained catalyst precursor 1 was packed in a quartz reaction tube having a diameter of 9 mm and a length of 35 mm installed in a fixed-bed circulation type reactor, and heated to 550 ° C. while circulating helium. Then, each condition was set so that the W / F of the pretreatment gas containing 85.8% by volume of helium and 14.2% by volume of isobutane was 0.12 g ⁇ min / ml. In this way, the pretreatment gas was circulated in the reaction tube for 3 hours to obtain a Ni—C / ⁇ -Al 2 O 3 catalyst in which carbon was supported on the catalyst precursor 1. In addition, powder X-ray analysis measurement of the obtained catalyst (Ni—C / ⁇ -Al 2 O 3 catalyst) was performed.
  • isobutene was produced from isobutane as follows. With the catalyst obtained as described above filled in the reaction tube as it was, a reaction gas adjusted to 73.7% by volume of helium, 14.2% by volume of isobutane, and 12.1% by volume of carbon dioxide was circulated. At that time, each condition was set so that the W / F was 0.017 g ⁇ min / ml. The reaction tube outlet gas 6 hours after the start of the reaction gas flow was measured by gas chromatography to determine the isobutane conversion rate, isobutene selectivity and isobutene yield. The results are shown in Table 1.
  • W / F Amount of catalyst precursor or catalyst filled in the reaction tube (g) / Supply rate of carbon-containing gas or reaction gas supplied into the reaction tube (ml / min)
  • the isobutane conversion rate, isobutene selectivity and isobutene yield are represented by the following formulas.
  • Isobutane conversion rate (%) (number of moles of reacted isobutane) / (number of moles of supplied isobutane)
  • Isobutene selectivity (%) (number of moles of produced isobutane) / (number of moles of reacted isobutane)
  • Isobutene yield (%) (number of moles of produced isobutane) / (number of moles of supplied isobutane)
  • Example 2 A catalyst (Ni—C / ⁇ -Al 2 O 3 catalyst) was prepared by the same method as in Example 1 except that the flow time of the pretreatment gas was changed to 5 hours, and subsequently, the same method as in Example 1. Isobutene was produced in the above. Further, the obtained catalyst (Ni-C / ⁇ -Al 2 O 3 catalyst) was heated to 1000 ° C. using simultaneous thermogravimetric and differential thermal measurement (TG-DTA), and was supported from the weight reduction at that time. The amount of carbon used was measured. In the weight change at this time, since the weight loss when heated to 200 ° C. was due to the desorption of adsorbed water, the carbon carrying the weight loss amount in the heating process from 200 ° C.
  • TG-DTA simultaneous thermogravimetric and differential thermal measurement
  • Example 3 A catalyst (Ni—C / ⁇ -Al 2 O 3 catalyst) was prepared by the same method as in Example 1 except that the flow time of the pretreatment gas was changed to 7 hours, and subsequently, the same method as in Example 1. Isobutene was produced in the above. The results are shown in Table 1.
  • Example 1 A Ni / ⁇ -Al 2 O 3 catalyst was produced by the same method as in Example 1 except that the pretreatment gas was not circulated, and then isobutylene was produced by the same method as in Example 1. The results are shown in Table 1.
  • Example 2 Change the pretreatment gas to a gas containing 80.0% by volume of helium and 20.0% by volume of hydrogen, set the W / F to 0.0042 g ⁇ min / ml, and set the flow time of the pretreatment gas to 1 hour.
  • a Ni / ⁇ -Al 2 O 3 catalyst was produced by the same method as in Example 1 except that each condition was changed, and then isobutene was produced by the same method as in Example 1. The results are shown in Table 1.
  • Example 4 A Ni / ⁇ -Al 2 O 3 catalyst was prepared by the same method as in Example 1 except that the flow time of the pretreatment gas was changed to 1 hour, and then isobutylene was produced by the same method as in Example 1. went. The results are shown in Table 1.

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JP2013509290A (ja) * 2009-10-29 2013-03-14 インフラ・テクノロジーズ・リミテッド Ｃｏおよびｈ２から炭化水素を合成するための触媒およびその製造方法
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