JP2016074622A - Diene production process and dehydrogenation catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a diene production process in which diene can be produced with a high selectivity by the dehydrogenation of a hydrocarbon compound.SOLUTION: The diene production process according to one aspect of the present invention includes a step for bringing a hydrocarbon compound and a dehydrogenation catalyst into contact to dehydrogenate the hydrocarbon compound, and in which the dehydrogenation catalyst has a carrier comprising a faujasite type zeolite, and a periodic table Group 10 element supported on the carrier.SELECTED DRAWING: None

Description

  The present invention relates to a process for producing a diene and a dehydrogenation catalyst.

  Dienes such as butadiene are extremely useful as basic raw materials in the petrochemical industry.

  As a method for producing a diene, a method is known in which a hydrocarbon compound and a dehydrogenation catalyst are brought into contact with each other to dehydrogenate the hydrocarbon compound.

Conventionally, as a dehydrogenation catalyst, for example, a catalyst containing chromium oxide, a catalyst containing platinum-tin, a catalyst containing platinum-zinc, a catalyst containing iron, and the like are known (for example, non-patent documents). 1-4). Moreover, as the catalyst containing platinum-tin, catalysts using alumina or ZnAl ₂ O ₄ as a carrier are known (see, for example, Non-Patent Documents 3 and 4). Catalysts having zeolite as a support are also known (see Patent Documents 1 to 5 below).

Japanese Patent Laid-Open No. 2-78439 US4433190 Specification US6197717 specification US6555724 Specification US Pat. No. 5,114,565

Catal. Today, 1999, 51, 223. Applied Catalysis, A: General, 2012, 417-418, 306. Kinetics and Catalysis, 2001, 42, 72. Catalysis Today, 2011, 164, 214.

  However, a sufficient diene selectivity cannot be obtained by dehydrogenation of a hydrocarbon compound using the conventional dehydrogenation catalyst.

  The present invention has been made in view of the above problems, and provides a method for producing a diene capable of producing a diene with high selectivity by dehydrogenation of a hydrocarbon compound, and a dehydrogenation catalyst used in the production method. The purpose is to do.

  A method for producing a diene according to one aspect of the present invention includes a step of bringing a hydrocarbon compound and a dehydrogenation catalyst into contact with each other to dehydrogenate the hydrocarbon compound, wherein the dehydrogenation catalyst includes a faujasite type zeolite. And a periodic table Group 10 element supported on a carrier.

  In the method for producing diene according to one aspect of the present invention, the Group 10 element of the periodic table may be Pt (platinum).

  In the method for producing diene according to one aspect of the present invention, at least one element selected from the group consisting of Group 6 elements of the periodic table, Group 8 elements of the periodic table, and lanthanoids may be supported on the carrier.

  In the method for producing diene according to one aspect of the present invention, Cr (chromium) may be supported on a carrier as a Group 6 element of the periodic table.

  In the method for producing diene according to one aspect of the present invention, Fe (iron) may be supported on a carrier as a Group 8 element of the periodic table.

  In the method for producing diene according to one aspect of the present invention, Ce (cerium) may be supported on a carrier as a lanthanoid.

  In the method for producing diene according to one aspect of the present invention, the Fe content may be 0.50 to 5.20% by mass based on the total mass of the dehydrogenation catalyst.

In the method for producing a diene according to one aspect of the present invention, the ratio _n Pt _{/ n Fe} molar number _{n Pt} of Pt to moles _{n Fe} of Fe may be 0.01-0.20.

  In the diene production method according to one aspect of the present invention, the faujasite type zeolite may be a Y type zeolite.

  In the diene production method according to one aspect of the present invention, the faujasite type zeolite may be a NaY type zeolite.

  In the method for producing diene according to one aspect of the present invention, the hydrocarbon compound may contain butane and / or butene.

  A dehydrogenation catalyst according to one aspect of the present invention is a dehydrogenation catalyst for generating a diene by dehydrogenation of a hydrocarbon compound, a carrier containing a faujasite type zeolite, and a periodic table group 10 carried on the carrier. And having elements.

  In the dehydrogenation catalyst according to one aspect of the present invention, at least one element selected from the group consisting of Group 6 elements of the periodic table, Group 8 elements of the periodic table, and lanthanoids may be supported on the support.

  In the dehydrogenation catalyst according to one aspect of the present invention, Fe is supported on the support as the Group 8 element of the periodic table, and the Fe content is 0.50 to the total mass of the dehydrogenation catalyst. It may be 5.20% by mass.

In the dehydrogenation catalyst in accordance with one aspect of the present invention, a Group 10 element of the Periodic Table is Pt, the ratio _n Pt _{/ n Fe} molar number _{n Pt} of Pt to moles _{n Fe} of Fe 0.01 to 0 .2 may be used.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the diene which can manufacture a diene with high selectivity by dehydrogenation of a hydrocarbon compound, and the dehydrogenation catalyst used in the said manufacturing method are provided.

  Hereinafter, a preferred embodiment of the present invention will be described. However, the present invention is not limited to the following embodiments.

  The manufacturing method of the diene which concerns on this embodiment is equipped with the process of making a hydrocarbon compound and a dehydrogenation catalyst contact, and dehydrogenating a hydrocarbon compound.

According to the method for producing a diene according to this embodiment, a side reaction accompanying dehydrogenation of a hydrocarbon compound (hereinafter, sometimes referred to as “dehydrogenation reaction”) can be suppressed. As a result, the hydrocarbon compound can be selectively converted to the corresponding diene. That is, the diene selectivity can be improved. The diene selectivity may be defined, for example, by Equation 1 below.
R _S = {m ₂ / (m ₀ −m ₁ )} × 100 (1)
R _S in Formula 1 is the diene selectivity (mol%). m ₀ is the number of moles of the hydrocarbon compound as the raw material. m ₁ is the number of moles of the raw material (unreacted hydrocarbon compound) remaining in the product of the dehydrogenation reaction. m ₂ is the number of moles of diene contained in the product.

Moreover, according to the manufacturing method of the diene which concerns on this embodiment, there exists a tendency for progress of a dehydrogenation reaction to be accelerated | stimulated. That is, the conversion rate of the hydrocarbon compound tends to improve, and the yield of diene tends to improve. The conversion rate of the hydrocarbon compound may be defined by the following formula 2, for example. The yield of diene may be defined, for example, by the following formula 3.
R _C = {1- (m ₁ / m ₀ )} × 100 (2)
R _Y = (m ₂ / m ₀ ) × 100 (3)
_RC in Formula 2 is the conversion rate (mol%) of the hydrocarbon compound. R _Y in Formula 3 is the diene yield (mol%).

  The carbon number of the hydrocarbon compound may be the same as the carbon number of the target diene. That is, it may be a hydrocarbon compound obtained when a double bond existing in a diene assumed as a product is hydrogenated. The hydrocarbon compound may have 3 to 10 carbon atoms, 4 to 10 carbon atoms, or 4 to 6 carbon atoms.

  The hydrocarbon compound may be, for example, a chain saturated aliphatic hydrocarbon or a structural isomer thereof. The hydrocarbon compound may be, for example, a chain-like unsaturated aliphatic hydrocarbon or a structural isomer thereof. The hydrocarbon compound may be, for example, a cyclic hydrocarbon or a structural isomer thereof. The chain saturated aliphatic hydrocarbon may be at least one selected from the group consisting of propane, butane, pentane, hexane, heptane, octane and decane, for example. The chain unsaturated aliphatic hydrocarbon may be at least one selected from the group consisting of propylene, butene, pentene, hexene, heptene, octene and decene, for example. The cyclic hydrocarbon may be at least one selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, cyclooctane and cyclodecane, for example. More specifically, the linear hydrocarbon compound is n-butane, n-butene, n-pentane, n-pentene, n-hexane, n-hexene, n-heptane, n-heptene, n-octane. , N-octene, n-decane and n-decene. The branched hydrocarbon compounds are isobutane, isobutene, isopentane, isopentene, 2-methylpentane, 2-methylpentene, 3-methylpentane, 3-methylpentene, 2,3-dimethylpentane, 2,3-dimethylpentene, It may be at least one selected from the group consisting of isoheptane, isooctane, isooctene, isodecane and isodecene.

  The hydrocarbon compound may have a substituent containing a hetero atom such as oxygen, nitrogen, halogen, or sulfur. Such substituents include, for example, halogen atoms (—F, —Cl, —Br, —I), hydroxyl groups (—OH), alkoxy groups (—OR), carboxyl groups (—COOH), ester groups (—COOR). ), An aldehyde group (—CHO) or an acyl group (—C (═O) R).

  In the method for producing a diene according to this embodiment, one of the above hydrocarbon compounds may be used alone, or two or more hydrocarbon compounds may be mixed and used in an arbitrary amount. For example, it may be a fraction containing butane obtained after separating butadiene and butene from a C4 fraction obtained in a naphtha pyrolysis furnace or a naphtha catalytic cracking furnace. It may be a fraction containing butane and butene obtained after separating butadiene from the C4 fraction. It may be a fraction containing pentane obtained after separating isoprene and pentene from a C5 fraction obtained in a naphtha pyrolysis furnace or a naphtha catalytic cracking furnace. It may be a fraction containing pentane and pentene obtained after separating isoprene from the C5 fraction. It may be LPG gas that is easily available as fuel. LPG gas is a mixture of propane, n-butane and isobutane. When a mixture containing a plurality of types of hydrocarbon compounds is used, the diene can be separated and purified after dehydrogenation. Separation and purification may be performed by known methods.

  The diene raw material may contain other components in addition to the hydrocarbon compound. The other component may be at least one selected from the group consisting of alcohols, ethers, and biofuels, for example.

  The diene raw material may contain impurities in addition to the hydrocarbon compound as long as the effects of the present invention are not impaired. The impurity may be at least one selected from the group consisting of hydrogen, carbon monoxide, carbon dioxide, methane, and dienes.

  The diene produced by dehydrogenation of the hydrocarbon compound is, for example, at least one selected from the group consisting of 1,3-butadiene, piperylene, isoprene, 1,5-hexadiene, 1,6-octadiene and 1,9-decadiene. It may be. Specifically, butadiene is easily obtained when butane or butene is used as the hydrocarbon compound. Piperylene is easily obtained when pentane or pentene is used as the hydrocarbon compound. Isoprene is easily obtained when isopentane or isopentene is used as the hydrocarbon compound. Dienes such as butadiene, piperylene and isoprene are industrially useful. In addition, according to the method for producing a diene according to the present embodiment, a thermodynamically stable conjugated diene is easily obtained.

  When butane and / or butene is used as the hydrocarbon compound, that is, when butadiene is produced, the effect of the present invention tends to be remarkable.

  Butadiene is a typical diene, and is used as a raw material for synthetic rubber such as SBR (styrene butadiene rubber) and NBR (acrylonitrile butadiene rubber), and as a raw material for ABS (acrylonitrile butadiene styrene) resin.

  Butadiene is usually produced by pyrolysis (cracking) of a hydrocarbon mixture such as naphtha. In such a production method, not only butadiene but also other by-products (for example, a large amount of ethylene or propylene) are obtained. Therefore, high selectivity of butadiene cannot be expected in the pyrolysis of hydrocarbon mixtures. For these reasons, a method for selectively producing only butadiene, such as a dehydrogenation method, has been desired. However, the dehydrogenation of n-butane or n-butene using a conventional dehydrogenation catalyst has a low butadiene selectivity. On the other hand, according to the production method according to the present embodiment, the production of by-products as described above can be suppressed, and butadiene can be produced with high selectivity.

  The dehydrogenation catalyst according to the present embodiment has a support containing faujasite type zeolite and a periodic table Group 10 element supported on the support. Here, the periodic table refers to a periodic table of long-period elements based on the provisions of IUPAC (International Pure Applied Chemistry Association). The faujasite-type zeolite is a zeolite represented by the FAU structure in the framework structure type in accordance with the IUPAC recommendation. The carrier may consist only of faujasite type zeolite. In addition to the faujasite type zeolite, the carrier may contain, for example, at least one selected from the group consisting of zeolites other than silica, alumina, silica-alumina, activated carbon, and faujasite type zeolite.

  The faujasite type zeolite has pores whose diameter is approximately the same as the size of a low molecular weight molecule, and therefore acts as a molecular sieve. Further, since the faujasite type zeolite is a solid acid, only specific molecules smaller than the pore diameter can be selectively adsorbed. The reason why the diene selectivity is improved by using the faujasite type zeolite is not clear. The present inventors consider that because a faujasite type zeolite has pores having a specific diameter, a specific hydrocarbon compound is likely to be selectively adsorbed to the pores. Further, the present inventors consider that the adsorbed hydrocarbon compound is easy to move in the pores of the faujasite type zeolite, and that the dehydrogenation reaction is likely to occur in the pores. For these reasons, the inventors speculate that the diene selectivity is improved.

The faujasite type zeolite is selected from the group consisting of H type, NH ₄ type, Na type, Li type, K type, Rb type, Cs type, Be type, Mg type, Ca type, Sr type, and Ba type. It may be at least one kind. Any type of these faujasite type zeolites can be used. The faujasite type zeolite is, for example, HY type zeolite, NH ₄ Y type zeolite, NaY type zeolite, LiY type zeolite, KY type zeolite, RbY type zeolite, CsY type zeolite, BeY type zeolite, MgY type zeolite, CaY type zeolite. , SrY zeolite, BaY zeolite, HX zeolite, NH ₄ X zeolite, NaX zeolite, LiX zeolite, KX zeolite, RbX zeolite, CsX zeolite, BeX zeolite, MgX zeolite, CaX zeolite , SrX type zeolite, and BaX type zeolite. Any type of these faujasite type zeolites can be used. The NaX type zeolite may be, for example, a faujasite type zeolite containing Na as a metal element (cation) and having a silica alumina ratio of more than 2 and less than 3. The NaY type zeolite may be, for example, a faujasite type zeolite containing Na as a metal element (cation) and having a silica alumina ratio of 3 or more. Among the faujasite-type zeolites, when NaY-type zeolite is used as the carrier, the diene selectivity tends to be further improved. “The faujasite type zeolite is H type, NH ₄ type, Na type, Li type, K type, Rb type, Cs type, Be type, Mg type, Ca type, Sr type, Ba type, etc.” Is a faujasite type zeolite at a point before a specific element such as a group 10 element of the periodic table to be described later is supported, H type, NH ₄ type, Na type, Li type, K type, Rb type, Cs It means that it is a type, Be type, Mg type, Ca type, Sr type, Ba type or the like. Therefore, in the dehydrogenation catalyst according to the present embodiment, cations (H ⁺ , NH ₄ ⁺ , Na ⁺ , Li ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Be ²⁺ , Mg ²⁺ , which the faujasite type zeolite has, Part or all of Ca ²⁺ , Sr ²⁺ , Ba ^2+, etc.) may be substituted with the specific element.

  In preparing the dehydrogenation catalyst, one of the above-mentioned faujasite type zeolites may be used alone, or two or more types of faujasite type zeolites may be used in combination.

The silica alumina ratio in the faujasite type zeolite is not particularly limited. The silica-alumina ratio, the number of moles of SiO ₂ constituting the zeolite _([SiO 2]), the ratio of the moles of _Al 2 _{O 3} constituting the zeolite _{([Al 2 O 3])} ([SiO 2] / [Al ₂ O ₃ ]). The silica alumina ratio may be 50 or less, for example, or 10 or less. When the silica-alumina ratio is in such a range, the diene selectivity tends to be further improved. The silica-alumina ratio can be adjusted, for example, by setting the ratio of Si and Al in the faujasite-type zeolite raw material or the ratio of silica and alumina in the raw material. Specifically, when preparing the faujasite type zeolite, the concentration of the aqueous solution in which the elements constituting the faujasite type zeolite are dissolved may be adjusted.

  The Group 10 element of the periodic table supported on the carrier may be at least one selected from the group consisting of nickel (Ni), palladium (Pd), and platinum (Pt), for example. Moreover, the combination of these elements may be sufficient. When Pt is supported on the carrier, the diene selectivity tends to be improved. Further, when Pt is supported on a carrier, the activity of the dehydrogenation catalyst is likely to be improved, and high activity tends to be maintained over a long period of time.

  The content of Group 10 element in the periodic table in the dehydrogenation catalyst is 0.10 to 5.00% by mass, 0.10 to 1.00% by mass, and 0.10 to 0.50% by mass based on the total mass of the catalyst. %, 0.10 to 0.40 mass%, 0.36 to 0.50 mass%, or 0.36 to 0.40 mass%. When content is 0.10 mass% or more, there exists a tendency for the selectivity of a diene to improve more. In addition, the catalytic activity in the dehydrogenation reaction is likely to improve, and high catalytic activity tends to be maintained over a long period of time. When the content is more than 5.00% by mass, it is difficult to obtain the effect of improving the selectivity of the diene and the effect of improving the catalytic activity just commensurate with the content. The content of the Group 10 element of the periodic table may be measured by inductively coupled plasma emission spectroscopy (ICP emission spectroscopy).

  The method for supporting the Group 10 element of the periodic table on the carrier is not particularly limited, and may be, for example, an impregnation method, a deposition method, a coprecipitation method, a kneading method, an ion exchange method, or a pore filling method. Here, the ion exchange method means substituting part or all of the elements constituting the carrier with Group 10 elements of the periodic table. According to the ion exchange method, the Group 10 elements of the periodic table are easily supported on the carrier in a uniform and highly dispersed manner.

  The method of ion exchange is not particularly limited. For example, ion exchange may be performed by adding faujasite-type zeolite to an aqueous solution in which Group 10 elements of the periodic table are dissolved in water as cations. The ion exchange may be performed while stirring the aqueous solution. The temperature of the aqueous solution at the time of ion exchange may be 0 to 90 ° C or 20 to 70 ° C. The time for ion exchange may be about one hour or several hours. After the ion exchange, the solid content in the aqueous solution may be separated by means such as filtration, and further washed with water or the like. Thereafter, the solid content may be dried. The drying temperature may be 50 to 200 ° C and 80 to 150 ° C. Ion exchange may be repeated.

  The aqueous solution of a periodic table group 10 element can be prepared by, for example, dissolving a salt or metal complex containing a periodic table group 10 element in water. The salt containing a Group 10 element in the periodic table may be, for example, an inorganic salt or an organic acid salt. Inorganic salts may be, for example, sulfates, nitrates, chlorides, phosphates. The organic salt may be, for example, acetate or oxalate. By adjusting the concentration of the aqueous solution of Group 10 element of the periodic table, the content of Group 10 element of the periodic table in the dehydrogenation catalyst can be adjusted.

  If necessary, the solid content obtained by ion exchange may be fired. Firing may be performed in one stage or in multiple stages including two or more stages. The firing temperature is not particularly limited as long as it is a temperature capable of decomposing a salt containing a Group 10 element in the periodic table. When firing in one step, the firing temperature may be 400-600 ° C. and the firing time may be 1-10 hours.

  When firing in two stages, for example, the first stage firing temperature may be 80 to 150 ° C., and the first stage firing time may be 0.5 to 5 hours. The second stage baking temperature may be 400 to 600 ° C., and the second stage baking time may be 1 to 10 hours. The carrier after ion exchange may contain a large amount of moisture, but by carrying out baking in two stages, there is a tendency that the collapse of the carrier due to rapid evaporation of moisture can be suppressed.

  The atmosphere during firing is not particularly limited as long as it does not contain a reducing gas. For example, the carrier after ion exchange may be baked under the flow of air.

  The carrier may carry at least one element selected from the group consisting of Group 6 elements of the periodic table, Group 8 elements of the periodic table, and lanthanoids (hereinafter sometimes referred to as “second component”). Good.

  The Group 6 element of the periodic table may be at least one selected from the group consisting of chromium (Cr), molybdenum (Mo), and tungsten (W). The group 8 element of the periodic table may be at least one selected from the group consisting of iron (Fe), ruthenium (Ru), and osmium (Os). The lanthanoid can be, for example, lanthanum (La) or cerium (Ce). The element supported on the carrier may be a combination of these elements. When Cr is supported on the carrier as a Group 6 element of the periodic table, the diene selectivity tends to be further improved. In addition, when Cr is supported on a support, the activity of the dehydrogenation catalyst is likely to be improved, and high activity tends to be maintained over a long period of time. When Fe is supported on the carrier as a Group 8 element of the periodic table, the diene selectivity tends to be further improved. Further, when Fe is supported on a carrier, the activity of the dehydrogenation catalyst is likely to be improved, and high activity tends to be maintained over a long period of time. When Ce is supported on the carrier as a lanthanoid, the diene selectivity tends to be further improved. In addition, when Ce is supported on a carrier, the activity of the dehydrogenation catalyst is likely to be improved, and high activity tends to be maintained over a long period of time.

  The method for supporting the specific element on the carrier is not particularly limited, but may be the same method as the method for supporting the Group 10 element of the periodic table on the carrier.

  The order in which the periodic table group 10 element and the second component are supported on the carrier is not particularly limited. When the second component is supported on the carrier after the Group 10 element of the periodic table is supported on the support, ion exchange between the Group 10 element of the periodic table and the second component can be suppressed.

  The content of the second component is 0.50 to 5.20% by mass, 0.59 to 5.10% by mass, 0.60 to 5.00% by mass, and 0.60 based on the total mass of the dehydrogenation catalyst. It may be -2.29 mass%, 1.39-5.00 mass%, or 1.39-2.29 mass%. When the content of the second component is 0.50% by mass or more, the diene selectivity tends to be further improved. Moreover, when content of a 2nd component is 0.50 mass% or more, there exists a tendency for the activity of a dehydrogenation catalyst to improve easily and to maintain high activity over a long period of time. When the content of the second component is more than 5.20% by mass, it is difficult to obtain an activity improvement corresponding to the increase in the content of the second component. The content of the second component may be measured by ICP emission spectroscopic analysis.

  When Fe is supported on the carrier as a Group 8 element of the periodic table, the content of Fe is 0.50 to 5.20% by mass, 0.59 to 5.10% by mass based on the total mass of the catalyst, It may be 0.60 to 5.00% by mass, 0.60 to 2.29% by mass, 1.39 to 5.00% by mass, or 1.39 to 2.29% by mass. When the Fe content is 0.50% by mass or more, the diene selectivity tends to be further improved. Moreover, when the content of Fe is 0.50% by mass or more, the activity of the dehydrogenation catalyst is likely to be improved, and high activity tends to be maintained over a long period of time. When the Fe content is more than 5.20% by mass, it is difficult to obtain an improvement in activity that is commensurate with the increase in Fe content.

If Fe is supported on a carrier as a periodic table group 8 element, a ratio _n Pt _{/ n Fe} molar number _{n Pt} of Pt to moles _{n Fe} of Fe is 0.01～0.20,0.02～ It may be 0.18, 0.03-0.17, 0.03-0.12, 0.05-0.17 or 0.05-0.12. When the molar ratio n _Pt / n _Fe is in the above range, the diene selectivity tends to be further improved. Further, when the molar ratio n _Pt / n _Fe is in the above range, the activity of the dehydrogenation catalyst tends to be improved, and high activity tends to be maintained over a long period of time.

  The carrier may carry elements other than Group 10 elements of the periodic table, Group 6 elements of the periodic table, Group 8 elements of the periodic table, and lanthanoids.

  The dehydrogenation catalyst may be molded by a method such as an extrusion molding method or a tableting molding method.

  The dehydrogenation catalyst may contain a molding aid as long as the physical properties and catalyst performance of the catalyst are not impaired from the viewpoint of improving the moldability in the molding process. The molding aid may be at least one selected from the group consisting of a thickener, a surfactant, a water retention agent, a plasticizer, and a binder raw material. In consideration of the reactivity of the molding aid, the molding process may be performed at an appropriate stage in the production process of the dehydrogenation catalyst.

  The shape of the shaped dehydrogenation catalyst is not particularly limited, and can be appropriately selected depending on the form in which the catalyst is used. For example, the shape of the dehydrogenation catalyst may be a pellet shape, a granule shape, a honeycomb shape, a sponge shape, or the like.

  As pretreatment, reduction treatment of the dehydrogenation catalyst may be performed. In the reduction treatment, for example, the dehydrogenation catalyst may be held at 400 to 1000 ° C. or 400 to 800 ° C. in a reducing gas atmosphere. The reducing gas may be, for example, hydrogen or carbon monoxide. The reducing gas may be appropriately diluted with water or nitrogen. It is not necessary to dilute the reducing gas. By using the dehydrogenation catalyst subjected to the reduction treatment, the initial induction period of the dehydrogenation reaction can be shortened. The induction period in the initial stage of the reaction refers to a state in which the metal elements contained in the catalyst are reduced and are in an active state, and the activity of the catalyst is low. In addition, since a dehydrogenation catalyst has sufficient activity, without performing a pretreatment, pretreatment is not essential.

  The method for producing a diene according to this embodiment can be carried out, for example, using a reactor filled with the dehydrogenation catalyst according to this embodiment.

  The reaction form of the dehydrogenation reaction is not particularly limited, and may be a known form. The reaction type of the dehydrogenation reaction may be, for example, a fixed bed type, a moving bed type, or a fluidized bed type. When a dehydrogenation reaction is performed by a fixed bed type, process design becomes easy.

  The dehydrogenation reaction may be a gas phase reaction. That is, the hydrocarbon compound may be dehydrogenated by bringing a gaseous material (raw material gas) containing the hydrocarbon compound into contact with the dehydrogenation catalyst.

  The reaction temperature, that is, the temperature in the reactor, may be 300 to 800 ° C., 400 to 700 ° C., or 500 to 650 ° C. from the viewpoint of reaction efficiency. If the reaction temperature is 300 ° C. or higher, the equilibrium conversion rate of the hydrocarbon compound does not become too low, and a sufficient diene yield tends to be obtained. If the reaction temperature is 800 ° C. or lower, the coking rate does not become too high, and the high activity of the dehydrogenation catalyst tends to be maintained over a long period of time.

  The reaction pressure, that is, the pressure of the reactor, may be 0.01 to 1 MPa, 0.05 to 0.8 MPa, and 0.1 to 0.5 MPa. If the reaction pressure is in the above range, the dehydrogenation reaction tends to proceed, and sufficient reaction efficiency tends to be obtained.

In the continuous reaction apparatus, the ratio of the mass W of the dehydrogenation catalyst to the feed rate (feed amount / hour) F of the hydrocarbon compound (hereinafter referred to as “W / F”) is not particularly limited. It may be in the range of 500 g · h · mol ⁻¹ , and may be in the range of ^{1 to} 200 g · h · mol ⁻¹ . When W / F is 500 g · h · mol ⁻¹ or more, a sufficient contact time between the hydrocarbon compound and the dehydrogenation catalyst can be secured, and the dehydrogenation reaction easily proceeds. When W / F is 0.1 g · h · mol ⁻¹ or less, the decomposition of the hydrocarbon compound does not proceed excessively, and the diene selectivity or yield is easily improved.

  Moreover, as long as the effect of this invention is not inhibited, you may make a hydrocarbon compound contact a dehydrogenation catalyst in presence of components other than a hydrocarbon compound and a dehydrogenation catalyst. Components other than the hydrocarbon compound and the dehydrogenation catalyst may be water, methane, hydrogen, carbon dioxide, for example. When the dehydrogenation reaction is performed in the presence of water or hydrogen, an increase in the coking rate is suppressed, and the high activity of the dehydrogenation catalyst tends to be maintained over a long period of time.

  The product of dehydrogenation of the hydrocarbon compound may contain components other than the target diene. The other components may be, for example, water, hydrogen, by-products, unreacted hydrocarbon compounds, dehydrogenation catalysts, or impurities contained in the raw material. The by-product may be paraffin (ethane, propane, etc.) having a reduced carbon number, or olefin (ethylene, propylene, etc.) having a reduced carbon number. These other components may be separated from the product by known methods.

  As described above, according to the method for producing a diene according to the present embodiment, the diene can be produced with a high selectivity. Moreover, the dehydrogenation catalyst which concerns on this embodiment has activity higher than the conventional dehydrogenation catalyst, and can maintain high activity over a long period of time. Therefore, the frequency of catalyst regeneration can be reduced by using the dehydrogenation catalyst according to the present embodiment. For these reasons, the diene production method according to the present embodiment and the dehydrogenation catalyst according to the present embodiment are very useful when industrially producing diene.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

The following carriers A to E were prepared as dehydrogenation catalyst carriers.
Support A: H-Y type zeolite (manufactured by Nikka Seiko Co., Ltd., silica alumina ratio = 5.6)
Support B: Na-Y type zeolite (manufactured by Nikka Seiko Co., Ltd., silica alumina ratio = 5.6)
Support C: TiO ₂ (manufactured by Kanto Chemical Co.)
Carrier D: SiO ₂ (manufactured by Fuji Silysia)
Support E: Al ₂ O ₃ (manufactured by Sumitomo Chemical Co., Ltd.)
-Support F: H-type beta zeolite-Support G: H-MOR (Mordenite) (manufactured by Nikka Seiko Co., Ltd.)
-Carrier H: ZSM-5 type zeolite (manufactured by Nikka Seiko Co., Ltd.)

[Preparation of Carrier F]
The carrier F was prepared by the following procedure.

Solution A was prepared by mixing 27.840 g of tetraethylammonium hydroxide (TEAOH) and 16 ml of ion-exchanged water and stirring them at room temperature for 10 minutes. While stirring the solution A, 20 g of colloidal silica, 0.3013 g of sodium hydroxide, and 0.9518 g of NaAlO ₃ were sequentially added to the solution A to prepare a solution B. Solution B was allowed to stand at room temperature for 2 hours and then dried at 80 ° C. for 5 to 6 hours. The dried solution B was allowed to stand at 175 ° C. for 16 hours to precipitate crystals (solid content). The solid was collected from solution B by filtration at room temperature. The resulting solid was dried at 120 ° C. overnight. The solid content after drying was calcined at 500 ° C. for 10 hours to obtain Na-type beta zeolite (BEA).

Solution C was prepared by dissolving 60.510 g of ammonium nitrate in 756 ml of ion-exchanged water. After 6 g of the above BEA was added to Solution C, Solution C was stirred at room temperature for 1 hour. The solid was then collected from solution C by filtration at room temperature. The solid content was dried at 80 ° C. for 1 hour, and further dried at 120 ° C. overnight. The dried solid content was calcined at 500 ° C. for 3 hours to obtain carrier F (H-BEA) in which Na ions (Na ⁺ ) in BEA were ion-exchanged with protons (H ⁺ ).

Example 1
[Preparation of dehydrogenation catalyst A]
49.8 mg of carrier A, 0.3970 mg of Pt compound, and 1.25 ml of ion-exchanged water were mixed and stirred at room temperature for 10 minutes to prepare a mixed solution. Subsequently, the mixture was stirred at 80 ° C. for 6 hours for ion exchange. After ion exchange, the solid content was collected from the mixture by filtration and dried at 120 ° C. overnight. The solid content after drying was fired at a firing temperature of 550 ° C. for 3 hours. Through these steps, Pt was supported on the carrier A to obtain the dehydrogenation catalyst A (Pt / HY) of Example 1. As the Pt compound, tetraammineplatinum nitrate (II) was used.

[ICP emission spectroscopy]
The Pt content (unit: mass%) in the dehydrogenation catalyst A was measured by ICP emission spectroscopic analysis. The Pt content in the dehydrogenation catalyst A is shown in Table 1 below.

[Dehydrogenation reaction]
50 mg of dehydrogenation catalyst A was filled into a tubular reactor (SUS tube), and the gap was filled with quartz sand. The reactor was connected to a flow reactor and heated to 500 ° C. with an electric furnace. A mixed gas (raw material gas) of 1-butene, argon and nitrogen was supplied to the reactor, and 1-butene in the raw material gas was dehydrogenated. Here, the molar ratio of 1-butene, argon and nitrogen in the raw material gas was adjusted to 2: 40: 2. The feed rate of the raw material gas to the tubular reactor was adjusted to 44 ml / min. The contact time W / F was adjusted to 9.59 gh / mol. The pressure of the raw material gas in the tubular reactor was adjusted to atmospheric pressure.

  When 40 minutes passed from the reaction start time, the product (product gas) of the dehydrogenation reaction was collected from the tubular reactor. When 100 minutes had elapsed from the reaction start time, the product (product gas) of the dehydrogenation reaction was collected from the tubular reactor. The reaction start time is the time when the supply of the source gas is started. The product gas collected at each time point was analyzed using a gas chromatograph equipped with a flame ionization detector and a gas chromatograph equipped with a thermal conductivity detector. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. The concentration of 1-butene (unit: mass%) and the concentration of butadiene (unit: mass%) in the product gas collected at each time point were quantified by the absolute calibration curve method based on the gas chromatograph.

From the concentrations of 1-butene and 1,3-butadiene in the product gas, the yield of butadiene and the selectivity for butadiene at each time point were calculated. The yield of butadiene is defined by the following formula 4. The selectivity of butadiene is defined by the following formula 5. The yield of butadiene at each time point is shown in Table 1 below. Table 1 below shows the selectivity of butadiene at each time point.
R _Y = M _b / M ₀ × 100 (4)
_{R S = M b / (M} 0 -M P) × 100 (5)
_RY in Formula 4 is the yield of butadiene. R _S in Formula 5 is the selectivity for butadiene. M _b in the formulas 4 and 5 is the number of moles of 1,3-butadiene in the product gas, and M ₀ is the number of moles of 1-butene in the raw material gas. M _P in the formula 5 is the number of moles of 1-butene in the product gas.

(Example 2)
[Preparation of dehydrogenation catalyst B]
49.253 mg of carrier A, 0.3970 mg of Pt compound, 3.961 mg of Fe compound and 1.25 ml of ion-exchanged water were mixed and stirred at room temperature for 10 minutes to prepare a mixed solution. Subsequently, the mixture was stirred at 80 ° C. for 6 hours for ion exchange. After ion exchange, the solid content was collected from the mixture by filtration and dried at 120 ° C. overnight. The solid content after drying was fired at 550 ° C. for 3 hours. Thereby, the dehydrogenation catalyst B (Pt / Fe / HY) of Example 2 was obtained. For the preparation of the dehydrogenation catalyst B, the same Pt compound as in the case of the dehydrogenation catalyst A was used. As the Fe compound, iron (III) nitrate nonahydrate was used.

[ICP emission spectroscopy]
The Pt content (unit: mass%) in the dehydrogenation catalyst B was measured by ICP emission spectroscopic analysis. The Fe content (unit: mass%) in the dehydrogenation catalyst B was measured by ICP emission spectroscopy. The Pt content and the Fe (second component) content in the dehydrogenation catalyst B are shown in Table 1 below. The number of moles of Fe per unit mass of the dehydrogenation catalyst B (unit: μmol / g) was calculated based on the measurement result by ICP emission spectroscopic analysis. The number of moles of Fe is shown in Table 1 below. Based on the measurement results by ICP emission spectrometry, it was calculated ratio _n Pt _{/ n Fe} molar number _{n Pt} of Pt dehydrogenation catalyst B to moles _{n Fe} in Fe in the dehydrogenation catalyst B. The n _Pt / n _Fe of the dehydrogenation catalyst B is shown in Table 1 below. In Table 1, n _Pt / n _Fe is expressed as “Pt / Fe”.

[Dehydrogenation reaction]
The dehydrogenation of Example 2 was performed in the same manner as in Example 1, except that dehydrogenation catalyst B was used instead of dehydrogenation catalyst A, and W / F was adjusted to the values shown in Table 1 below. Reaction was performed. Subsequently, the product gas of Example 2 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas of Example 2 contained 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 2 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 1.

(Example 3)
[Preparation of dehydrogenation catalyst C]
The dehydrogenation catalyst C (Pt / Cr / C) of Example 3 was prepared in the same manner as in Example 2 except that 49.4 mg of carrier A was used and 3.08 mg of Cr compound was used instead of Fe compound. HY) was prepared. As the Cr compound, chromium (III) nitrate hexahydrate was used.

[ICP emission spectroscopy]
The Pt content (unit: mass%) in the dehydrogenation catalyst C was measured by ICP emission spectroscopic analysis. The content (unit: mass%) of Cr in the dehydrogenation catalyst C was measured by ICP emission spectroscopic analysis. The Pt content and the Cr (second component) content in the dehydrogenation catalyst C are shown in Table 1 below. The number of moles of Cr per unit mass of the dehydrogenation catalyst C (unit: μmol / g) was calculated based on the analysis result by ICP emission spectroscopic analysis. The number of moles of Cr is shown in Table 1 below.

[Dehydrogenation reaction]
The dehydrogenation of Example 3 was performed in the same manner as in Example 1, except that dehydrogenation catalyst C was used instead of dehydrogenation catalyst A, and W / F was adjusted to the values shown in Table 1 below. Reaction was performed. Subsequently, the product gas of Example 3 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 3 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 1.

Example 4
[Preparation of dehydrogenation catalyst D]
The dehydrogenation catalyst D (Pt / Ce / P) of Example 4 was prepared in the same manner as in Example 2, except that 47.8 mg of support A was used and 6.2 mg of Ce compound was used instead of Fe compound. HY) was prepared. As the Ce compound, cerium (III) nitrate hexahydrate was used.

[ICP emission spectroscopy]
The Pt content (unit: mass%) in the dehydrogenation catalyst D was measured by ICP emission spectroscopic analysis. The Ce content (unit: mass%) in the dehydrogenation catalyst D was measured by ICP emission spectroscopy. Table 1 below shows the content of Pt and the content of Ce (second component) in the dehydrogenation catalyst D. Based on the analysis result by ICP emission spectroscopy, the number of moles of Ce per unit mass of the dehydrogenation catalyst D (unit: μmol / g) was calculated. The number of moles of Ce is shown in Table 1 below.

[Dehydrogenation reaction]
The dehydrogenation of Example 4 was performed in the same manner as in Example 1, except that dehydrogenation catalyst D was used instead of dehydrogenation catalyst A, and W / F was adjusted to the values shown in Table 1 below. Reaction was performed. Subsequently, the product gas of Example 4 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 4 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 1.

(Example 5)
A dehydrogenation catalyst E (Pt / Fe / HY) of Example 5 was prepared in the same manner as in Example 2, except that the amount of Fe compound used was adjusted.

  The composition of the dehydrogenation catalyst E of Example 5 was analyzed by ICP emission spectroscopic analysis similar to that of Example 2. The analysis results are shown in Table 1 below.

  The dehydrogenation of Example 5 was carried out in the same manner as in Example 1, except that dehydrogenation catalyst E was used instead of dehydrogenation catalyst A, and W / F was adjusted to the values shown in Table 1 below. Reaction was performed. Subsequently, the product gas of Example 5 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 5 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 1.

(Example 6)
The dehydrogenation reaction of Example 6 was performed in the same manner as in Example 5 except that the amount of use of dehydrogenation catalyst E and W / F were adjusted to the values shown in Table 1 below. Subsequently, the product gas of Example 6 was analyzed in the same manner as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 6 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 1.

(Example 7)
The dehydrogenation reaction of Example 7 was performed in the same manner as in Example 5 except that the amount of dehydrogenation catalyst E and W / F were adjusted to the values shown in Table 1 below. Subsequently, the product gas of Example 7 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 7 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 1.

(Example 8)
A dehydrogenation catalyst F (Pt / Fe / H-Y) of Example 8 was prepared in the same manner as in Example 2, except that the amounts of the Pt compound and Fe compound were adjusted.

  The composition of the dehydrogenation catalyst F of Example 8 was analyzed by ICP emission spectral analysis similar to that of Example 2. The analysis results are shown in Table 2 below.

  The dehydrogenation of Example 8 was carried out in the same manner as in Example 1 except that the dehydrogenation catalyst F was used instead of the dehydrogenation catalyst A and that W / F was adjusted to the values shown in Table 2 below. Reaction was performed. Subsequently, the product gas of Example 8 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 8 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 2.

Example 9
A dehydrogenation catalyst G (Pt / Fe / H-Y) of Example 9 was prepared in the same manner as in Example 2 except that the respective amounts of the Pt compound and Fe compound were prepared.

  The composition of the dehydrogenation catalyst G of Example 9 was analyzed by ICP emission spectroscopic analysis similar to that of Example 2. The analysis results are shown in Table 2 below.

  The dehydrogenation of Example 9 was carried out in the same manner as in Example 1 except that the dehydrogenation catalyst G was used instead of the dehydrogenation catalyst A and that W / F was adjusted to the values shown in Table 2 below. Reaction was performed. Subsequently, the product gas of Example 9 was analyzed in the same manner as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 9 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 2.

(Example 10)
A dehydrogenation catalyst H (Pt / Fe / H-Y) of Example 10 was prepared in the same manner as in Example 2 except that the respective amounts of the Pt compound and Fe compound were prepared.

  The composition of the dehydrogenation catalyst H of Example 10 was analyzed by ICP emission spectral analysis similar to that of Example 2. The analysis results are shown in Table 2 below.

  The dehydrogenation of Example 10 was carried out in the same manner as in Example 1 except that the dehydrogenation catalyst H was used instead of the dehydrogenation catalyst A and that W / F was adjusted to the values shown in Table 2 below. Reaction was performed. Subsequently, the product gas of Example 10 was analyzed in the same manner as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 10 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 2.

(Example 11)
In Example 11, carrier B was used instead of carrier A. Moreover, in Example 11, the usage-amount of each of the compound of Pt and the compound of Fe was adjusted to the quantity different from Example 2, and the usage-amount of ion-exchange water was 150 ml. In Example 11, the mixture was stirred at room temperature for 24 hours for ion exchange. A dehydrogenation catalyst I (Pt / Fe / Na—Y) of Example 11 was prepared in the same manner as in Example 2 except for the above.

  The composition of the dehydrogenation catalyst I of Example 11 was analyzed by ICP emission spectroscopic analysis similar to that of Example 2. The analysis results are shown in Table 2 below.

  The dehydrogenation of Example 11 was carried out in the same manner as in Example 1 except that dehydrogenation catalyst I was used instead of dehydrogenation catalyst A and that W / F was adjusted to the values shown in Table 2 below. Reaction was performed. Subsequently, the product gas of Example 11 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 11 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 2.

(Example 12)
A dehydrogenation catalyst J (Pt / Fe / Na-Y) of Example 12 was prepared in the same manner as in Example 11 except that the respective amounts of the Pt compound and Fe compound were prepared.

  The composition of the dehydrogenation catalyst J of Example 12 was analyzed by ICP emission spectroscopic analysis similar to that of Example 2. The analysis results are shown in Table 2 below.

  The dehydrogenation of Example 12 was performed in the same manner as in Example 1 except that dehydrogenation catalyst J was used instead of dehydrogenation catalyst A, and W / F was adjusted to the values shown in Table 2 below. Reaction was performed. Subsequently, the product gas of Example 12 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Example 12 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 2.

(Example 13)
In the dehydrogenation reaction of Example 13, a mixed gas of n-butane and argon was used. The molar ratio of n-butane and argon in the raw material gas was adjusted to 2:42. In the dehydrogenation reaction of Example 13, W / F was adjusted to the values shown in Table 2 below. Except these matters, the dehydrogenation reaction of Example 13 was performed in the same manner as in Example 11. Subsequently, the product gas of Example 13 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas of Example 13 contains 1,3-butadiene. Based on the analysis results, the butadiene yield and butadiene selectivity in Example 13 were calculated in the same manner as in Example 1. However, in Example 13, not only the concentrations of n-butene (1-butene and 2-butene) and 1,3-butadiene in the product gas, but also the concentration of n-butane in the product gas was quantified. . Based on the concentrations of n-butene, 1,3-butadiene and n-butane in the product gas, the yield of butadiene and the selectivity for butadiene in Example 13 were calculated. The butadiene yield of Example 13 is defined by Equation 6 below. The selectivity for butadiene in Example 13 is defined by Equation 7 below. The yield of butadiene and the selectivity for butadiene are shown in Table 2 below.
R ′ _Y = M _b / M ′ ₀ × 100 (6)
R ′ _S = {M _b / (M ′ ₀ −M ′ _P −M _P )} × 100 (7)
R ′ _Y in Formula 6 is the yield of butadiene. R ′ _S in Formula 7 is the selectivity of butadiene. M _b in the formulas 6 and 7 is the number of moles of 1,3-butadiene in the product gas, and M ′ ₀ is the number of moles of n-butane in the raw material gas.
The M _'P in Formula 7 is the number of moles of n- butane in the product gas, M _P is the number of moles of in the product gas n- butene.

(Comparative Example 1)
49.8 mg of carrier C, 0.3970 mg of Pt compound and 2.5 ml of ion exchange water were mixed, and these were degassed and stirred at room temperature for 2 hours to obtain a mixed solution. The mixture was stirred at room temperature for 2 hours and further dried at 80 ° C. for 1 hour to obtain a solid content. The solid was left at 120 ° C. overnight and then calcined at 550 ° C. for 3 hours. Through these steps, Pt was supported on the carrier C to obtain the dehydrogenation catalyst (Pt / TiO ₂ ) of Comparative Example 1. In Comparative Example 1, the same Pt compound as that used in Example 1 was used.

  The composition of the dehydrogenation catalyst of Comparative Example 1 was analyzed by ICP emission spectroscopic analysis similar to that of Example 1. The analysis results are shown in Table 3 below.

  The dehydrogenation reaction of Comparative Example 1 was performed in the same manner as in Example 1 except that the dehydrogenation catalyst of Comparative Example 1 was used and that W / F was adjusted to the values shown in Table 3 below. . Subsequently, the product gas of Comparative Example 1 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Comparative Example 1 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 3.

(Comparative Example 2)
A dehydrogenation catalyst (Pt / SiO ₂ ) of Comparative Example 2 was prepared by the same method as Comparative Example 1 except that Support D was used instead of Support C.

  The composition of the dehydrogenation catalyst of Comparative Example 2 was analyzed by ICP emission spectroscopic analysis similar to that of Example 1. The analysis results are shown in Table 3 below.

  The dehydrogenation reaction of Comparative Example 2 was performed in the same manner as in Example 1 except that the dehydrogenation catalyst of Comparative Example 2 was used and that W / F was adjusted to the values shown in Table 3 below. . Subsequently, the product gas of Comparative Example 2 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Comparative Example 2 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 3.

(Comparative Example 3)
A dehydrogenation catalyst (Pt / Al ₂ O ₃ ) of Comparative Example 3 was prepared by the same method as Comparative Example 1 except that Support E was used instead of Support C.

  The composition of the dehydrogenation catalyst of Comparative Example 3 was analyzed by ICP emission spectroscopic analysis similar to that of Example 1. The analysis results are shown in Table 3 below.

  The dehydrogenation reaction of Comparative Example 3 was performed in the same manner as in Example 1 except that the dehydrogenation catalyst of Comparative Example 3 was used and that W / F was adjusted to the values shown in Table 3 below. . Subsequently, the product gas of Comparative Example 3 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Comparative Example 3 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 3.

(Comparative Example 4)
The dehydrogenation catalyst (Pt / H-BEA) of Comparative Example 4 was prepared in the same manner as in Example 1 except that the support F was used instead of the support A and the calcination temperature was adjusted to 500 ° C. Prepared.

  The composition of the dehydrogenation catalyst of Comparative Example 4 was analyzed by ICP emission spectroscopic analysis similar to that of Example 1. The analysis results are shown in Table 3 below.

  The dehydrogenation reaction of Comparative Example 4 was performed in the same manner as in Example 1 except that the dehydrogenation catalyst of Comparative Example 4 was used and that W / F was adjusted to the values shown in Table 3 below. . Subsequently, the product gas of Comparative Example 4 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Comparative Example 4 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 3.

(Comparative Example 5)
A dehydrogenation catalyst (Pt / H-MOR) of Comparative Example 5 was prepared in the same manner as in Comparative Example 4 except that Support G was used instead of Support F.

  The composition of the dehydrogenation catalyst of Comparative Example 5 was analyzed by ICP emission spectroscopic analysis similar to that of Example 1. The analysis results are shown in Table 3 below.

  The dehydrogenation reaction of Comparative Example 5 was performed in the same manner as in Example 1 except that the dehydrogenation catalyst of Comparative Example 5 was used and that W / F was adjusted to the values shown in Table 3 below. . Subsequently, the product gas of Comparative Example 5 was analyzed by the same method as in Example 1. As a result of analysis, it was confirmed that the product gas contains 1,3-butadiene. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Comparative Example 5 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 3.

(Comparative Example 6)
A dehydrogenation catalyst (Pt / ZSM-5) of Comparative Example 6 was prepared in the same manner as in Comparative Example 4 except that Support H was used instead of Support F.

  The composition of the dehydrogenation catalyst of Comparative Example 6 was analyzed by ICP emission spectroscopic analysis similar to Example 1. The analysis results are shown in Table 3 below.

  The dehydrogenation reaction of Comparative Example 6 was performed in the same manner as in Example 1 except that the dehydrogenation catalyst of Comparative Example 6 was used and that W / F was adjusted to the values shown in Table 3 below. . Subsequently, the product gas of Comparative Example 6 was analyzed by the same method as in Example 1. Based on the analysis results, the yield of butadiene and the selectivity for butadiene in Comparative Example 6 were calculated in the same manner as in Example 1. The yield of butadiene and the selectivity of butadiene are shown in Table 3.

Claims (15)

Contacting the hydrocarbon compound with a dehydrogenation catalyst to dehydrogenate the hydrocarbon compound,
The dehydrogenation catalyst has a support containing faujasite-type zeolite, and a periodic table Group 10 element supported on the support.
Diene production method. The periodic table Group 10 element is Pt;
The method for producing a diene according to claim 1. At least one element selected from the group consisting of Group 6 elements of the periodic table, Group 8 elements of the periodic table, and lanthanoids is supported on the carrier,
The method for producing a diene according to claim 1 or 2. As the Group 6 element of the periodic table, Cr is supported on the carrier,
The method for producing a diene according to claim 3. As the Group 8 element of the periodic table, Fe is supported on the carrier,
The method for producing a diene according to claim 3 or 4. Ce is supported on the carrier as the lanthanoid,
The manufacturing method of the diene as described in any one of Claims 3-5. The content of Fe is 0.50 to 5.20% by mass based on the total mass of the dehydrogenation catalyst.
The method for producing a diene according to claim 5 or 6. The ratio _n Pt _{/ n Fe} molar number _{n Pt} of Pt to moles _{n Fe} of Fe is 0.01 to 0.20,
The manufacturing method of the diene as described in any one of Claims 5-7. The faujasite type zeolite is a Y type zeolite,
The manufacturing method of the diene as described in any one of Claims 1-8. The faujasite type zeolite is NaY type zeolite,
The manufacturing method of the diene as described in any one of Claims 1-9. The hydrocarbon compound comprises butane and / or butene,
The manufacturing method of the diene as described in any one of Claims 1-10. A dehydrogenation catalyst for producing a diene by dehydrogenation of a hydrocarbon compound,
A carrier containing faujasite-type zeolite, and a periodic table Group 10 element supported on the carrier,
Dehydrogenation catalyst. At least one element selected from the group consisting of Group 6 elements of the periodic table, Group 8 elements of the periodic table, and lanthanoids is supported on the carrier,
The dehydrogenation catalyst according to claim 12. As the Group 8 element of the periodic table, Fe is supported on the carrier,
The content of Fe is 0.50 to 5.20% by mass based on the total mass of the dehydrogenation catalyst.
The dehydrogenation catalyst according to claim 13. The periodic table group 10 element is Pt,
The ratio _n Pt _{/ n Fe} molar number _{n Pt} of Pt to moles _{n Fe} of Fe is 0.01 to 0.20,
The dehydrogenation catalyst according to claim 14.