Classifications

• • 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
• • 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
  • C07C11/10—Alkenes with five carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C11/00—Aliphatic unsaturated hydrocarbons
  • C07C11/12—Alkadienes
  • C07C11/173—Alkadienes with five carbon atoms
  • C07C11/18—Isoprene
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
  • C07C5/46—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with sulfur or a sulfur-containing compound as an acceptor

Definitions

• the present invention relates to a method for producing an olefin by dehydrogenating a saturated hydrocarbon having 5 carbon atoms.
• Saturated hydrocarbons with 5 carbon atoms are components contained in fuel oil in the petroleum refining process, and as long as demand for fuel oils is expected to some extent, the problem of surplus saturated hydrocarbons with 5 carbon atoms does not occur. ..
• One of the countermeasures is to dehydrogenate a saturated hydrocarbon having 5 carbon atoms to convert it into an olefin having 5 carbon atoms and use it as a petrochemical raw material.
• Patent Documents 1 and 2 are not a method for producing an olefin having 5 carbon atoms by dehydrocarbonating a saturated hydrocarbon having 5 carbon atoms.
• the olefins obtained by dehydrogenation using saturated hydrocarbons having 5 carbon atoms include monoolefins and diolefins, and diolefins are useful in that they are used in synthetic rubbers, fine chemicals, resins, and the like. Is high. Therefore, it is desired to develop a method for producing an olefin having a high selectivity of diolefin in a product by dehydrogenating a saturated hydrocarbon having 5 carbon atoms.
• an object of the present invention is to provide a method for producing an olefin by dehydrogenation of a saturated hydrocarbon having 5 carbon atoms, which has a high selectivity of diolefin in the product.
• the present invention provides a method for producing an olefin, which comprises performing a dehydrogenation reaction of a saturated hydrocarbon having 5 carbon atoms.
• the volume ratio of the hydrogen sulfide to the saturated hydrocarbon having 5 carbon atoms is 0.2 to 3.0.
• the volume ratio of the hydrogen sulfide to the saturated hydrocarbon having 5 carbon atoms is 1.0 to 3.0.
• the present invention (4) provides a method for producing an olefin according to any one of (1) to (3), wherein the reaction temperature of the dehydrogenation reaction is 500 to 700 ° C.
• the present invention (5) provides a method for producing an olefin according to any one of (1) to (3), wherein the reaction temperature of the dehydrogenation reaction is 500 to 650 ° C.
• the present invention (6) provides the method for producing an olefin of (4), which is characterized in that the reaction temperature of the dehydrogenation reaction is 500 to 550 ° C.
• the present invention (7) provides the method for producing an olefin (4), which is characterized in that the reaction temperature of the dehydrogenation reaction is 550 to 650 ° C.
• the method for producing an olefin of the present invention comprises contacting a saturated hydrocarbon having 5 carbon atoms with a dehydrogenation catalyst containing at least one metal selected from transition metals in the presence of hydrogen sulfide.
• a method for producing an olefin which comprises performing a dehydrogenation reaction of a saturated hydrocarbon having 5 carbon atoms.
• the saturated hydrocarbon having 5 carbon atoms according to the method for producing an olefin of the present invention is a raw material that comes into contact with a dehydrogenation catalyst and is a target to be dehydrogenated by a dehydrogenation reaction.
• Saturated hydrocarbons having 5 carbon atoms are hydrocarbons represented by C5 H12 , and are n-pentane and 2-methylbutane.
• the saturated hydrocarbon having 5 carbon atoms may be any one of n-pentane and 2-methylbutane, or may be a mixture of two or more.
• 2-methylbutane is preferable in that the radical cation is more stable in the tertiary carbon than in the secondary carbon and the yield of the olefin is improved.
• the saturated hydrocarbon having 5 carbon atoms is a hydrocarbon other than the saturated hydrocarbon having 5 carbon atoms, for example, a saturated or unsaturated hydrocarbon having 3 carbon atoms and a saturated or unsaturated hydrocarbon having 4 carbon atoms. , May contain unsaturated hydrocarbons having 5 carbon atoms.
• the purity of the saturated hydrocarbon having 5 carbon atoms is not particularly limited, but is preferably 80% by mass or more, more preferably 85% by mass or more, and particularly preferably 90% by mass or more.
• the dehydrogenation catalyst according to the method for producing an olefin of the present invention is a dehydrogenation catalyst containing at least one metal selected from transition metals.
• the transition metal contained in the dehydrogenation catalyst include Fe, Co, Ni, Mn, Cu, Mo, Cr, V, Ti, Ru, Pd and the like, and among these, the catalyst life is long. Fe, Ni and Co are preferable, and Fe is particularly preferable.
• the transition metal contained in the dehydrogenation catalyst is usually supported on a carrier.
• Carriers for such transition metals include silica (SiO 2 ), alumina (Al 2 O 3 ), zirconia (ZrO 2 ), ceria (CeO 2 ), magnesia (MgO), titania (TiO 2 ) and their oxidation. Examples thereof include a composite sulfide of a substance and hydrogen sulfide, and among these, silica and alumina are preferable in terms of high stability and high selectivity of the product.
• the amount of the transition metal supported in the dehydrogenation catalyst is preferably 0.5 to 70% by mass, particularly preferably 3 to 20% by mass, in terms of atomic value, with respect to the total mass of the dehydrogenation catalyst.
• the oxide-equivalent carrying amount (%) of the transition metal in the dehydrogenation catalyst with respect to the total mass of the dehydrogenation catalyst is "(mass of the transition metal present in the dehydrogenation catalyst in terms of oxide / total mass of the dehydrogenation catalyst). ) ⁇ 100 ”is a value calculated by the formula.
• the saturated hydrocarbon having 5 carbon atoms and the dehydrogenation catalyst are brought into contact with each other in the presence of hydrogen sulfide, so that the hydrocarbon raw material has 5 carbon atoms.
• a dehydrogenation reaction of a saturated hydrocarbon is carried out to obtain an olefin having 5 carbon water.
• the life of the catalyst can be extended by contacting the saturated hydrocarbon having 5 carbon atoms with the dehydrogenation catalyst in the presence of hydrogen sulfide.
• the life of the catalyst is shortened.
• pre-sulfurization of a dehydrogenation catalyst in which hydrogen sulfide is brought into contact with a dehydrogenation catalyst is performed in advance, and then contact between a saturated hydrocarbon having 5 carbon atoms and the dehydrogenation catalyst is performed.
• the method of contacting a saturated hydrocarbon having 5 carbon atoms and a dehydrogenation catalyst in the presence of hydrogen sulfide is not particularly limited, and is, for example, (i) continuous.
• a dehydrogenation catalyst is filled in the flow-type reaction tower, and saturated hydrocarbon having 5 carbon atoms is supplied together with the carrier to one end side of the reaction tower, and hydrogen sulfide is supplied at the same time to one end side in the reaction tower.
• a dehydrogenation catalyst is filled, and a saturated hydrocarbon supply line with 5 carbon atoms is connected to one end side of the reaction tower. While supplying hydrogen together with the carrier, hydrogen sulfide is supplied in the middle of the supply line of saturated dehydrogenation having 5 carbon atoms, and the saturated dehydrogenation having 5 carbon atoms in the supply line of saturated dehydrogenation having 5 carbon atoms. And hydrogen sulfide are mixed, the mixture is supplied to one end side of the reaction column, the mixture is brought into contact with the dehydrogenation catalyst, and the reaction product is discharged from the other end side of the reaction column.
• the volume ratio of hydrogen sulfide to a saturated hydrocarbon having 5 carbon atoms is preferably 0.2 to 3.0.
• the selectivity of diolefin in the product is high.
• the volume ratio of hydrogen sulfide to a saturated hydrocarbon having 5 carbon atoms is more preferably 1.0 to 3.0. ..
• the selectivity of the diolefin in the product is high, and the selectivity of the dehydrogenated product in the product (mono).
• the total selectivity of olefins and diolefins) is high. Since monoolefin also has value as a petrochemical raw material, it is more preferable that the dehydrogenation rate is high.
• the supply rate of a saturated hydrocarbon having 5 carbon atoms is preferably 0.1 to 50 mL / min, particularly preferably 1 to 10 mL / min.
• the reaction temperature of the dehydrogenation reaction is preferably 500 to 700 ° C, particularly preferably 500 to 650 ° C in that the selectivity of the diolefin in the product is high.
• the reaction temperature of the dehydrogenation reaction when increasing the selectivity of monoolefin in a dehydrogenated product, is preferably 500 to 550 ° C. Further, in the method for producing an olefin of the present invention, when increasing the selectivity of the diolefin in the dehydrogenated product, the reaction temperature of the dehydrogenation reaction is preferably 550 to 650 ° C.
• a monoolefin and a diolefin are produced by a dehydrogenation reaction of a saturated hydrocarbon having 5 carbon atoms.
• a hydrocarbon having 1 to 4 carbon atoms which is a decomposition product, and an isomerized saturated hydrocarbon having 5 carbon atoms are by-produced.
• 2-methylbutene is used as a saturated hydrocarbon having 5 carbon atoms
• 2-methyl-1-butene and 2-methyl-2-butene are produced as monoolefins
• 2-methyl as a diolefin when 2-methylbutene is used as a saturated hydrocarbon having 5 carbon atoms, 2-methyl-1-butene and 2-methyl-2-butene are produced as monoolefins, and 2-methyl as a diolefin.
• -1,3-butadiene is produced, and hydrocarbons having 1 to 4 carbon atoms and n-pentane are by-produced.
• hydrocarbons having 1 to 4 carbon atoms and n-pentane are by-produced.
• 1-pentene and 2-pentene are produced as monoolefins
• 1,3-pentadiene and 1,4 are used as diolefins.
• -Pentadiene and 2,3-pentadiene are produced, and hydrocarbons having 1 to 4 carbon atoms and 2-methylbutane are by-produced.
• Example 1 A reactor having an inner diameter of 8 mm and a length of 300 mm was filled with the dehydrogenation catalyst (catalyst amount: 500 mg) obtained above. Next, 2-methylbutane, hydrogen sulfide and carrier gas (helium gas) were added to the reactor at a ratio of hydrogen sulfide / 2-methylbutane volume ratio of 0.2 and 2-methylbutane / carrier gas volume ratio of 0.1. While supplying at a supply rate of 50 mL / min, the reaction solution was discharged from the reactor, and a dehydrogenation reaction was carried out at a reaction temperature of 550 ° C.
• the dehydrogenation catalyst catalyst amount: 500 mg
• reaction solution was analyzed by gas chromatograph (column: VZ-7 (GL Sciences), analysis conditions: GC-FID, INJ 35 ° C., COL 35 ° C., DET 50 ° C., flow rate 25 mL / min) to produce a product.
• gas chromatograph column: VZ-7 (GL Sciences), analysis conditions: GC-FID, INJ 35 ° C., COL 35 ° C., DET 50 ° C., flow rate 25 mL / min
• Examples 2 to 17, Comparative Example 1 The same procedure as in Example 1 was carried out except that the hydrogen sulfide / 2-methylbutane volume ratio and the reaction temperature were as shown in Tables 1 to 4. The results are shown in Tables 1 to 4.
• Example 2 A catalyst was prepared in the same manner as in Example 1 except that the amount of metal of the catalyst was 20% by mass with respect to the total weight of the dehydrogenation catalyst and the firing temperature was 700 ° C.
• the reaction was the same as in Example 1 except that n-butane was used instead of 2-methylbutane, the hydrogen sulfide / n-butane volume ratio and the reaction temperature were as shown in Table 5, and the supply rate was 25 mL / min. Was done. The results are shown in Table 5.

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• 2021
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