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  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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  • B01J35/615—100-500 m2/g
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
  • C07C303/20—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by addition of sulfurous acid or salts thereof to compounds having carbon-to-carbon multiple bonds
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  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
  • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
  • C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
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  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
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  • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
  • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
• • C—CHEMISTRY; METALLURGY
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  • C07C2527/14—Phosphorus; Compounds thereof
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  • C07C2527/14—Phosphorus; Compounds thereof
  • C07C2527/16—Phosphorus; Compounds thereof containing oxygen
  • C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-

Definitions

• the present invention relates to a method for producing a long-chain olefin.
• Patent Document 1 discloses a method for producing an olefin compound by dehydration reaction of a tertiary alcohol in a gas phase at a reaction temperature of 200 to 400 ° C. in the presence of an aluminosilicate as a solid catalyst.
• Patent Document 2 discloses a method for producing ethylene by dehydration of ethanol in the gas phase in the presence of a catalyst prepared by adding phosphate to activated alumina.
• JP 2008-56671 A Japanese Patent Publication No.59-40057 International Publication No. 2011/052732
• the present invention relates to a method for producing an olefin by dehydration reaction of an alcohol having 8 to 22 carbon atoms in the presence of a solid acid catalyst, wherein the solid acid catalyst is more electric than aluminum to aluminum oxide.
• the present invention relates to a method for producing an olefin that supports an oxide of an element having a high degree of negativeness.
• Patent Document 1 or 2 In the gas phase reaction typified by the method described in Patent Document 1 or 2, it is necessary to vaporize all the raw materials, and particularly for a long-chain aliphatic alcohol having a high boiling point, energy consumption is large, and the cost is low. Is also disadvantageous. Furthermore, in the silica alumina catalyst used in Patent Document 1, branching by alkyl rearrangement and olefin multimerization are likely to occur simultaneously, resulting in a problem of reduced product yield. Further, Patent Document 2 only describes suppression of carbonaceous precipitation, and does not describe any suppression of branching due to alkyl transfer or increase in the number of olefins.
• the olefin obtained by the method described in Patent Document 3 has few by-products due to multimerization or branching, but development of a more efficient production method is desired.
• the present invention relates to a method for producing a long-chain olefin in a high yield in a short reaction time in a dehydration reaction of a long-chain aliphatic alcohol.
• the present inventor has found that a long-chain olefin can be produced in a high yield in a short reaction time by performing a dehydration reaction of a long-chain aliphatic alcohol in the presence of a specific catalyst. That is, the method for producing olefin of the present invention is a method for producing olefin by alcohol dehydration reaction in the presence of a solid acid catalyst, wherein the solid acid catalyst has an electronegativity higher than that of aluminum with respect to aluminum oxide. Is an oxide of a high element.
• the production method of the present invention can provide a method for producing a long-chain olefin with high yield and high selectivity in a short reaction time in a dehydration reaction of a long-chain aliphatic alcohol.
• the olefin production method of the present invention is a method for producing an olefin by a dehydration reaction of an alcohol using a solid acid catalyst in which an oxide of an element having higher electronegativity than aluminum is supported on aluminum oxide. is there.
• the present invention aluminum oxide carrying an element oxide having a higher electronegativity than aluminum is used as the solid acid catalyst.
• the value of electronegativity in the present invention refers to the value of Pauling's electronegativity.
• the electronegativity is preferably 1.6 or more, more preferably 1.7 or more, still more preferably 1.8 or more, and preferably 2.6 or less, more preferably 2 from the viewpoint of suppressing side reactions. 0.0 or less.
• Elements having higher electronegativity than aluminum (Al: 1.5) include sulfur (S: 2.5), tungsten (W: 1.7), phosphorus (P: 2.1), silicon (Si: 1.8), molybdenum (Mo: 1.8), iron (Fe: 1.8), cobalt (Co: 1.8), nickel (Ni: 1.8), copper (Cu: 1.9), Zinc (Zn: 1.6), Boron (B: 2.0), Gallium (Ga: 1.6), Indium (In: 1.7), Germanium (Ge: 1.8), Tin (Sn: 1) .8), antimony (Sb: 1.9), bismuth (Bi: 1.9), and selenium (Se: 2.4).
• sulfur (S) Tungsten (W), phosphorus (P), and silicon (Si) are preferable.
• the values in parentheses indicate Pauling's electronegativity values.
• the compound serving as the oxide source of the element is preferably one or more selected from water-soluble ammonium salts, metal alkoxides, oxoacids and salts thereof from the viewpoint of catalytic activity, specifically, ammonium sulfate, Examples thereof include water-soluble ammonium salts such as ammonium tungstate, metal alkoxides such as tetramethylorthosilicate and tetraethylorthosilicate which are dissolved in water, oxoacids such as silicotungstic acid and phosphotungstic acid, and salts thereof.
• the catalytic activity is a reaction rate when the catalyst is used in the dehydration reaction according to the present invention.
• More specific compounds include sulfuric acid, ammonium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, sodium thiosulfate, ammonium thiosulfate, tungstic acid, ammonium tungstate, sodium tungstate, potassium tungstate, calcium tungstate, Ammonium paratungstate, ammonium metatungstate, silicotungstic acid, phosphotungstic acid, ammonium phosphotungstate, sodium phosphotungstate, potassium phosphotungstate, colloidal silica, silica gel, water glass, tetramethylammonium silicate, tetramethylorthosilicate , Tetraethylorthosilicate, phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, phosphorus Sodium, potassium phosphate, magnesium phosphate, one selected from calcium phosphate or two or more are preferred.
• ammonium sulfate, ammonium tungstate, diammonium hydrogen phosphate, and tetraethylorthosilicate are preferably used as the oxide source from the viewpoint of catalytic activity.
• the dehydration reaction of the long chain alcohol proceeds rapidly, and the target long chain olefin can be obtained in a high yield.
• the supported amount of the oxide of the element with respect to aluminum oxide is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and even more. Preferably, it is 0.8% by mass or more, and from the same viewpoint, preferably 10% by mass or less, more preferably 9% by mass or less, still more preferably 8% by mass or less, still more preferably 7% by mass or less, More preferably, it is 2 mass% or less. If the amount of oxide of the element is within the above range, the reaction can be completed in a short time.
• the catalyst used in the present invention can be prepared by evaporation to dryness, adsorption, equilibrium adsorption, pore filling, spraying, precipitation, and the like.
• a specific preparation method from the viewpoint of catalytic activity, an aqueous suspension or hydrated solid of aluminum oxide, a compound serving as an oxide source of the element or an oxide of the element, and ion-exchanged water are mixed and impregnated. The method of preparing a thing and drying and baking the obtained impregnation thing is mentioned.
• the aluminum oxide serving as the carrier can be obtained by, for example, a precipitation method, a sol-gel method, or an alkoxide method. From the same viewpoint, aluminum oxide calcined at 900 ° C. or lower, more preferably 850 ° C. or lower, and still more preferably 800 ° C. or lower is preferable.
• ⁇ -alumina is preferable from the viewpoint of catalytic activity.
• the temperature for impregnating aluminum oxide with the compound serving as the oxide source of the element or the oxide of the element is preferably 0 ° C. or more, more preferably 20 ° C., from the viewpoint of the loading speed and the uniformity of the resulting catalyst. Or more, more preferably 50 ° C or higher, still more preferably 60 ° C or higher, and preferably 100 ° C or lower, more preferably 95 ° C or lower, still more preferably 90 ° C or lower, and still more preferably 80 ° C or lower. .
• the impregnation time is preferably 0.1 hour or more, more preferably 0.2 hour or more, still more preferably 0.5 hour or more, from the viewpoint of the carrying speed and the uniformity of the resulting catalyst, and preferably It is 10 hours or less, More preferably, it is 5 hours or less, More preferably, it is 2 hours or less.
• the calcination temperature after impregnation is preferably 300 ° C. or higher, more preferably 400 ° C. or higher, and still more preferably 450 ° C. or higher, from the viewpoint of catalyst activity. Therefore, it is preferably 900 ° C. or lower, more preferably 850 ° C. or lower, still more preferably 800 ° C. or lower, still more preferably 700 ° C. or lower, and still more preferably 600 ° C. or lower.
• the calcination time is preferably 1 hour or more, more preferably 2 hours or more from the viewpoint of catalyst activity, and preferably 10 hours or less, more preferably from the viewpoint of prevention of catalyst surface area reduction or degree of dispersion of supported elements. Is 5 hours or less.
• the firing atmosphere is not particularly limited, and can be performed under an inert gas, an oxidizing atmosphere, or a reducing atmosphere. Moreover, it may be a sealed state or a gas flow state. In the present invention, from the viewpoint of catalytic activity, air or an oxygen stream is preferred. Since the catalyst thus obtained is in an agglomerated state, it can be appropriately pulverized into powder, granules, or formed into noodles, pellets, or the like.
• the average particle size of the powder is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, still more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more, from the viewpoint of easy recovery of the catalyst after completion of the reaction. More preferably, it is 30 ⁇ m or more, and from the viewpoint of catalytic activity, it is preferably 300 ⁇ m or less, more preferably 250 ⁇ m or less, still more preferably 200 ⁇ m or less, still more preferably 150 ⁇ m or less, even more preferably 100 ⁇ m or less, more More preferably, it is 50 ⁇ m or less.
• BET specific surface area of the catalyst from the viewpoint of catalytic activity, preferably 100 m 2 / g or more, more preferably 120 m 2 / g or more, further preferably 140 m 2 / g or more, and, the durability and strength of the catalyst From the viewpoint, it is preferably 500 m 2 / g or less, more preferably 400 m 2 / g or less, still more preferably 300 m 2 / g or less, and still more preferably 200 m 2 / g or less.
• the average pore diameter of the catalyst is preferably 5 nm or more, more preferably 7 nm or more, still more preferably 9 nm or more from the viewpoint of catalytic activity, and from the same viewpoint, preferably 50 nm or less, more preferably 40 nm or less, More preferably, it is 25 nm or less, More preferably, it is 20 nm or less, More preferably, it is 15 nm or less.
• the pore volume of the catalyst is preferably 0.20 cm 3 / g or more, more preferably 0.25 cm 3 / g or more, still more preferably 0.30 cm 3 / g or more, and the like
• it is 0.7 cm ⁇ 3 > / g or less.
• the average particle size was measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by HORIBA Ltd.) in ethanol (Kanto Chemical Co., Ltd., deer grade 1) as a measurement solvent.
• the dispersion was measured while stirring (05 g) (stirring speed; level 4), and the median diameter was calculated with a refractive index of 1.10.
• the measurement of a BET specific surface area, an average pore diameter, and a pore volume can be performed as follows. Using a specific surface area / pore distribution measuring device “ASAP2020” manufactured by Micromeritics, the sample was pre-heated at 250 ° C.
• the pore volume can be calculated by the BJH method (Barrett-Joyner-Halenda method), and the peak top of the pore distribution is taken as the average pore diameter.
• the BJH method is calculated by using cylindrical pores that are not connected to other pores as a model, and is a method for obtaining pore distribution from capillary condensation of nitrogen gas and multimolecular adsorption. The details are described in “Shimadzu review” (Vol. 48, No. 1, pp. 35-44, published in 1991).
• the amount of the catalyst used is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and still more based on the raw material alcohol.
• the amount is preferably 2% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 12% by mass or less.
• the reaction temperature can be kept low, which is economical.
• reaction proceeds as follows. That is, it is considered that the acid strength of aluminum oxide is moderately improved and the reaction activity is improved by the supported element having high electronegativity.
• the number of carbon atoms of the alcohol used as a raw material in the present invention is 8 or more, preferably 12 or more, more preferably 14 or more, and 22 or less, preferably 20 or less, more preferably, from the viewpoint of the usefulness of the olefin. 18 or less, and from the same viewpoint, it is 8 or more and 22 or less, preferably 12 or more and 20 or less, more preferably 14 or more and 18 or less, and these primary alcohols are more preferable.
• the raw material alcohol examples include 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-dodecanol from the viewpoint of the usefulness of olefins.
• One or more selected from octadecanol, 1-nonadecanol, and 1-eicosanol are preferred.
• an organic solvent may be used as necessary.
• the organic solvent that can be used in the present invention is not particularly limited as long as it is liquid at the reaction temperature, is compatible with the substrate and the product, and does not inhibit the reaction, and may be a mixture. Moreover, what can isolate
• hydrocarbon-based organic solvents such as saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, and aromatic hydrocarbons are preferable.
• the saturated aliphatic hydrocarbon may be linear or branched. Specific examples of the saturated aliphatic hydrocarbon include compounds having 10 to 35 carbon atoms such as tridecane, hexadecane, octadecane, eicosane, docosane, triacontane, squalane and the like.
• the saturated aliphatic hydrocarbon may be a mixture such as liquid paraffin, naphthene hydrocarbon, and isoparaffin hydrocarbon. Moreover, what is solid at normal temperature but liquid at the reaction temperature, such as solid paraffin, can also be used.
• oligomers such as propylene and isobutene can be used as the saturated aliphatic hydrocarbon.
• the unsaturated aliphatic hydrocarbon may be linear or branched.
• the number of carbon atoms such as eicosene, heicosene, dococene, tricosene, squalene is preferably 15 or more, more preferably 30 or more, and preferably 35 or less, more preferably 30.
• the following compounds are mentioned.
• the unsaturated aliphatic hydrocarbon may be a mixture.
• aromatic hydrocarbon examples include alkylbenzene and alkylnaphthalene such as n-dodecylbenzene, n-tridecylbenzene, n-tetradecylbenzene, n-pentadecylbenzene, n-hexadecylbenzene, diisopropylnaphthalene and the like.
• the reaction in the method of the present invention is a dehydration reaction of alcohol, and if the by-produced water stays in the system, the reaction rate may decrease. Therefore, from the viewpoint of improving the reaction rate, an inert gas such as nitrogen or argon is introduced into the reaction system under stirring, usually at a reduced pressure of 0.03 MPa or more and 0.09 MPa or less, or at normal pressure, and the generated water is discharged outside the system. It is preferable to carry out the reaction while removing it.
• the reaction temperature is preferably not higher than the boiling point of the raw material alcohol from the viewpoint of the reaction rate and the suppression of side reactions such as alkyl rearrangement and multimerization.
• the specific reaction temperature is preferably 150 ° C.
• Is 270 ° C. or higher and is preferably 350 ° C. or lower, more preferably 310 ° C. or lower, still more preferably 295 ° C. or lower, and even more preferably 290 ° C. or lower, from the viewpoint of energy efficiency and equipment load.
• the olefination reaction is preferably a liquid phase reaction.
• the liquid phase reaction refers to a reaction below the boiling point of the raw alcohol, that is, below the temperature at which the liquid phase exists. In the case of a liquid phase reaction, it is not necessary to vaporize all the raw materials, so that the manufacturing cost can be suppressed. In addition, since branching due to alkyl rearrangement and olefin multimerization can be suppressed, the desired product can be obtained in high yield.
• the reaction time is preferably such that the alcohol reaction rate is preferably 95% or more, more preferably 97% or more, and still more preferably 98% or more, from the viewpoint of the yield of the desired olefin.
• Such a reaction time may vary depending on the reaction temperature, the type of organic solvent, the type of catalyst and the amount of the catalyst used, etc.
• it is preferably 0.1 hour or more, more preferably 0. .5 hours or more, more preferably 1 hour or more, and preferably 20 hours or less, more preferably 10 hours or less, still more preferably 7 hours or less.
• the LHSV (liquid space velocity) in the fixed bed reaction is preferably 0.05 / h or more, more preferably 0.1 / h or more, still more preferably 0.2 / h or more, from the viewpoint of yield, and From the same viewpoint, it is preferably 10 / h or less, more preferably 7 / h or less, and still more preferably 5 / h or less.
• the alcohol reaction rate is usually 80% or more, preferably 90% or more, and the olefin yield is usually 90% or more.
• generation rate of the branched olefin and dimerization body which are contained in olefin becomes normally 5% or less, respectively.
• the olefin obtained by the production method of the present invention has a high ratio of those internally isomerized, and those having 30% or more of all olefins internally isomerized can be easily obtained.
• olefin may be purified by distillation from the reaction product obtained as described above.
• Highly purified olefins obtained by distillation purification are useful as raw materials or intermediate raw materials for surfactants, organic solvents, softeners, sizing agents and the like.
• the method for producing an olefin sulfonate of the present invention comprises a step of obtaining a sulfonated product by sulfonating the olefin obtained by the method of the present invention, and after neutralizing the sulfonated product, And a step of hydrolyzing the hydrate.
• the sulfonation reaction in the step of obtaining the sulfonated product can be carried out by reacting sulfur trioxide gas or sulfuric acid anhydride with 1 mol of olefin, preferably 1 mol or more and 1.2 mol or less.
• the reaction temperature in the sulfonation reaction is preferably 0 ° C. or higher and 40 ° C. or lower from the viewpoint of yield.
• the reaction temperature in the sulfonation reaction is more preferably 0 ° C. or higher and 20 ° C. or lower, more preferably 0 ° C. or higher and 10 ° C. or lower, from the viewpoint of yield.
• neutralization can be performed by reacting an alkali aqueous solution having a molar amount of 1 to 1.5 mol times the theoretical value of the sulfonic acid group.
• alkaline aqueous solution examples include an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution, and an aqueous 2-aminoethanol solution.
• the hydrolysis reaction can be carried out by reacting at 90 ° C. or more and 200 ° C. or less for 30 minutes or more and 4 hours or less in the presence of water.
• the sulfonation reaction and neutralization reaction can be performed continuously. After completion of the neutralization reaction, purification can be performed by extraction, washing and the like.
• the present invention discloses the following olefin production method.
• the electronegativity of the oxide of the element is preferably 1.6 or more, more preferably 1.7 or more, still more preferably 1.8 or more, and preferably 2.6 or less, more preferably. Is 2.0 or less, The manufacturing method of the olefin as described in said ⁇ 1>.
• the supported amount of the oxide of the element with respect to the aluminum oxide is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and still more preferably. 0.8% by mass or more, and preferably 10% by mass or less, more preferably 9% by mass or less, still more preferably 8% by mass or less, still more preferably 7% by mass or less, and 2% by mass or less.
• a preparation method in which an oxide of the element is supported on aluminum oxide includes an aqueous suspension of aluminum oxide or a water-containing solid, a compound serving as an oxide source of the element or an oxide of the element, and ion-exchanged water.
• the compound serving as the oxide source of the element is preferably a water-soluble ammonium salt, metal alkoxide, oxo acid or a salt thereof, more preferably ammonium sulfate, ammonium tungstate, tetraethylorthosilicate, diammonium hydrogen phosphate
• the method for producing an olefin according to the above ⁇ 5> which is one or more selected from the group consisting of ammonium sulfate, ammonium tungstate, diammonium hydrogen phosphate, and tetraethylorthosilicate.
• the temperature when impregnating aluminum oxide with the compound serving as the oxide source of the element or the oxide of the element is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and even more preferably 50 ° C. or higher. More preferably, it is 60 ° C. or higher, and preferably 100 ° C. or lower, more preferably 95 ° C. or lower, still more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower, in the above ⁇ 5> or ⁇ 6>
• the manufacturing method of the olefin of description is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and even more preferably 50 ° C. or higher. More preferably, it is 60 ° C. or higher, and preferably 100 ° C. or lower, more preferably 95 ° C. or lower, still more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower, in the above ⁇ 5> or ⁇
• the calcination temperature after impregnation is preferably 300 ° C. or higher, more preferably 400 ° C. or higher, more preferably 450 ° C. or higher, and preferably 900 ° C. or lower, more preferably 850 ° C. or lower, still more preferably.
• ⁇ 9> Any of the above ⁇ 5> to ⁇ 8>, wherein the firing time is preferably 1 hour or more, more preferably 2 hours or more, and preferably 10 hours or less, more preferably 5 hours or less.
• ⁇ 10> The method for producing an olefin according to any one of ⁇ 5> to ⁇ 9>, wherein the calcination is performed in an inert gas, an oxidizing atmosphere, or a reducing atmosphere.
• ⁇ 12> The method for producing an olefin according to any one of ⁇ 1> to ⁇ 11>, wherein the aluminum oxide is ⁇ -alumina.
• the catalyst is prepared by one or more methods selected from an evaporation to dryness method, an adsorption method, an equilibrium adsorption method, a pore filling method, a spray method, and a precipitation method, The method for producing an olefin according to any one of 1> to ⁇ 12>.
• the average particle diameter of the catalyst is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, still more preferably 10 ⁇ m or more, still more preferably 20 ⁇ m or more, still more preferably 30 ⁇ m or more, and preferably 300 ⁇ m or less.
• it is 250 ⁇ m or less, more preferably 200 ⁇ m or less, even more preferably 150 ⁇ m or less, even more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less, according to any one of ⁇ 1> to ⁇ 13> above Production method of olefin.
• BET specific surface area of the catalyst is preferably 100 m 2 / g or more, more preferably 120 m 2 / g or more, further preferably 140 m 2 / g or more, and, preferably 500 meters 2 / g or less, more
• the average pore diameter of the catalyst is preferably 5 nm or more, more preferably 7 nm or more, still more preferably 9 nm or more, and preferably 50 nm or less, more preferably 40 nm or less, still more preferably 25 nm or less, more
• the pore volume of the ⁇ 17> catalyst is preferably 0.20 cm 3 / g or more, more preferably 0.25 cm 3 / g or more, still more preferably 0.30 cm 3 / g or more, and preferably 2. 0 cm 3 / g or less, more preferably 1.5 cm 3 / g or less, more preferably 1.2 cm 3 / g or less, even more preferably 1.0 cm 3 / g or less, even more preferably 0.7 cm 3 / g.
• ⁇ 18> The method for producing an olefin according to any one of ⁇ 1> to ⁇ 17>, wherein the alcohol is a primary alcohol.
• the carbon number of the alcohol is preferably 8 or more, more preferably 12 or more, still more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, still more preferably 18 or less.
• ⁇ 20> The method for producing an olefin according to any one of ⁇ 1> to ⁇ 19>, wherein the alcohol has 8 to 22 carbon atoms, preferably 12 to 20 carbon atoms, more preferably 14 to 18 carbon atoms. . ⁇ 21>
• ⁇ 22> The method for producing an olefin according to any one of ⁇ 1> to ⁇ 21>, wherein the dehydration reaction is performed by introducing an inert gas.
• the dehydration reaction is preferably performed at a reduced pressure of 0.03 MPa or more and 0.09 MPa or less or at normal pressure.
• the dehydration reaction is preferably not more than the boiling point of the raw material alcohol, specifically, preferably 150 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 220 ° C. or higher, even more preferably 230 ° C. or higher, and even more. Any one of the above ⁇ 1> to ⁇ 23>, preferably performed at 270 ° C. or higher, and preferably performed at 350 ° C. or lower, more preferably 310 ° C. or lower, still more preferably 295 ° C. or lower, and even more preferably 290 ° C. or lower.
• the manufacturing method of the olefin as described in any one of. ⁇ 25> The method for producing an olefin according to any one of ⁇ 1> to ⁇ 24>, wherein the dehydration reaction is performed in a liquid phase.
• Catalyst preparation example 1 In a 500 mL eggplant flask, aluminum oxide “GP-20” (manufactured by Mizusawa Chemical Co., Ltd., BET specific surface area 189 m 2 / g, average particle size 33 ⁇ m, average pore size 12.1 nm, pore volume 0.44 cm 3 / g) 10.0 g, ammonium sulfate 0.69 g (manufactured by Wako Pure Chemical Industries, Ltd., 5% by mass with respect to aluminum oxide in terms of SO 4 ), 100 g of ion-exchanged water are charged, and water is added using a rotary evaporator (70 ° C., 30 mmHg). Evaporate to dryness.
• GP-20 manufactured by Mizusawa Chemical Co., Ltd., BET specific surface area 189 m 2 / g, average particle size 33 ⁇ m, average pore size 12.1 nm, pore volume 0.44 cm 3 / g
• the obtained powder was dried at 120 ° C. for 12 hours and calcined in air at 500 ° C. for 3 hours to prepare a solid acid catalyst.
• the obtained solid acid catalyst had a BET specific surface area of 162 m 2 / g, an average particle diameter of 36 ⁇ m, an average pore diameter of 11.8 nm, and a pore volume of 0.41 cm 3 / g.
• Catalyst preparation example 2 Instead of ammonium sulfate, a solid was prepared in the same manner as in Catalyst Preparation Example 1 except that 0.56 g of ammonium tungstate (manufactured by Wako Pure Chemical Industries, Ltd., 5 mass% with respect to aluminum oxide in terms of WO 3 ) was used. An acid catalyst was prepared. The obtained solid acid catalyst had a BET specific surface area of 159 m 2 / g, an average particle diameter of 34 ⁇ m, an average pore diameter of 11.7 nm, and a pore volume of 0.40 cm 3 / g.
• Catalyst preparation example 3 In the same manner as in Catalyst Preparation Example 1, except that 0.65 g of diammonium hydrogen phosphate (manufactured by Wako Pure Chemical Industries, Ltd., 5% by mass with respect to aluminum oxide in terms of PO 4 ) was used instead of ammonium sulfate. A solid acid catalyst was prepared. The obtained solid acid catalyst had a BET specific surface area of 154 m 2 / g, an average particle diameter of 33 ⁇ m, an average pore diameter of 11.9 nm, and a pore volume of 0.41 cm 3 / g.
• Catalyst preparation example 4 In place of ammonium sulfate, except that 1.73 g of tetraethyl orthosilicate (Wako Pure Chemical Industries, Ltd., 5 mass% with respect to aluminum oxide in terms of SiO 2 ) and 0.2 g of 0.1 N nitric acid aqueous solution were used, A solid acid catalyst was prepared in the same manner as in Catalyst Preparation Example 1. The obtained solid acid catalyst had a BET specific surface area of 158 m 2 / g, an average particle diameter of 38 ⁇ m, an average pore diameter of 11.8 nm, and a pore volume of 0.42 cm 3 / g.
• Catalyst preparation example 5 A solid acid catalyst was prepared in the same manner as in Catalyst Preparation Example 1, except that 0.14 g of ammonium sulfate was added (Wako Pure Chemical Industries, Ltd., 1% by mass with respect to aluminum oxide in terms of SO 4 ). did.
• the obtained solid acid catalyst had a BET specific surface area of 164 m 2 / g, an average particle diameter of 35 ⁇ m, an average pore diameter of 11.9 nm, and a pore volume of 0.42 cm 3 / g.
• Catalyst preparation example 6 Instead of ammonium sulfate, 0.12 g of ammonium tungstate (Wako Pure Chemical Industries, Ltd., 1% by mass with respect to aluminum oxide in terms of WO 3 ) was used, and the solid was prepared in the same manner as in Catalyst Preparation Example 1. An acid catalyst was prepared. The obtained solid acid catalyst had a BET specific surface area of 152 m 2 / g, an average particle diameter of 36 ⁇ m, an average pore diameter of 12.0 nm, and a pore volume of 0.41 cm 3 / g.
• Catalyst preparation example 7 Instead of ammonium sulfate, except that 0.35 g of tetraethylorthosilicate (Wako Pure Chemical Industries, Ltd., 1% by mass with respect to aluminum oxide in terms of SiO 2 ) and 0.1 g of 0.1 N nitric acid aqueous solution were used, A solid acid catalyst was prepared in the same manner as in Catalyst Preparation Example 1. The obtained solid acid catalyst had a BET specific surface area of 110 m 2 / g, an average particle diameter of 35 ⁇ m, an average pore diameter of 11.9 nm, and a pore volume of 0.41 cm 3 / g.
• Comparative catalyst preparation example 1 A solid acid was prepared in the same manner as in Catalyst Preparation Example 1 except that 1.25 g of cerium nitrate (Wako Pure Chemical Industries, Ltd., 5% by mass with respect to aluminum oxide in terms of CeO 2 ) was used instead of ammonium sulfate. A catalyst was prepared. The obtained solid acid catalyst had a BET specific surface area of 154 m 2 / g, an average particle diameter of 35 ⁇ m, an average pore diameter of 11.9 nm, and a pore volume of 0.41 cm 3 / g.
• Comparative catalyst preparation example 2 The same as in Catalyst Preparation Example 1 except that 1.33 g of lanthanum nitrate (Wako Pure Chemical Industries, Ltd., 2.5% by mass with respect to aluminum oxide in terms of La 2 O 3 ) was used instead of ammonium sulfate.
• a solid acid catalyst was prepared by the method. The obtained solid acid catalyst had a BET specific surface area of 159 m 2 / g, an average particle diameter of 34 ⁇ m, an average pore diameter of 11.9 nm, and a pore volume of 0.42 cm 3 / g.
• Example 1 [Olefination reaction] In a four-necked flask equipped with a 100 mL stirrer, 50.0 g (0.19 mol) of 1-octadecanol “CALCOAL 8098” (manufactured by Kao Corporation), 1.5 g of the solid acid catalyst prepared in Catalyst Preparation Example 1 ( 3% by mass with respect to the alcohol) was stirred, and the reaction was carried out for 1 hour while stirring and flowing nitrogen through the system at 280 ° C. (nitrogen flow rate: 50 mL / min).
• CALCOAL 8098 manufactured by Kao Corporation
• Comparative Examples 1 to 4 [Olefination reaction] Except that the catalyst used and the reaction conditions were changed as shown in Table 1, the reaction was carried out in the same manner as in Example 1, and the solution after completion of the reaction was measured. The reaction conditions and results are summarized in Table 1. In Comparative Example 1, only the aluminum oxide used in Catalyst Preparation Example 1 was used as a catalyst.
• the production method of the present invention can produce a long-chain olefin in a high yield in a short reaction time in the dehydration reaction of a long-chain aliphatic primary alcohol.
• Example 10 [Sulfonation reaction] Step of obtaining a sulfonated product A mechanical stirrer and a thermometer were attached to a 3000 mL four-necked flask, and two dropping funnels were further attached. After reducing the pressure in this four-necked flask to atmospheric pressure with nitrogen and replacing with nitrogen, 211 g of 1,4-dioxane (Wako Pure Chemical Industries, Ltd.) and chloroform (Wako Pure Chemical Industries, Ltd.) 975 g) was added and cooled in an ice bath so that the temperature of the solution in the four-necked flask was 5 ° C. or lower.
• Step of neutralization and hydrolysis treatment In a 3000 mL SUS beaker, 119 g of a 48 mass% sodium hydroxide aqueous solution and 302 g of ion-exchanged water were cooled in an ice bath. After sufficiently cooling, the mixture was stirred with a homomixer while gradually adding the liquid obtained in the reaction step while cooling in an ice bath. The whole amount of the liquid obtained in the reaction step was charged into the beaker, and then stirred at 5000 rpm for 3 hours.
• the liquid obtained in the neutralization step was filled into an eggplant-shaped flask, and chloroform, 1,4-dioxane, and water were distilled off by a rotary evaporator while heating in a hot water bath at 55 ° C.
• 670 g of ion-exchanged water was added to prepare an aqueous solution containing 40% by mass sodium olefin sulfonate.
• 400 g of the aqueous solution was placed in a 1 L autoclave and reacted at 160 ° C. for 3 hours to obtain 385 g of an aqueous sodium olefin sulfonate solution.
• the effective component of the obtained aqueous sodium olefin sulfonate solution was 16% by mass.
• the amount of the active ingredient was determined by potentiometric titration using a benzethonium chloride solution (synthetic detergent test method JIS K3362).

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