Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
  • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
  • C07C5/25—Migration of carbon-to-carbon double bonds
  • C07C5/2506—Catalytic processes
  • C07C5/2518—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
• • 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
  • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
  • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
  • C07C5/25—Migration of carbon-to-carbon double bonds
  • C07C5/2506—Catalytic processes
  • C07C5/2512—Catalytic processes with metal oxides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
  • C07C2521/04—Alumina
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Definitions

• the present invention relates to a method for producing internal olefins.
• Patent Document 1 discloses a method for isomerizing a 1-alkene to an internal alkene, comprising: a) combining at least one 1-alkene with a catalyst in a liquid phase at a temperature of from about 50° C.
• the catalyst is (i) at least one Group VIII formed by contacting a transition metal salt and (ii) at least one alkylaluminum compound to obtain a first mixture; and b) combining the first mixture of step a) with at least one acid washed clay at a temperature of about 100° C. to about 300° C. to form a final mixture.
• the present invention relates to a process for producing an internal olefin, comprising the following steps 1 and 2 in this order.
• Step 1 Step of isomerizing a raw material olefin having 8 to 36 carbon atoms to obtain an internal olefin containing 1-olefin
• Step 2 The 1-olefin contained in the internal olefin obtained in Step 1 is heated to the reaction temperature Lower temperature isomerization process
• the olefin isomerization process described in US Pat. No. 5,900,006 allows for the isomerization of alpha olefins (1-olefins) to yield final products containing internal alkenes and low levels of oligomers, The amount of residual alpha olefins is not considered.
• the present invention relates to a method for producing an internal olefin with a reduced 1-olefin content while suppressing changes in the double bond distribution of the internal olefin.
• the present inventors isomerized a raw material olefin having a specific number of carbon atoms to obtain an internal olefin containing a 1-olefin, and then isomerized the internal olefin at a lower reaction temperature to improve the double bond distribution of the internal olefin.
• the present invention relates to the following [1]. [1] A method for producing an internal olefin, comprising steps 1 and 2 in this order.
• Step 1 Step of isomerizing a raw material olefin having 8 to 36 carbon atoms to obtain an internal olefin containing 1-olefin
• Step 2 The 1-olefin contained in the internal olefin obtained in Step 1 is heated to the reaction temperature Lower temperature isomerization process
• a method for producing an internal olefin with a reduced 1-olefin content while suppressing changes in the double bond distribution of the internal olefin is provided.
• Step 1 Step of isomerizing a raw material olefin having 8 to 36 carbon atoms to obtain an internal olefin containing 1-olefin
• Step 2 The 1-olefin contained in the internal olefin obtained in Step 1 is heated to the reaction temperature Step of Isomerizing at a Lower Temperature
• a method for producing an internal olefin with a reduced 1-olefin content while suppressing changes in the double bond distribution of the internal olefin Step 2: Step of isomerizing a raw material olefin having 8 to 36 carbon atoms to obtain an internal olefin containing 1-olefin
• Step 2 The 1-olefin contained in the internal olefin obtained in Step 1 is heated to the reaction temperature Step of Isomerizing at a Lower Temperature
• Internal olefins are produced by isomerizing raw material olefins, that is, rearranging double bond positions.
• isomerization (isomerization reaction) may be internal isomerization (internal isomerization reaction).
• the double bonds of internal olefins have a distribution in their positions.
• Internal olefins have different physical properties such as fluidity, melting point, and cloud point depending on the distribution of their double bond positions. Therefore, internal olefins have an appropriate double bond distribution depending on the application.
• the amount of 1-olefin in the internal olefin has a great influence on the above physical properties. For example, according to International Publication No.
• the pour point can be lowered from about -10°C to -22°C (at least systems containing one C14-C24 olefin).
• the amount of 1-olefin in the internal olefin is large, the quality tends to be deteriorated, such as reduced fluidity.
• step 2 provides a method for reducing the 1-olefin content while suppressing changes in the double bond distribution of the internal olefin.
• a 1-olefin having 8 to 36 carbon atoms is used as a starting material and isomerized to obtain an internal olefin, the reaction proceeds as follows.
• R represents an alkyl group having 4 to 32 carbon atoms.
• a 1-olefin (raw material olefin) (1) having 8 or more carbon atoms undergoes an internal isomerization reaction represented by (I) to produce an internal olefin (2). Further, internal olefin (2) is further subjected to rearrangement reaction (internal isomerization reaction) at the double bond position represented by (II) to produce internal olefin (3).
• Such isomerization of double bonds of olefins proceeds by successive equilibrium reactions.
• the equilibrium constant K (2-3) is about 1
• the equilibrium constant after the subsequent isomerization reaction (III) is about 1.
• the equilibrium constant K (1-2) tends to increase as the temperature decreases. That is, it is considered that the isomerization reaction of 1-olefin (1) to 2-olefin (2) proceeds more favorably at a lower temperature than the subsequent isomerization reaction of internal double bonds.
• step 1 after obtaining an internal olefin having the desired average double bond position, in step 2, by isomerizing at a temperature lower than the reaction temperature of step 1 (isomerization reaction temperature) In step 2, internal isomerization of 1-olefins to 2-olefins occurs preferentially, thereby suppressing changes in the double bond distribution of the internal olefins and producing internal olefins with a reduced 1-olefin content. is presumed to have been obtained. It should be noted that the above mechanism regarding the effect of the present invention is an assumption, and is not limited to this. Hereinafter, after explaining the raw material olefin and the catalyst used in the present invention, Step 1 and Step 2 will be explained in detail.
• the raw material olefin is an olefin having 8 or more and 36 or less carbon atoms from the viewpoint of reactivity.
• the number of carbon atoms in the starting olefin is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, still more preferably 14 or more, still more preferably 16 or more, from the viewpoint of usefulness of the resulting internal olefin, and , preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, still more preferably 18 or less.
• starting olefins examples include octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, heneicosene, docosene, tricosene, tetracosene, and the like. , hexadecene and octadecene are preferred.
• the double bond position of the starting olefin is not particularly limited, but is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, still more preferably 1 or 2 from the viewpoint of availability. That is, the raw material olefin is preferably 1-olefin, 2-olefin, 3-olefin or 4-olefin, more preferably 1-olefin, 2-olefin or 3-olefin, still more preferably 1-olefin or 2-olefin is an olefin.
• the starting olefin may be a mixture of two or more olefins having different double bond positions.
• the raw material olefin preferably contains at least 1-olefin, and the 1-olefin is preferably a linear 1-olefin.
• the average double bond position of the starting olefin is preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.8 or less, and 1.0 or more.
• the starting olefin may be obtained by any method, and commercially available olefins having 8 to 36 carbon atoms, preferably 1-olefins having 8 to 36 carbon atoms may be used as starting olefins. It may be produced by a dehydration reaction using an aliphatic primary alcohol having 8 or more and 36 or less (linear aliphatic primary alcohol having 8 or more and 36 or less carbon atoms) as a raw material (raw material alcohol).
• a reaction formula is represented as follows.
• R represents an alkyl group having 4 or more carbon atoms, and from the viewpoint of usefulness, it is preferably a linear alkyl group having 4 or more carbon atoms.
• Aliphatic primary alcohol (raw material alcohol) (10) produces 1-olefin (1) by intramolecular dehydration represented by (IV), and as shown in (V) and (VI), Intermolecular dehydration produces 1-olefin (1) via reaction intermediate dialkyl ether (11). A part of the produced 1-olefin (1) becomes internal olefins such as 2-olefins with the double bond position closer to the terminal by isomerization reaction.
• the raw material alcohol may be either petroleum-derived alcohol or natural raw material-derived alcohol.
• Naturally derived aliphatic primary alcohols include those derived from coconut oil, palm oil, palm kernel oil, soybean oil, rapeseed oil, beef tallow, lard, tall oil, fish oil, and the like.
• aliphatic primary alcohols include n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n- tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol, n-nonadecanol, n-eicosanol, n-heneicosanol, n-docosanol , n-tricosanol, n-tetracosanol, etc.
• n-hexadecanol and n-octadecanol are preferred.
• the method for producing the raw material olefin from the raw material alcohol is not particularly limited, and it may be produced by a known method, but it is preferably produced by a liquid-phase dehydration reaction in the presence of a solid catalyst, preferably in the presence of a solid acid catalyst.
• a metal oxide containing aluminum is preferable as the solid catalyst.
• the reaction temperature of the liquid-phase dehydration reaction is preferably 255° C. or higher and 300° C. or lower.
• the reaction pressure is more preferably normal pressure.
• Steps 1 and 2 are preferably carried out in the presence of a catalyst from the viewpoint of the reactivity of the isomerization reaction.
• the catalyst for steps 1 and 2 preferably contains elements of the 3rd to 5th periods, more preferably aluminum (Al), silicon (Si), and titanium (Ti). , iron (Fe), zinc (Zn), yttrium (Y), zirconium (Zr), and tin (Sn), and more preferably at least aluminum.
• the catalyst is preferably a solid catalyst, more preferably a solid acid catalyst.
• the catalyst is preferably selected from aluminum oxide catalysts (hereinafter also simply referred to as "aluminum oxide”), aluminum phosphate catalysts, and zeolite (aluminosilicate) catalysts. at least one catalyst, more preferably an aluminum oxide catalyst.
• aluminum oxide aluminum oxide catalysts
• zeolite aluminosilicate
• at least one catalyst more preferably an aluminum oxide catalyst.
• reactivity means high catalytic activity in the internal isomerization reaction
• reaction selectivity means reactions other than the internal isomerization reaction, such as dimerization reaction, etc., are unlikely to occur.
• Crystal forms of aluminum oxide (Al 2 O 3 ) include ⁇ , ⁇ , ⁇ , etc.
• the aluminum oxide is preferably ⁇ -alumina.
• the purity of aluminum oxide in the aluminum oxide catalyst is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass, from the viewpoint of reactivity and reaction selectivity.
• the upper limit is not particularly limited, and is 100% by mass.
• the average pore diameter of the catalyst is preferably 0.6 nm or more, more preferably 3 nm or more, still more preferably 6 nm or more, and preferably 20 nm or less, more preferably 15 nm or less, from the viewpoint of reactivity and reaction selectivity. , and more preferably 12.3 nm or less.
• the average pore diameter of the solid catalyst is measured by the method described in Examples.
• the pore volume of the catalyst is preferably 0.1 mL/g or more, more preferably 0.15 mL/g or more, still more preferably 0.2 mL/g or more, still more preferably 0, from the viewpoint of reactivity and reaction selectivity. .3 mL/g or more, and preferably 2.0 mL/g or less, more preferably 1.8 mL/g or less, even more preferably 1.6 mL/g or less, even more preferably 0.8 mL/g or less, and further It is preferably 0.6 mL/g or less.
• the BET specific surface area of the catalyst is preferably 80 m 2 /g or more, more preferably 100 m 2 /g or more, still more preferably 120 m 2 /g or more, and preferably 700 m 2 /g or more. 2 /g or less, more preferably 600 m 2 /g or less, still more preferably 300 m 2 /g or less, still more preferably 280 m 2 /g or less, still more preferably 250 m 2 /g or less.
• the pore volume and BET specific surface area of the solid catalyst are measured by the methods described in Examples.
• the catalyst may be prepared by any method, but the precipitation method, impregnation method, sol-gel method, alkoxide method, pH swing method, etc. are preferred from the viewpoint of preparing a catalyst having desired physical properties and obtaining high catalytic activity.
• the method for preparing aluminum oxide which is a suitable catalyst in the present embodiment, is preferably a precipitation method, a sol-gel method, an alkoxide method, a pH swing method, or the like, and more preferably a pH swing method. be.
• the obtained aluminum oxide is preferably calcined, and from the viewpoint of obtaining high catalytic activity, the calcination temperature is preferably 400° C. or higher, more preferably 450° C.
• the atmosphere for firing is not particularly limited, and can be performed under an inert gas, an oxidizing atmosphere, or a reducing atmosphere. Further, it may be in a sealed state or in a gas circulation state. In the present invention, from the viewpoint of catalytic activity, it is preferably under a stream of air or oxygen.
• the pH swing method is one of precipitation methods, and is a precipitation method using an aluminum salt and an inorganic base as raw materials, in which aqueous solutions of both raw materials are alternately added to form a precipitate while raising and lowering the pH.
• the pH swing method is one of precipitation methods, and is a precipitation method using an aluminum salt and an inorganic base as raw materials, in which aqueous solutions of both raw materials are alternately added to form a precipitate while raising and lowering the pH.
• aluminum chloride and ammonia are used as raw materials, if ammonia water is gradually added to the aluminum chloride aqueous solution, the pH will rise and exceed 9. After that, when the aluminum chloride aqueous solution is gradually added, the pH drops to less than 4.
• the pH change to an amplitude that is outside the range of 4 to 9, which is the precipitation formation pH of aluminum
• the fine crystals of aluminum generated in the range of 4 to 9, which is the precipitation formation pH are dissolved, and the pH is lowered. It can be used for crystal growth when it falls within the precipitation formation pH, and can gradually increase the crystal grain size.
• the crystal grain size, specific surface area, and pore structure can be adjusted by adjusting the temperature, holding time, raw material concentration, pH amplitude, swing number, etc., and the crystal grain size after firing and the gap between the crystal grains. Pore diameter, pore volume, specific surface area, etc. can be adjusted.
• the catalyst obtained as described above is in an agglomerated state. It is preferable to use In the case of molding into a noodle shape, it is preferable to obtain a noodle-shaped molded product by extrusion molding, and in the case of molding into a pellet shape, it is preferable to obtain a pellet-shaped molded product by tablet compression molding. In the case of molding into granules, noodles, pellets, etc., the mixture may be kneaded with a small amount of binder, dried if necessary, molded, and then fired. Examples of the binder used here include polymer compounds and inorganic compounds.
• polymer compounds include cellulose-based resins such as carboxymethyl cellulose and hydroxyethyl cellulose; fluorine-based resins such as polytetrafluoroethylene and polyvinylidene fluoride; urethane resins; epoxy resins; polyester resins; Polycarbotitanium; polytitanocarbosilane and the like are exemplified.
• inorganic compounds include inorganic compound sols such as silica and alumina. As the binder, a polymer compound is preferable from the viewpoint of productivity of the catalyst.
• the average particle size of the powder is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, still more preferably 5 ⁇ m or more, still more preferably 8 ⁇ m or more, from the viewpoint of reactivity. It is 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, and still more preferably 30 ⁇ m or less.
• the average particle size is measured by the method described in Examples.
• the average particle size of the granules is preferably 0.2 mm or more, more preferably 0.4 mm or more, and still more preferably 0.4 mm or more, from the viewpoints of ease of catalyst recovery and reactivity. It is 6 mm or more, and preferably 2.0 mm or less, more preferably 1.3 mm or less, and even more preferably 0.8 mm or less.
• the average particle size of the granules is measured as follows.
• the average diameter is preferably 0.3 mm or more, more preferably 0.5 mm or more, still more preferably 0.7 mm or more, from the viewpoint of catalyst strength and reactivity. is 2.5 mm or less, more preferably 2.3 mm or less, still more preferably 2.0 mm or less.
• the average length is preferably 8 mm or less, more preferably 6 mm or less, and even more preferably 5 mm or less, from the viewpoint of uniformity during filling and catalyst strength. is 2 mm or more, more preferably 3 mm or more, and still more preferably 4 mm or more. The average diameter and average length are measured with vernier calipers.
• the average diameter and average height are preferably 1.5 mm or more, more preferably 2.0 mm or more, and still more preferably 2.5 mm or more, from the viewpoint of catalyst strength and reactivity. , and preferably 5.0 mm or less, more preferably 4.0 mm or less, and even more preferably 3.0 mm or less.
• the average diameter and average height are measured with vernier calipers.
• the average diameter is preferably 1.0 mm or more, more preferably 1.5 mm or more, still more preferably 2.0 mm or more, from the viewpoint of ease of recovery and reactivity. is 5.0 mm or less, more preferably 4.0 mm or less, still more preferably 3.0 mm or less.
• the average diameter is measured with vernier calipers.
• the acid amount of the solid acid catalyst is preferably 0.1 mmol/g or more, more preferably 0.15 mmol/g or more, still more preferably 0, from the viewpoint of reactivity and reaction selectivity. .2 mmol/g or more, and preferably 1.5 mmol/g or less, more preferably 1.0 mmol/g or less, still more preferably 0.9 mmol/g or less, even more preferably 0.85 mmol/g or less, and further Preferably, it is 0.8 mmol/g or less.
• the acid content of the solid acid catalyst can be measured by a method generally used to determine the acid content, such as the ammonia temperature programmed desorption method (NH 3 -TPD).
• a commonly used measuring method can be used. For example, pretreatment, NH 3 adsorption treatment, and vacuum treatment are performed in order under the following conditions, and then TPD measurement is performed.
• Pretreatment Heat up to 200°C in helium over 20 minutes, hold for 1 hour
• NH3 adsorption treatment Adsorb NH3 at 50°C and 2.7 kPa for 10 minutes
• Vacuum treatment Treat at 50°C for 4 hours.
• Degree of vacuum 2.7kPa TPD measurement Flow helium gas at 50 mL/min, heat up to 600°C at a heating rate of 5°C/min
• the crushing strength of the solid catalyst is preferably 1 daN or more, more preferably 1.5 daN or more, still more preferably 2 daN or more, and preferably 11 daN or less, more preferably 10 daN or less, and still more preferably 9 daN or less.
• the crushing strength can be measured, for example, by applying a compressive force to the granulated or molded catalyst using a fracture tester or the like.
• the crushing pressure in the present specification is indicated by the magnitude of the force at which cracks start to occur in the catalyst when a compressing force is applied to the granulated or molded catalyst.
• the amount of the catalyst used is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass with respect to 100 parts by mass of the raw olefin from the viewpoint of reactivity. It is at least 50 parts by mass, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less.
• Organic solvent In the production method of the present invention, it is desirable that substantially no organic solvent is used from the viewpoint of productivity. However, in the production method of the present invention, 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 starting olefin and the internal olefin as the product, and does not inhibit the reaction, and may be a mixture. may Moreover, after the reaction, those which can be separated from the product by utilizing the boiling point difference are preferable.
• hydrocarbon-based organic solvents such as saturated aliphatic hydrocarbons and aromatic hydrocarbons are preferred.
• the saturated aliphatic hydrocarbon may be linear or branched. Specific examples of saturated aliphatic hydrocarbons include compounds having 10 to 35 carbon atoms such as tridecane, hexadecane, octadecane, eicosane, docosane, triacontane and squalane.
• the saturated aliphatic hydrocarbons may be liquid paraffin, naphthenic hydrocarbons, and mixtures such as isoparaffinic hydrocarbons. In addition, it is possible to use those that are solid at room temperature but liquid at the reaction temperature, such as solid paraffin. Oligomers such as propylene and isobutene can also be used as saturated aliphatic hydrocarbons.
• aromatic hydrocarbons include alkylbenzenes and alkylnaphthalenes such as n-dodecylbenzene, n-tridecylbenzene, n-tetradecylbenzene, n-pentadecylbenzene, n-hexadecylbenzene and diisopropylnaphthalene. .
• Step 1 is a step of isomerizing a raw material olefin having 8 to 36 carbon atoms to obtain an internal olefin containing a 1-olefin.
• the isomerization (isomerization reaction) in step 1 is preferably an internal isomerization reaction as the main reaction, but may include an isomerization reaction in which 2-olefin becomes 1-olefin.
• the reaction system in step 1 is not particularly limited, and may be either a heterogeneous system or a homogeneous system.
• a heterogeneous system is preferable from the viewpoint of efficiently recovering internal olefins including the produced 1-olefin.
• the reaction mode is not particularly limited, and a batch system or a continuous system can be selected as appropriate.
• the reaction system is a continuous system, either a fixed bed method or a suspended bed method may be employed. Among these, the fixed bed method is preferable from the viewpoint of ease of operation.
• reaction temperature is preferably 100° C. or higher, more preferably 120° C. or higher, and still more preferably 140° C. or higher. From the same point of view, the temperature is preferably 400° C. or lower, more preferably 350° C. or lower, and even more preferably 300° C. or lower.
• the reaction temperature is preferably 120° C. or higher, more preferably 140° C. or higher, still more preferably 160° C. or higher, still more preferably 180° C., from the viewpoints of reactivity and reaction selectivity. As mentioned above, it is more preferably 200° C.
• the reaction temperature is preferably 100° C. or higher, more preferably 120° C. or higher, from the viewpoint of reactivity and reaction selectivity. It is 400° C. or lower, more preferably 350° C. or lower, still more preferably 300° C. or lower, still more preferably 250° C. or lower, still more preferably 200° C. or lower, still more preferably 160° C. or lower.
• the reaction temperature (T 1 ) in step 1 may be an average value.
• the reaction temperature (T 1 ) in step 1 is preferably maintained at a constant temperature. That is, it is preferable that the fluctuation width of the reaction temperature (T 1 ) in step 1 is within a certain range.
• the fluctuation range of the reaction temperature (T 1 ) in step 1 is preferably 10° C. or less, more preferably 5° C. or less, even more preferably 3° C. or less, and even more preferably 1° C. or less.
• the range of variation may be 0°C or higher, or greater than 0°C.
• reaction pressure The pressure in the reaction vessel during the reaction is not particularly limited, and from the viewpoint of ease of reaction operation, the absolute pressure is preferably 1 MPa or less, more preferably 0.5 MPa or less, and still more preferably 0.1 MPa or less, that is, a large pressure. Atmospheric pressure is more preferred.
• reaction atmosphere An inert gas can be introduced into the reaction vessel during the reaction.
• the inert gas include nitrogen, argon, helium, etc. Nitrogen is preferable from the viewpoint of availability.
• reaction time When the reaction format is a batch type, the reaction time is preferably 0.25 hr or longer, more preferably 0.5 hr or longer, and still more preferably 1.0 hr or longer, from the viewpoint of reactivity and suppression of side reactions, And, it is preferably 20 hours or less, more preferably 16 hours or less, still more preferably 12 hours or less, still more preferably 8 hours or less, still more preferably 5 hours or less.
• the reaction format is a batch type, it is preferable to stir during the reaction in order to keep the inside of the system uniform. From the viewpoint, it is preferably 800 rpm or less, more preferably 700 rpm or less, and still more preferably 600 rpm or less. In addition, the stirring rotation speed is preferably 10 rpm or higher, more preferably 50 rpm or higher, and still more preferably 200 rpm or higher, from the viewpoint of reaction efficiency.
• the LHSV (liquid hourly space velocity) during the reaction is preferably 0.05/hr or more, more preferably 0.1/hr or more, and still more preferably 0.15 from the viewpoint of reaction efficiency. /hr or more, more preferably 0.5/hr or more, more preferably 1.0/hr or more, still more preferably 2.0/hr or more, and preferably 5.0/hr or less, more preferably 3.0/hr or less.
• the average double bond position of the internal olefin at the end of the reaction in Step 1 is preferably deeper than the average double bond position of the starting olefin (from the inside).
• the average double bond position of the internal olefin at the end of the reaction may be deeper (closer to the inside) than the raw material olefin, and from the viewpoint of the usefulness of the internal olefin, it is preferably 1.5 or more, more preferably 2.0 or more, more preferably 2.5 or more, more preferably 3.0 or more, still more preferably 3.3 or more, and preferably 8.0 or less, more preferably 6.0 or less, still more preferably is 5.5 or less, more preferably 5.0 or less, still more preferably 4.6 or less.
• the internal olefin obtained in step 1 can be obtained by separating the reactants and the catalyst.
• the internal olefin obtained in step 1 in the present specification (hereinafter also referred to as "reactant”) refers to the reactant obtained after isomerizing the raw material olefin, and at least 1-olefin and internal olefin and may contain side reaction products such as branched olefins and dimerized olefins.
• the content of the 1-olefin in the internal olefin containing the 1-olefin obtained in step 1 is preferably 20 mol parts per 100 mol parts of the total amount of the 1-olefin and the internal olefin, from the viewpoint of usefulness. Below, more preferably 15 mol parts or less, still more preferably 12 mol parts or less, still more preferably 10 mol parts or less, even more preferably 5 mol parts or less, still more preferably 3 mol parts or less. Although the lower limit is not particularly limited, it exceeds 0 mol parts, preferably 0.5 mol parts or more, and more preferably 1.0 mol parts or more, from the viewpoint of ease of production.
• Step 2 is a step of isomerizing the 1-olefin contained in the internal olefin obtained in Step 1 at a temperature lower than the reaction temperature of Step 1.
• Isomerization may be internal isomerization (internal isomerization reaction).
• the reaction system in Step 2 is not particularly limited, and may be either a heterogeneous system or a homogeneous system. A heterogeneous system is preferable from the viewpoint of efficiently recovering the internal olefin produced.
• the reaction mode is not particularly limited, and a batch system or a continuous system can be selected as appropriate.
• the reaction system is a continuous system, either a fixed bed method or a suspended bed method may be employed. Among these, the fixed bed method is preferable from the viewpoint of ease of operation.
• step 1 is a batch type
• step 1 and step 2 may be performed in the same reactor.
• reaction temperature From the viewpoint of reducing 1-olefins and suppressing changes in the average double bond position, the reaction is carried out at a temperature lower than that in step 1.
• the reaction temperature in step 2 is preferably 30° C. or more lower than the reaction temperature in step 1, more preferably 35° C. or more, from the viewpoint of reducing 1-olefin and suppressing the change in the average double bond position. temperature, more preferably 50° C. or more lower, more preferably 80° C. or more lower. That is, when the reaction temperature in step 1 is T 1 (° C.) and the reaction temperature in step 2 is T 2 (° C.), T 1 ⁇ T 2 (hereinafter also referred to as ⁇ T) is preferably 30° C.
• the reaction temperature (T 2 ) in step 2 may be appropriately selected in relation to the reaction temperature (T 1 ) in step 1 so that ⁇ T is within the above range.
• the reaction temperature T2 is preferably 30° C. or higher, more preferably 40° C. or higher, and preferably 350° C. or lower, more preferably 300° C. or lower, and still more preferably. is 250° C. or less, more preferably 225° C. or less.
• the reaction temperature T2 is preferably 30° C. or higher, more preferably 40° C. or higher, from the viewpoint of reducing 1-olefins and suppressing changes in the average double bond position.
• the reaction temperature T2 is preferably 30° C. or higher, more preferably 40° C. or higher, and preferably 350° C. or lower, more preferably 300° C. or lower, from the same viewpoint. , more preferably 250° C. or less, more preferably 225° C. or less, still more preferably 200° C. or less, still more preferably 150° C. or less, still more preferably 100° C. or less, still more preferably 60° C. or less.
• reaction temperature (T 2 ) in step 2 may be an average value.
• ⁇ T may be the difference between the average values of the reaction temperature (T 1 ) and the reaction temperature (T 2 ).
• the reaction temperature (T 2 ) in step 2 is preferably kept constant from the viewpoint of reducing 1-olefin. That is, it is preferable that the fluctuation width of the reaction temperature (T 2 ) in step 2 is within a certain range.
• the fluctuation range of the reaction temperature (T 2 ) in step 2 is preferably 50° C. or less, more preferably 40° C. or less, and even more preferably 40° C. or less, from the viewpoint of reducing 1-olefins and suppressing changes in the average double bond position. is 30° C. or lower, more preferably 20° C. or lower, still more preferably 10° C. or lower, even more preferably 5° C. or lower, still more preferably 3° C. or lower, and even more preferably 1° C. or lower.
• the range of variation may be 0°C or higher, or greater than 0°C.
• reaction pressure The pressure in the reaction vessel during the reaction is not particularly limited, and from the viewpoint of ease of reaction operation, the absolute pressure is preferably 1 MPa or less, more preferably 0.5 MPa or less, and still more preferably 0.1 MPa or less, that is, a large pressure. Atmospheric pressure is more preferred.
• reaction atmosphere An inert gas can be introduced into the reaction vessel during the reaction.
• the inert gas include nitrogen, argon, helium, etc. Nitrogen is preferable from the viewpoint of availability.
• reaction time When the reaction format is a batch system, the reaction time is preferably 0.05 hr or longer, more preferably 0.1 hr or longer, and still more preferably 0.1 hr or longer, from the viewpoint of reducing 1-olefins and suppressing changes in the average double bond position. is 0.15 hr or more, more preferably 0.25 hr or more, still more preferably 0.5 hr or more, still more preferably 0.8 hr or more, still more preferably 1.2 hr or more, still more preferably 1.7 hr or more, and It is preferably 60 hours or less, more preferably 50 hours or less, still more preferably 45 hours or less, and still more preferably 40 hours or less.
• the reaction format is a batch type, it is preferable to stir during the reaction in order to keep the inside of the system uniform. From the viewpoint, it is preferably 800 rpm or less, more preferably 700 rpm or less, and still more preferably 600 rpm or less. In addition, the rotational speed of stirring is preferably 20 rpm or higher, more preferably 100 rpm or higher, and still more preferably 300 rpm or higher, from the viewpoint of reaction efficiency.
• the LHSV (liquid hourly space velocity) during the reaction is preferably 0.05/hr or more, more preferably 0.1/hr, from the viewpoint of reducing 1-olefin and from the viewpoint of reaction efficiency. above, more preferably 0.15/hr or more, and preferably 5.0/hr or less, more preferably 3.0/hr or less, still more preferably 1.5/hr or less, still more preferably 0.5/hr or less. It is 7/hr or less, more preferably 0.5/hr or less, and still more preferably 0.3/hr or less.
• step 2 (Change in average double bond position of internal olefin)
• the average double bond position of the internal olefin at the end of the reaction in step 2 is ADBP 2
• ADBP 1 being the average double bond position of the internal olefin at the end of the reaction in step 1
• ⁇ ADBP being the absolute value of the difference between ADBP 2 and ADBP 1 (
• ⁇ ADBP is , preferably 0.1 or less, more preferably 0.08 or less, still more preferably 0.06 or less, still more preferably 0.04 or less, still more preferably 0.03 or less.
• the lower limit is not particularly limited, and is 0 or more.
• the internal olefin obtained in step 2 can be obtained by separating the reactants and the catalyst.
• the internal olefin obtained in step 2 has a lower 1-olefin content than the content of 1-olefin contained in the internal olefin obtained in step 1, and a change in the average double bond position. is suppressed.
• the internal olefin is useful as a raw material or intermediate raw material for surfactants, organic solvents, softeners, sizing agents, etc., and is useful as a raw material for surfactants.
• an ionic compound may be produced by introducing an ionic group into the internal olefin obtained by the production method of the present invention.
• sulfonating the obtained internal olefin to obtain an internal olefin sulfonate is exemplified.
• the method for producing the internal olefin sulfonate preferably comprises the following steps A to C.
• Step A Step of sulfonating the internal olefin produced by the method for producing an internal olefin of the present invention
• Step B Step of neutralizing the sulfonated product obtained in Step A
• Step C The medium obtained in Step B Step of hydrolyzing the hydrate
• the step A is also the next step.
• Step A is a step of sulfonating the internal olefin produced by the method for producing an internal olefin of the present invention, and a sulfonated product is obtained by this step A.
• the sulfonation reaction in step A can be carried out by reacting 1 mol of internal olefin with sulfur trioxide gas or sulfuric anhydride, preferably 1 mol or more and 1.2 mol or less.
• the reaction temperature in the sulfonation reaction is preferably 20° C. or higher and 40° C. or lower from the viewpoint of yield.
• the sulfonation reaction can also be carried out using liquid anhydrous sulfuric acid instead of sulfur trioxide gas under conditions of a reaction temperature of 0° C. or higher and 10° C. or lower.
• Step B is a step of neutralizing the sulfonated product obtained in step A, and the neutralized sulfonated product is obtained by this step B.
• Neutralization in step B can be carried out by reacting with an alkaline aqueous solution containing 1 to 1.5 molar times the theoretical amount of sulfonic acid groups.
• an alkaline aqueous solution used for neutralization an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution are preferably used.
• Step C is a step of hydrolyzing the neutralized product obtained in step B, and this step C yields an olefin sulfonate.
• the hydrolysis treatment in step C can be performed by reacting at 90° C. or higher and 200° C. or lower in the presence of water for 30 minutes or longer and 4 hours or shorter.
• the resulting internal olefin sulfonate is useful as a surfactant.
• the present invention discloses the following method for producing an internal olefin.
• a method for producing an internal olefin comprising steps 1 and 2 in this order.
• Step 1 Step of isomerizing a raw material olefin having 8 to 36 carbon atoms to obtain an internal olefin containing 1-olefin
• Step 2 The 1-olefin contained in the internal olefin obtained in Step 1 is heated to the reaction temperature Lower temperature isomerization process
• the reaction temperature in step 1 is preferably 100°C or higher, more preferably 120°C or higher, still more preferably 140°C or higher, and is preferably 400°C or lower, more preferably 350°C or lower, still more preferably
• the method for producing an internal olefin according to ⁇ 1>, wherein the temperature is 300°C or lower.
• the method for producing an internal olefin according to ⁇ 1>, wherein the reaction temperature in step 1 is 100°C or higher and 300°C or lower.
• the fluctuation range of the reaction temperature in step 1 is preferably 10° C. or less, more preferably 5° C. or less, still more preferably 3° C. or less, still more preferably 1° C.
• the pressure in the reaction vessel during the reaction in step 1 is preferably 1 MPa or less, more preferably 0.5 MPa or less, still more preferably 0.1 MPa or less, in absolute pressure, that is, the atmospheric pressure.
• ⁇ 7> The method for producing an internal olefin according to ⁇ 6>, wherein the inert gas is preferably nitrogen, argon or helium, more preferably nitrogen.
• the reaction type in step 1 is a batch type.
• the reaction time in step 1 is preferably 0.25 hr or longer, more preferably 0.5 hr or longer, still more preferably 1.0 hr or longer, and is preferably 20 hr or shorter, more preferably 16 hr or shorter, still more preferably is 12 hours or less, more preferably 8 hours or less, and still more preferably 5 hours or less.
• ⁇ 10> The method for producing an internal olefin according to ⁇ 8> or ⁇ 9>, wherein the reaction in step 1 is stirred.
• the rotational speed of stirring during the reaction in step 1 is preferably 800 rpm or less, more preferably 700 rpm or less, still more preferably 600 rpm or less, preferably 10 rpm or more, more preferably 50 rpm or more, and still more preferably The method for producing an internal olefin according to ⁇ 10>, wherein the speed is 200 rpm or more.
• ⁇ 12> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 7>, wherein the reaction mode of step 1 is a continuous system.
• the LHSV (liquid hourly space velocity) during the reaction in step 1 is preferably 0.05/hr or more, more preferably 0.1/hr or more, still more preferably 0.15/hr or more, and still more preferably 0 .5/hr or more, more preferably 1.0/hr or more, still more preferably 2.0/hr or more, and preferably 5.0/hr or less, more preferably 3.0/hr or less , the method for producing an internal olefin according to ⁇ 12>.
• ⁇ 14> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 13>, wherein the reaction temperature in step 2 is lower than the reaction temperature in step 1 by 30°C or more.
• the difference T 1 -T 2 (hereinafter also referred to as ⁇ T) between the reaction temperature T 1 (°C) in step 1 and the reaction temperature T 2 (°C) in step 2 is preferably 35°C or more, more preferably 50° C. or higher, more preferably 80° C. or higher, and preferably 240° C. or lower, more preferably 200° C. or lower, still more preferably 150° C. or lower, according to any one of ⁇ 1> to ⁇ 14> A method for producing internal olefins.
• the reaction temperature T2 in step 2 is preferably 30°C or higher, more preferably 40°C or higher, and is preferably 350°C or lower, more preferably 300°C or lower, further preferably 250°C or lower, and further preferably The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 15>, wherein the temperature is preferably 225°C or lower.
• the fluctuation range of the reaction temperature in step 2 is preferably 50° C. or less, more preferably 40° C. or less, still more preferably 30° C. or less, still more preferably 20° C. or less, still more preferably 10° C.
• the carbon number of the starting olefin is preferably 10 or more, more preferably 12 or more, still more preferably 14 or more, still more preferably 16 or more, and preferably 24 or less, more preferably 22 or less, and still more preferably is 20 or less, more preferably 18 or less.
• ⁇ 20> The method for producing an internal olefin according to ⁇ 19>, wherein the 1-olefin is a linear 1-olefin.
• ⁇ 21> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 20>, wherein steps 1 and 2 are performed in the presence of a catalyst.
• the catalyst preferably contains a 3rd to 5th period element, more preferably aluminum (Al), silicon (Si), titanium (Ti), iron (Fe), zinc (Zn), yttrium
• the method for producing an internal olefin according to ⁇ 21> which contains at least one selected from (Y), zirconium (Zr), and tin (Sn), more preferably at least aluminum.
• Y aluminum
• Zr zirconium
• Sn tin
• ⁇ 24> The method for producing an internal olefin according to any one of ⁇ 21> to ⁇ 23>, wherein the catalyst is a solid acid catalyst.
• the catalyst is an aluminum oxide catalyst.
• the reaction temperature in step 1 is preferably 120°C or higher, more preferably 140°C or higher, still more preferably 160°C or higher, still more preferably 180°C or higher, still more preferably 200°C or higher, and preferably The method for producing an internal olefin according to ⁇ 25>, wherein the temperature is 400°C or lower, more preferably 350°C or lower, and still more preferably 300°C or lower.
• the reaction temperature in step 2 is preferably 30°C or higher, more preferably 40°C or higher, still more preferably 60°C or higher, still more preferably 80°C or higher, still more preferably 120°C or higher, and preferably The method for producing an internal olefin according to ⁇ 25> or ⁇ 26>, wherein the temperature is 350°C or lower, more preferably 300°C or lower, still more preferably 250°C or lower, and even more preferably 225°C or lower.
• the fluctuation range of the reaction temperature in step 2 is preferably 50°C or less, more preferably 40°C or less, still more preferably 30°C or less, still more preferably 20°C or less, still more preferably 10°C or less, and even more preferably Production of the internal olefin according to any one of ⁇ 25> to ⁇ 27>, wherein the temperature is 5°C or lower, more preferably 3°C or lower, more preferably 1°C or lower, and 0°C or higher or higher than 0°C.
• Method. ⁇ 29> The method for producing an internal olefin according to any one of ⁇ 21> to ⁇ 24>, wherein the catalyst is a zeolite catalyst.
• the reaction temperature in step 1 is preferably 100°C or higher, more preferably 120°C or higher, and is preferably 400°C or lower, more preferably 350°C or lower, still more preferably 300°C or lower, still more preferably
• the reaction temperature in step 2 is preferably 30°C or higher, more preferably 40°C or higher, and is preferably 350°C or lower, more preferably 300°C or lower, still more preferably 250°C or lower, and still more preferably
• the fluctuation range of the reaction temperature in step 2 is preferably 50°C or less, more preferably 40°C or less, still more preferably 30°C or less, still more preferably 20°C or less, still more preferably 10°C or less, and even more preferably Production of internal olefin according to any one of ⁇ 29> to ⁇ 31>, wherein the temperature is 5°C or lower, more preferably 3°C or lower, more preferably 1°C or lower, and 0°C or higher or higher than 0°C. Method.
• the absolute value of the difference between the average double bond position of the internal olefin obtained in step 1 and the average double bond position of the internal olefin obtained in step 2 is preferably 0.1 or less, more preferably is 0.08 or less, more preferably 0.06 or less, still more preferably 0.04 or less, still more preferably 0.03 or less.
• ⁇ 34> The internal olefin according to any one of ⁇ 1> to ⁇ 33>, wherein the average double bond position of the internal olefin at the end of the reaction in step 1 is further inward than the average double bond position of the starting olefin. manufacturing method.
• the average double bond position of the internal olefin at the end of the reaction in step 1 is preferably 1.5 or more, more preferably 2.0 or more, still more preferably 2.5 or more, still more preferably 3.0 or more.
• the content of 1-olefin in the internal olefin containing 1-olefin obtained in step 1 is preferably 20 mole parts or less, more than preferably 15 mol parts or less, more preferably 12 mol parts or less, still more preferably 10 mol parts or less, still more preferably 5 mol parts or less, still more preferably 3 mol parts or less, and more than 0 mol parts, preferably is 0.5 mol parts or more, more preferably 1.0 mol parts or more.
• ⁇ 37> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 36>, wherein an inert gas is introduced into the reaction vessel during the reaction in step 2.
• the inert gas is preferably nitrogen, argon, or helium, more preferably nitrogen.
• the isomerization reaction in step 2 is a batch system.
• the method for producing an internal olefin according to ⁇ 39>, wherein the reaction time in step 2 is 0.05 hr or more and 60 hr or less.
• the reaction time in step 2 is preferably 0.05 hr or longer, more preferably 0.1 hr or longer, still more preferably 0.15 hr or longer, still more preferably 0.25 hr or longer, still more preferably 0.5 hr or longer, and further preferably 0.5 hr or longer. preferably 0.8 hr or more, more preferably 1.2 hr or more, still more preferably 1.7 hr or more, and preferably 60 hr or less, more preferably 50 hr or less, still more preferably 45 hr or less, still more preferably 40 hr or less.
• ⁇ 42> The method for producing an internal olefin according to any one of ⁇ 39> to ⁇ 41>, wherein the reaction in step 2 is stirred.
• the rotation speed of stirring during the reaction in step 2 is preferably 800 rpm or less, more preferably 700 rpm or less, still more preferably 600 rpm or less, and is preferably 20 rpm or more, more preferably 100 rpm or more, and still more preferably The method for producing an internal olefin according to ⁇ 42>, wherein the speed is 300 rpm or more.
• ⁇ 44> The process for producing an internal olefin according to any one of ⁇ 1> to ⁇ 38>, wherein the isomerization reaction in step 2 is continuous.
• the LHSV (liquid hourly space velocity) during the reaction in step 2 is preferably 0.05/hr or more, more preferably 0.1/hr or more, still more preferably 0.15/hr or more, and , preferably 5.0/hr or less, more preferably 3.0/hr or less, still more preferably 1.5/hr or less, still more preferably 0.7/hr or less, still more preferably 0.5/hr or less,
• the method for producing an internal olefin according to ⁇ 44> or ⁇ 45> which is more preferably 0.3/hr or less.
• the 1-olefin content (mol%) in the 1-olefin and internal olefin obtained in step 2 %) is preferably 0.1 mol % or more, more preferably 0.2 mol % or more, the internal olefin production method according to any one of ⁇ 1> to ⁇ 46>.
• ⁇ 48> A method for producing an internal olefin sulfonate, comprising sulfonating an internal olefin produced by the method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 47>.
• a method for producing an internal olefin sulfonate comprising producing an internal olefin by the method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 48>, and then sulfonating the internal olefin.
• Example 1 [Step 1, isomerization reaction] In a 3,000 mL four-neck flask, 1,562.6 g of 1-hexadecene as a raw material olefin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 78.1 g of ⁇ -alumina as a catalyst (manufactured by Mizusawa Chemical Industry Co., Ltd., product Name "GP-20", ⁇ -Al 2 O 3 ) (5% by mass with respect to the raw material olefin) was charged, and under stirring at 500 rpm, nitrogen was passed through the system at 260 ° C. (nitrogen flow rate: 100 mL / min), the reaction was carried out for 2.6 hours. At this time, the fluctuation range of the reaction temperature in step 1 was 1° C. or less. After cooling the reaction solution to room temperature, the catalyst was filtered off to obtain an internal olefin.
• 1-hexadecene as a raw material olefin
• the device "Agilent 6890A” (manufactured by Agilent Technology) was equipped with a column “Ultra ALLOY-1” (manufactured by Frontier Lab Co., Ltd.: capillary column 30.0 m ⁇ 250 ⁇ m), and injection was performed using a flame ion detector (FID). Temperature: 300° C., detector temperature: 350° C., He flow rate: 0.8 mL/min, and the product was quantified.
• FID flame ion detector
• Step 2 In a 300 mL separable flask, 100.0 g of the internal olefin obtained in step 1 and 5.0 g of ⁇ -alumina as a catalyst (manufactured by Mizusawa Chemical Industry Co., Ltd., trade name "GP-20", ⁇ -Al 2 O 3 ) (5% by mass with respect to the olefin) was charged, and under stirring at 500 rpm, the reaction was carried out for 27 hours while passing nitrogen through the system (nitrogen flow: 100 mL/min) at 160°C. At this time, the fluctuation range of the reaction temperature in step 2 was 1° C. or less. After completion of the reaction, the product was quantified in the same manner as in step 1.
• Example 2 to 8 Comparative Example 1 An internal olefin was obtained in the same manner as in Example 1, except that the type and amount of the catalyst used, the reaction temperature, the reaction time, and the starting olefin were changed as shown in Table 1.
• the zeolite, which is the catalyst used in Examples 4 and 7, is trade name "CP814E” manufactured by Zeolyst International.
• 1-octadecene used as a raw material olefin in Example 8 is manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
• the physical properties of the used catalyst were measured by the following methods. Specific surface area, pore diameter, pore volume: Specific surface area and pore diameter distribution analysis was performed using ASAP 2020 (manufactured by Shimadzu Corporation). Acid amount: BELCAT (manufactured by Nippon Bell Co., Ltd.) was heated to 500°C at 10°C/min, held at 500°C for 1 hour, and then NH 3 with 5% NH 3 -He at 100°C. performed adsorption. Physically adsorbed NH 3 was removed by flowing He at 100° C. for 15 min. Temperature-programmed desorption was performed by heating up to 610°C at 10°C/min, and desorbed NH 3 was observed by TCD and MS.
• BELCAT manufactured by Nippon Bell Co., Ltd.
• GP-20 ⁇ -Al 2 O 3 manufactured by Mizusawa Chemical Industry Co., Ltd.
• ⁇ Average particle size 26 ⁇ m
• BET specific surface area 189 m 2 /g
• ⁇ Average pore diameter 12.1 nm
• ⁇ Pore volume 0.50 mL/g
• Acid amount 0.28 mmol / g
• CP814E Zeolyst International, zeolite
• ⁇ Average particle size 9.9 ⁇ m ⁇ BET specific surface area: 656 m 2 /g ⁇ Average pore diameter: ⁇ 1 nm ⁇ Pore volume: >0.62 mL/g ⁇ Acid amount: 0.76 mmol / g
• Example 9 [Step 1: Isomerization reaction]
• a ⁇ -alumina catalyst manufactured by Mizusawa Chemical Industry Co., Ltd., product name “Neobead GB-13”, ⁇ -Al 2 O 3 , bead shape, diameter 2.0 mm, specific surface area 180 m 2 /g was used as a catalyst in the catalyst continuous evaluation device.
• average pore diameter 11.1 nm, pore volume 0.50 mL / g, acid amount 0.28 mmol / g, crushing strength 2.6 daN) is filled with 400 mL, and 1-hexadecene (Fujifilm Wako Pure Chemical Industries, Ltd.) is used as a raw material olefin.
• Step 2 A ⁇ -alumina catalyst (manufactured by Mizusawa Chemical Industry Co., Ltd., product name “Neobead GB-13”, ⁇ -Al 2 O 3 , bead shape, diameter 2.0 mm, specific surface area 180 m 2 /g was used as a catalyst in the catalyst continuous evaluation device. , average pore diameter of 11.1 nm, pore volume of 0.50 mL/g, acid content of 0.28 mmol/g, crushing strength of 2.6 daN), and the internal olefin obtained in step 1 as the starting olefin was LHSV 0.0.
• a continuous reaction was carried out under conditions of a pressure of 0.1 MPaG and a reaction temperature of 160° C.
• the fluctuation range of the reaction temperature in step 2 was 1° C. or less.
• Example 10 [Step 1: Isomerization reaction] An olefin isomerization reaction was carried out in the same manner as in Step 1 of Example 9.
• Step 2 A ⁇ -alumina catalyst (manufactured by Mizusawa Chemical Industry Co., Ltd., product name “Neobead GB-13”, ⁇ -Al 2 O 3 , bead shape, diameter 2.0 mm, specific surface area 180 m 2 /g was used as a catalyst in the catalyst continuous evaluation device. , average pore diameter of 11.1 nm, pore volume of 0.50 mL/g, acid content of 0.28 mmol/g, crushing strength of 2.6 daN), and the internal olefin obtained in step 1 as the starting olefin was LHSV 0.0.
• a continuous reaction was carried out under conditions of a pressure of 0.1 MPaG and a reaction temperature of 160° C.
• the fluctuation range of the reaction temperature in step 2 was 1° C. or less.
• the method for producing an internal olefin of the present invention provides a method for producing an internal olefin in which the 1-olefin content is reduced while suppressing changes in the double bond distribution of the internal olefin. be.
• the internal olefin obtained by the method for producing an internal olefin tail of the present invention is useful as a raw material or intermediate raw material for surfactants, organic solvents, softeners, sizing agents, etc., and is useful as a raw material for surfactants.

Landscapes

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

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=85602938

Family Applications (1)

Country Status (4)

Citations (13)

Family Cites Families (5)

• 2022
  • 2022-09-16 US US18/692,123 patent/US20250136532A1/en active Pending
  • 2022-09-16 WO PCT/JP2022/034661 patent/WO2023042898A1/ja not_active Ceased
  • 2022-09-16 JP JP2023548511A patent/JPWO2023042898A1/ja active Pending
  • 2022-09-16 EP EP22870045.6A patent/EP4403540A4/en active Pending

Patent Citations (13)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events