Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • 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
  • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • 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
  • C07C303/04—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 substitution of hydrogen atoms by sulfo or halosulfonyl groups
  • C07C303/06—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 substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
• • 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

Definitions

• the present invention relates to a method for producing an internal olefin, a method for producing an internal olefin sulfonate using the internal olefin, and a method for low temperature stabilization.
• anionic surfactants especially alkyl sulfates and polyoxyalkylene alkyl ether sulfates
• anionic surfactants As one of anionic surfactants, an olefin sulfonate, particularly an internal olefin sulfonate obtained from an internal olefin having a double bond not at the end but inside the olefin, has been reported.
• the internal olefin sulfonate is generally obtained by reacting an internal olefin with sulfur trioxide to sulfonate it, neutralizing the obtained sulfonate, and then preferably hydrolyzing it.
• Patent Document 1 a step of obtaining an internal olefin from a primary aliphatic alcohol having 8 to 24 carbon atoms, a step of sulfonating the internal olefin to obtain a sulfonated product, and the sulfonation production and a step of hydrolyzing the neutralized product after neutralizing the product.
• the present invention provides a method for producing an internal olefin for obtaining an internal olefin sulfonate with high low temperature stability, a method for producing an internal olefin sulfonate using the internal olefin, and a method for stabilization at low temperature.
• the present invention is a method for producing an internal olefin, comprising a step of internally isomerizing an ⁇ -olefin having 8 to 24 carbon atoms using a fixed bed reactor filled with solid acid catalyst particles in a reaction tube,
• the present invention relates to a method for producing an internal olefin, wherein the ratio (D/dp) of the inner diameter D of the reaction tube to the average particle diameter dp of the solid acid catalyst particles is 25 or more.
• the present invention also relates to a method for producing an internal olefin sulfonate, comprising a step of sulfonating the internal olefin obtained by the above production method.
• the present invention relates to a method for stabilizing an internal olefin sulfonate at low temperatures, comprising sulfonating the internal olefin obtained by the production method and further neutralizing to obtain an internal olefin sulfonate.
• the ratio of the inner diameter D of the reaction tube of the fixed bed reactor to the average particle diameter dp of the solid acid catalyst particles (D / dp ) to 25 or more it is possible to produce an internal olefin for obtaining an internal olefin sulfonate with high low-temperature stability.
• the internal olefin sulfonate produced using the internal olefin obtained by the production method of the present invention has high low-temperature stability, and is characterized by the fact that precipitates are less likely to occur even when stored in a low-temperature environment of around 0°C. .
• the method for producing an internal olefin of the present invention includes a step of internally isomerizing an ⁇ -olefin having 8 to 24 carbon atoms using a fixed bed reactor filled with solid acid catalyst particles in a reaction tube.
• An internal olefin is an olefin that has a double bond other than the end of the carbon chain, that is, an olefin that has a double bond at the 2nd or higher position of the carbon chain.
• internal isomerization of ⁇ -olefins refers to conversion of the double bond at the ⁇ -position to the 2nd or higher position of the carbon chain to convert the ⁇ -olefin to an olefin having a double bond other than the end of the carbon chain (internal olefin).
• the number of carbon atoms in the ⁇ -olefin is preferably 10 or more, more preferably 12 or more, still more preferably 14 or more, from the viewpoint of cleaning performance when the internal olefin sulfonate is used as a cleaning agent. is 22 or less, more preferably 18 or less.
• a fixed bed reactor filled with solid acid catalyst particles in the reaction tube can be used.
• the solid acid catalyst particles are preferably solid acid catalyst particles containing one or more elements selected from aluminum, iron, and gallium from the viewpoint of increasing the conversion rate of ⁇ -olefins to internal olefins, more preferably Solid acid catalyst particles containing aluminum, more preferably ⁇ -alumina and/or aluminum phosphate.
• the average particle diameter dp (equivalent sphere diameter) of the solid acid catalyst particles is preferably 0.5 mm or more, more preferably 1 mm or more, from the viewpoint of handleability, catalytic activity, and relationship with the inner diameter D of the reaction tube. and is preferably 6 mm or less, more preferably 5 mm or less.
• the filling height of the solid acid catalyst particles is preferably 100 mm or more, more preferably 1000 mm or more, from the viewpoint of internal olefin production efficiency. Also, the upper limit of the filling height is preferably 8000 mm or less from the viewpoint of the installation space of the reaction tube.
• the inner diameter D of the reaction tube may be, for example, 10 mm or more, and is preferably 50 mm or more, more preferably 500 mm, from the viewpoint of the relationship between the internal olefin production efficiency and the average particle diameter dp of the solid acid catalyst particles. and preferably 2500 mm or less, more preferably 2000 mm or less.
• the fixed bed reactor is preferably a fixed bed reactor in which reaction tubes are installed vertically, from the viewpoints of handling of the solid acid catalyst particles and installation space of the fixed bed reactor. Further, the fixed bed reactor is preferably a single tube type with one reaction tube from the viewpoint of simplification of equipment and reduction of pressure loss. A multi-tube type having a plurality of tubes is preferred.
• the average The particle diameter dp and the inner diameter D of the reaction tube are adjusted.
• D/dp is preferably 200 or more, more preferably 400 or more, from the viewpoint of obtaining an internal olefin which is a raw material for producing an internal olefin sulfonate having high low-temperature stability.
• the upper limit of D/dp is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 1,000 or less, from the viewpoints of handleability of the solid acid catalyst particles and installation space of the fixed bed reactor.
• the reaction temperature for internal isomerization of ⁇ -olefin is preferably 300° C. or less, more preferably 290° C., from the viewpoint of obtaining internal olefin which is a raw material for producing internal olefin sulfonate having high low-temperature stability. 280° C. or less, more preferably 280° C. or less.
• the lower limit of the reaction temperature is preferably 100.degree. C. or higher, more preferably 150.degree.
• the pressure during internal isomerization of ⁇ -olefins is considered to increase the conversion rate from ⁇ -olefins to internal olefins, and to obtain internal olefins that are raw materials for producing internal olefin sulfonates with high low-temperature stability.
• the absolute pressure is preferably 0.03 MPa or more, more preferably 0.05 MPa or more, still more preferably 0.1 MPa or more, and is preferably 1 MPa or less, more preferably 0.5 MPa or less, and still more preferably 0 .2 MPa or less.
• an inert gas may be introduced into the fixed bed reactor.
• the inert gas include nitrogen, argon, helium, etc. Nitrogen is preferable from the viewpoint of availability.
• the amount of inert gas introduced is preferably 0.1 mol or more, more preferably 0.2 mol or more, relative to 1 mol of ⁇ -olefin as a raw material, from the viewpoint of improving the reaction rate and productivity, Also, it is preferably 10 mol or less, more preferably 1 mol or less.
• WHSV mass of ⁇ -olefin supplied per unit mass of solid acid catalyst per hour
• an internal olefin sulfonate with high reaction efficiency and low-temperature stability.
• an internal olefin which is a raw material for and is preferably 7/hr or less, more preferably 5/hr or less, still more preferably 2.5/hr or less, still more preferably 2/hr or less, still more preferably 1.5/hr or less, still more preferably is 1/hr or less.
• LHSV liquid hourly space velocity
• 0.03/hr or more is determined from the viewpoint of reaction efficiency and from the viewpoint of obtaining an internal olefin that is a raw material for producing an internal olefin sulfonate having high low-temperature stability.
• the internal olefin obtained by the above process may be purified by distillation or the like in order to remove by-products such as ⁇ -olefins and dimers that are raw materials.
• the average double bond position of the internal olefin is preferably 2 or more, more preferably 3 or more, still more preferably 3.5 or more, still more preferably 4 or more, and preferably 4.8 or less, more preferably 4.6 or less, still more preferably 4.5 or less be.
• the internal olefin may be used singly or in combination of two or more.
• an internal olefin having 16 carbon atoms and an internal olefin having 18 carbon atoms from the viewpoint of cleaning performance when using an internal olefin sulfonate as a cleaning agent. Used in combination.
• the method for producing an internal olefin sulfonate of the present invention includes a step of sulfonating the internal olefin obtained by the above production method.
• the sulfonation step is preferably a sulfonation step of reacting the internal olefin obtained by the production method with sulfur trioxide to obtain a sulfonated product.
• the method for producing an internal olefin sulfonate of the present invention preferably includes a neutralization step of neutralizing the obtained sulfonate to obtain a neutralized product, and further preferably the obtained neutralized product to obtain a hydrolyzed product.
• the internal olefin sulfonate is a sulfonate obtained by sulfonating the internal olefin, further sulfonating it, preferably neutralizing it, further neutralizing it, and more preferably hydrolyzing it. be. That is, sulfonation of the internal olefins converts them to ⁇ -sultones, ⁇ -sultones and olefinsulfonic acids, which undergo a neutralization step, and preferably a hydrolysis step, to form hydroxysulfonates and olefinsulfonic acids. convert to salt.
• the products obtained are mainly mixtures of these. In the present invention, each of these products and mixtures thereof are collectively referred to as internal olefin sulfonates.
• the sulfonation step is a step of sulfonating the internal olefin, preferably a step of reacting the internal olefin with sulfur trioxide to obtain a sulfonated product.
• sulfur trioxide is preferably reacted as sulfur trioxide gas.
• the sulfur trioxide gas is an inert gas such as air or nitrogen, preferably diluted to 1 to 30% by volume, more preferably 1.5 to 10% by volume.
• the amount of sulfur trioxide used is preferably 0.8 mol or more, more preferably 0.9 mol or more, and still more preferably 0.95 mol, per 1 mol of the internal olefin. It is preferably 1.2 mol or less, more preferably 1.1 mol or less, still more preferably 1.05 mol or less from the viewpoint of economy and suppression of coloration of the sulfonated product.
• the treatment temperature in the sulfonation step is preferably 0°C or higher from the viewpoint of preventing solidification of sulfur trioxide and sulfonated substances, and preferably 50°C or lower from the viewpoint of suppressing coloring of sulfonated substances.
• the sulfonation reaction is an exothermic reaction, it is preferable to cool the sulfonation reactor by providing an external jacket and passing cooling water through it.
• the temperature of the cooling water passed through the outer jacket of the sulfonation reactor is preferably 0° C. or higher from the viewpoint of improving the reaction rate, and suppresses side reactions to reduce the internal olefin sulfone finally obtained.
• the temperature is preferably 30° C. or lower, more preferably 20° C. or lower.
• the sulfonation reaction rate is preferably 95% or higher, more preferably 97% or higher, and still more preferably 98% or higher, from the viewpoint of improving the yield of the sulfonated product. from the viewpoint of suppressing, it is preferably 99.8% or less.
• the neutralization step is a step of neutralizing the sulfonated product obtained in the sulfonation step to obtain a neutralized product.
• the alkaline compound used for neutralization may be an inorganic alkaline compound or an organic alkaline compound.
• inorganic alkali compounds that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate.
• alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
• alkali metal carbonates such as sodium carbonate and potassium carbonate.
• organic alkali compounds that can be used include amine compounds having 1 to 6 carbon atoms such as ammonia and 2-aminoethanol.
• the alkali compound used for neutralization is preferably an inorganic alkali compound, more preferably an alkali metal hydroxide, from the viewpoint of availability and economy.
• at least one selected from sodium hydroxide and potassium hydroxide is more preferable, sodium hydroxide is more preferable from the viewpoint of ease of use, and potassium hydroxide is still more preferable from the viewpoint of low temperature stability.
• the alkaline compound used for neutralization is preferably used as an alkaline aqueous solution from the viewpoint of ease of handling.
• the concentration of the alkaline aqueous solution is preferably 1% by mass or more, more preferably 4.5% by mass or more, and still more preferably 7% by mass, from the viewpoint of economy and from the viewpoint of suppressing the formation of impurities such as internal olefins and inorganic salts. Above, more preferably 10% by mass or more, still more preferably 12% by mass or more. Further, from the viewpoint of productivity in the hydrolysis step, the % by mass or less.
• the amount of the alkali compound used for neutralization is preferably 1 mol or more, or more, than the sulfonic acid group. It is preferably 1.03 mol times or more, and is preferably 2.5 mol times or less, more preferably 2.0 mol, from the viewpoint of economy and suppression of the formation of impurities such as internal olefins and inorganic salts. It is 1.5 mol times or less, more preferably 1.5 mol times or less.
• the temperature at which the sulfonated product and the alkaline aqueous solution are mixed and the temperature at which the neutralization reaction is performed are preferably 40°C from the viewpoint of suppressing the formation of impurities such as internal olefins and inorganic salts due to side reactions. or less, more preferably 35° C. or less, still more preferably 30° C. or less, still more preferably 25° C. or less, and from the viewpoint of improving reactivity, preferably 0° C. or more, more preferably 10° C. or more. , more preferably 15° C. or higher, and even more preferably 20° C. or higher.
• any type of mixer may be used as long as it can efficiently mix the sulfonated substance and the alkaline aqueous solution and apply a shearing force to the oily substance.
• Such mixers include static mixers, impingement mixers, impeller mixers, vibrating mixers, and the like.
• the static mixer include a static mixer manufactured by Noritake Co., Ltd., and the like.
• the impingement mixer include a high-pressure emulsifier manufactured by Nanomizer.
• the agitating blade type mixer include Milder manufactured by Matsubo Co., Ltd. and Homoxar manufactured by Primix. Among these, a stirring blade type mixer is preferable from the viewpoint of equipment cost.
• the sulfonated compound and the alkaline aqueous solution are added while circulating the reaction solution using a loop reactor from the viewpoint of suppressing the production of by-products and productivity, and at the same time, the reaction solution is withdrawn.
• a continuous process is preferred.
• the neutralization time is preferably 5 minutes or longer, more preferably 8 minutes or longer, even more preferably 10 minutes or longer, still more preferably 12 minutes or longer, from the viewpoint of sufficiently performing the neutralization reaction. In addition, from the viewpoint of improving productivity, the 15 minutes or less.
• the neutralization time can be expressed as the average residence time obtained by dividing the capacity of the loop reactor by the total amount of sulfonate and alkaline aqueous solution added per unit time.
• the average residence time is preferably 8 minutes or more, more preferably 10 minutes or more, and still more preferably 12 minutes or more from the viewpoint of suppressing heat of neutralization, and is preferably 100 minutes or less, more preferably 100 minutes or less, from the viewpoint of improving productivity. is 60 minutes or less, more preferably 40 minutes or less, even more preferably 30 minutes or less, even more preferably 20 minutes or less, and even more preferably 15 minutes or less.
• the circulation ratio of the reaction solution is preferably 3 times or more, more preferably 6 times or more, and still more preferably 9 times or more from the viewpoint of improving reactivity, and the pressure rise in the reactor is suppressed. From the viewpoint of suppression, it is preferably 30 times or less, more preferably 20 times or less, and still more preferably 15 times or less.
• the circulation ratio is the ratio of the total content circulating in the reactor to the flow rate introduced into the reactor, (total circulation in the reactor) / (into the reactor input amount).
• water-soluble organic solvents such as alcohol and acetone
• surfactants such as polyoxyethylene alkyl ether and ⁇ -olefin sulfonic acid
• coexisting substances are preferably not used because they change in quality during the neutralization reaction, remain in the final product, or impose a load on the purification process. Below, more preferably 10% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less.
• the production method of the present invention preferably includes a hydrolysis step of hydrolyzing the obtained neutralized product.
• the temperature during hydrolysis is preferably 120° C. or higher, more preferably 140° C. or higher, and still more preferably 160° C. or higher from the viewpoint of improving reactivity, and suppresses decomposition of the product. from the viewpoint of reducing the temperature, the temperature is preferably 220° C. or lower, more preferably 180° C. or lower.
• the hydrolysis reaction may be carried out in a batch reactor or a continuous reactor.
• the treatment time of the hydrolysis step is preferably 30 minutes or more, more preferably 45 minutes or more, from the viewpoint of completing the reaction, and is preferably 4 hours or less, more preferably 3 hours from the viewpoint of improving productivity. 0.5 hours or less, more preferably 3 hours or less, even more preferably 2 hours or less, and even more preferably 90 minutes or less.
• the concentration of the internal olefin sulfonate aqueous solution obtained by the hydrolysis step is preferably 15% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and even more preferably 40% by mass. % or more, more preferably 45 mass % or more, still more preferably 48 mass % or more, still more preferably 50 mass % or more, and from the viewpoint of the viscosity of the aqueous solution, etc., preferably 75 mass % or less, more preferably is 70% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less.
• the internal olefin sulfonate can be used for various purposes as it is, but it may be further purified by desalting, decolorization, and the like.
• the internal olefin sulfonate obtained by the production method of the present invention has high low-temperature stability, and deposits are less likely to occur even when stored in a low-temperature environment of around 0°C.
• the internal olefin sulfonate since the internal olefin sulfonate has good purity and color, it can be suitably used for various applications such as body cleansers, shampoos, laundry detergents, and dishwashing agents.
• ⁇ Low temperature stabilization method> By sulfonating the internal olefin obtained by the production method of the present invention and further neutralizing to obtain an internal olefin sulfonate, the obtained internal olefin sulfonate can be stabilized at low temperatures.
• the internal olefins and internal olefin sulfonates refer to the internal olefins and internal olefin sulfonates described above.
• the term "stabilized at low temperature” means that a change in state is unlikely to occur at room temperature or lower, and can be confirmed, for example, by a decrease in the generation of precipitates at a temperature of -5°C under normal pressure.
• a method for producing an internal olefin comprising a step of internally isomerizing an ⁇ -olefin having 8 to 24 carbon atoms using a fixed bed reactor filled with solid acid catalyst particles in a reaction tube,
• the solid acid catalyst particles are preferably solid acid catalyst particles containing one or more elements selected from aluminum, iron, and gallium, more preferably solid acid catalyst particles containing aluminum, and still more preferably ⁇ -
• the average particle diameter dp of the solid acid catalyst particles is preferably 0.5 mm or more, more preferably 1 mm or more, and is preferably 6 mm or less, more preferably 5 mm or less.
• the inner diameter D of the reaction tube may be 10 mm or more, preferably 50 mm or more, more preferably 500 mm or more, preferably 2500 mm or less, more preferably 2000 mm or less, any of ⁇ 1> to ⁇ 6>
• the fixed-bed reactor is a fixed-bed reactor in which reaction tubes are installed vertically, and is preferably a single-tube type or multi-tube type. Production method.
• ⁇ 9> Any one of ⁇ 1> to ⁇ 8>, wherein the ratio (D/dp) of the inner diameter D of the reaction tube to the average particle diameter dp of the solid acid catalyst particles is preferably 200 or more, more preferably 400 or more.
• ⁇ 10> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 9>, wherein the upper limit of D/dp is preferably 2000 or less, more preferably 1500 or less, and still more preferably 1000 or less.
• ⁇ 11> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 10>, wherein the D/dp is preferably 200 or more and 2000 or less, more preferably 400 or more and 1500 or less, still more preferably 400 or more and 1000 or less.
• ⁇ 12> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 11>, wherein the internal isomerization of the ⁇ -olefin is carried out at a reaction temperature of 300° C. or lower.
• ⁇ 13> The internal reaction according to any one of ⁇ 1> to ⁇ 12>, wherein the internal A method for producing olefins.
• the lower limit of the reaction temperature for internal isomerization of ⁇ -olefin is preferably 100° C. or higher, more preferably 150° C. or higher, and still more preferably 170° C. or higher, any of ⁇ 1> to ⁇ 13> A process for the preparation of the internal olefins described.
• the pressure during internal isomerization of ⁇ -olefin is preferably 0.03 MPa or more, more preferably 0.05 MPa or more, still more preferably 0.1 MPa or more, preferably 1 MPa or less, more preferably 0 in terms of absolute pressure.
• an inert gas may be introduced into the fixed bed reactor, and the inert gas is preferably nitrogen, any of ⁇ 1> to ⁇ 15>
• the amount of the inert gas introduced is preferably 0.1 mol or more, more preferably 0.2 mol or more, preferably 10 mol or less, more preferably 1 mol or more, relative to 1 mol of the raw ⁇ -olefin.
• WHSV mass of ⁇ -olefin supplied per hour with respect to unit mass of solid acid catalyst
• hr or more preferably 7/hr or less, more preferably 5/hr or less, still more preferably 2.5/hr or less, still more preferably 2/hr or less, still more preferably 1.5/hr or less, still more preferably is 1/hr or less, the method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 18>.
• the WHSV is preferably 0.03/hr or more and 7/hr or less, more preferably 0.05/hr or more and 5/hr or less, still more preferably 0.07/hr or more and 2.5/hr or less, still more preferably 0.09/hr or more and 2/hr or less, more preferably 0.09/hr or more and 1.5/hr or less, still more preferably 0.09/hr or more and 1/hr or less, ⁇ 1> to ⁇ 19> A method for producing an internal olefin according to any one of .
• LHSV liquid hourly space velocity
• LHSV liquid hourly space velocity
• 0.03/hr or more is preferably 0.03/hr or more, more preferably 0.05/hr or more, and still more preferably 0.07/hr or more, Preferably 5/hr or less, more preferably 4/hr or less, still more preferably 2.5/hr or less, still more preferably 2/hr or less, still more preferably 1.5/hr or less, still more preferably 1/hr or less.
• the LHSV is preferably 0.03/hr or more and 5/hr or less, more preferably 0.05/hr or more and 4/hr or less, still more preferably 0.07/hr or more and 2.5/hr or less, still more preferably 0.07/hr or more and 2/hr or less, more preferably 0.07/hr or more and 1.5/hr or less, still more preferably 0.07/hr or more and 1/hr or less, ⁇ 1> to ⁇ 22> A method for producing an internal olefin according to any one of .
• ⁇ 24> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 23>, wherein the internal olefin has an average double bond position of 2 or more and 4.8 or less.
• the average number of double bond positions in the internal olefin is preferably 2 or more, more preferably 3 or more, still more preferably 3.5 or more, still more preferably 4 or more, and preferably 4.8 or less, more preferably 4.5. 6 or less, more preferably 4.5 or less, the method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 24>.
• ⁇ 26> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 25>, wherein the internal olefin is preferably a combination of an internal olefin having 16 carbon atoms and an internal olefin having 18 carbon atoms.
• ⁇ 28> The method for producing an internal olefin sulfonate according to ⁇ 27>, wherein the sulfonation step is a sulfonation step of reacting the internal olefin with sulfur trioxide to obtain a sulfonated product.
• ⁇ 29> The method for producing an internal olefin sulfonate according to ⁇ 28>, wherein the sulfur trioxide is reacted as sulfur trioxide gas.
• the sulfur trioxide gas is an inert gas such as air and nitrogen, preferably diluted to 1 to 30% by volume, more preferably diluted to 1.5 to 10% by volume, ⁇ 29 A method for producing an internal olefin sulfonate according to >.
• the amount of sulfur trioxide to be used is preferably 0.8 mol or more, more preferably 0.9 mol or more, still more preferably 0.95 mol or more, and 1.2 mol or less, relative to 1 mol of the internal olefin.
• ⁇ 32> The internal olefin sulfonate according to any one of ⁇ 28> to ⁇ 31>, wherein the sulfonation reaction for reacting the internal olefin with sulfur trioxide uses a thin-film sulfonation reactor equipped with an external jacket. Production method.
• ⁇ 33> The process for producing an internal olefin sulfonate according to any one of ⁇ 27> to ⁇ 32>, wherein the treatment temperature in the sulfonation step is preferably 0°C or higher and preferably 50°C or lower.
• ⁇ 34> The method for producing an internal olefin sulfonate according to ⁇ 32> or ⁇ 33>, wherein the sulfonation reactor is provided with an external jacket and cooled by passing cooling water.
• ⁇ 35> The internal olefin sulfonic acid according to ⁇ 34>, wherein the temperature of the cooling water that flows through the outer jacket of the sulfonation reactor is preferably 0°C or higher, preferably 30°C or lower, and more preferably 20°C or lower.
• the sulfonation reaction rate is preferably 95% or more, more preferably 97% or more, still more preferably 98% or more, and preferably 99.8% or less.
• method for producing an internal olefin sulfonate of ⁇ 37> comprising a neutralization step of neutralizing the obtained sulfonated product to obtain a neutralized product.
• the alkali compound used for neutralization is preferably an inorganic alkali compound, more preferably an alkali metal hydroxide, still more preferably at least one selected from sodium hydroxide and potassium hydroxide, still more preferably sodium hydroxide, and more preferably sodium hydroxide.
• the concentration of the alkaline aqueous solution is preferably 1% by mass or more, more preferably 4.5% by mass or more, still more preferably 7% by mass or more, even more preferably 10% by mass or more, and even more preferably 12% by mass or more.
• the amount of the alkali compound to be used is preferably 1 mol or more, more preferably 1.03 mol or more, preferably 2.5 mol or less, more preferably 2.0 mol, relative to the sulfonic acid group.
• the temperature at which the sulfonated product and the alkaline aqueous solution are mixed and the temperature at which the neutralization reaction is performed are preferably 40°C or lower, more preferably 35°C or lower, and still more preferably 30°C or lower. Any one of ⁇ 37> to ⁇ 41> which is even more preferably 25° C. or lower, preferably 0° C. or higher, more preferably 10° C. or higher, even more preferably 15° C. or higher, and still more preferably 20° C. or higher. 3.
• ⁇ 43> The method for producing an internal olefin sulfonate according to any one of ⁇ 37> to ⁇ 42>, wherein the mixer in the neutralization step is a stirring blade type mixer.
• the neutralization step is carried out by a so-called continuous method in which the sulfonated product and the alkaline aqueous solution are added while the reaction solution is circulated using a loop reactor, and the reaction solution is withdrawn at the same time ⁇ 37> to ⁇ 43>.
• the neutralization time is preferably 5 minutes or longer, more preferably 8 minutes or longer, still more preferably 10 minutes or longer, still more preferably 12 minutes or longer, preferably 100 minutes or shorter, more preferably 50 minutes or shorter, and even more preferably Production of the internal olefin sulfonate according to any one of ⁇ 37> to ⁇ 44>, wherein the time is 40 minutes or less, more preferably 30 minutes or less, even more preferably 20 minutes or less, and even more preferably 15 minutes or less.
• the average residence time in the continuous process is preferably 8 minutes or longer, more preferably 10 minutes or longer, still more preferably 12 minutes or longer, preferably 100 minutes or shorter, more preferably 60 minutes or shorter, and still more preferably 40 minutes or shorter.
• the method for producing an internal olefin sulfonate according to ⁇ 44> or ⁇ 45> which is more preferably 30 minutes or less, still more preferably 20 minutes or less, and still more preferably 15 minutes or less.
• the circulation ratio of the reaction solution in the continuous method is preferably 3 times or more, more preferably 6 times or more, still more preferably 9 times or more, preferably 30 times or less, more preferably 20 times or less, and still more preferably 15 times.
• the method for producing an internal olefin sulfonate according to any one of ⁇ 44> to ⁇ 46> which is the following.
• ⁇ 48> The method for producing an internal olefin sulfonate according to any one of ⁇ 37> to ⁇ 47>, wherein no surfactant (coexisting substance) is used in the neutralization step.
• the surfactant is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 2% by mass or less in the mixed liquid.
• the temperature during hydrolysis is preferably 120° C. or higher, more preferably 140° C. or higher, still more preferably 160° C. or higher, and preferably 220° C. or lower and more preferably 180° C. or lower, according to ⁇ 50>
• the treatment time of the hydrolysis step is preferably 30 minutes or longer, more preferably 45 minutes or longer, preferably 4 hours or shorter, more preferably 3.5 hours or shorter, still more preferably 3 hours or shorter, and even more preferably 2 hours.
• the concentration of the internal olefin sulfonate aqueous solution obtained by the hydrolysis step is preferably 15% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, still more preferably 40% by mass or more, and even more preferably 40% by mass or more.
• ⁇ 54> Use of the internal olefin sulfonate obtained by the production method according to any one of ⁇ 27> to ⁇ 53> in body cleansing agents, shampoos, laundry detergents, or dishwashing agents.
• a method for stabilizing an internal olefin sulfonate at low temperatures comprising sulfonating the internal olefin obtained by the production method according to any one of ⁇ 1> to ⁇ 26> and further neutralizing to obtain an internal olefin sulfonate.
• ⁇ Method for measuring average particle diameter dp (equivalent sphere diameter) of solid acid catalyst particles 50 solid acid catalyst particles were randomly extracted, and the short axis diameter and long axis diameter were measured with a vernier caliper. Using the arithmetic average value of the minor axis diameter and the arithmetic average value of the major axis diameter, the specific surface area of the cylinder having the diameter and height of the bottom surface, respectively, was calculated. The diameter of a sphere having the same specific surface area was defined as the average particle diameter dp (equivalent sphere diameter) of the solid acid catalyst particles.
• GC gas chromatography
• the internal olefin was reacted with dimethyl disulfide to obtain a dithio derivative, and each component was separated by GC.
• the double bond position of the internal olefin was obtained from each peak area, and the average double bond position was calculated by the following formula.
• the apparatus and measurement conditions used for the measurement are as follows.
• GC device HP6890 (manufactured by HEWLETT PACKARD)
• Column Ultra-Alloy-1HT capillary column, 30 m ⁇ 250 ⁇ m ⁇ 0.15 ⁇ m (manufactured by Frontier Labs)
• Detector Flame ion detector (FID)
• Injection temperature 300°C
• Detector temperature 350°C
• He flow rate 4.6 mL/min
• n is the number of carbon atoms in the olefin
• m is the position of the double bond in the olefin
• Y is the percentage of m-olefin in the olefin having n carbon atoms.
• 1-hexadecanol product name: Calcol 6098, manufactured by Kao Corporation
• An internal isomerization reaction was carried out by supplying at atmospheric pressure from the upper part of the reactor so that the molar amount was doubled.
• the reaction tube outlet liquid was cooled to 70° C. to recover an internal olefin having 16 carbon atoms.
• the resulting internal olefin had an average double bond position of 4.1.
• C16IOS Method for producing C16 internal olefin sulfonate (C16IOS)
• C16IOS C16 internal olefin sulfonate
• the produced internal olefin having 16 carbon atoms is placed in a thin film sulfonation reactor having an external jacket, and sulfur trioxide gas (1.1 volume %, balance air) was used to carry out the sulfonation reaction.
• the SO 3 /internal olefin molar ratio during the sulfonation reaction was set at 1.005.
• the resulting sulfonated product was mixed with an alkaline aqueous solution (potassium hydroxide 17% by mass, the balance being water) prepared with 1.05 moles of potassium hydroxide (alkaline agent) relative to the theoretical acid value, and subjected to a continuous process (milder Neutralization was carried out at 30° C. using a mixer (product name: Milder MDN303V, manufactured by Matsubo Co., Ltd.) with an average retention time of 30 minutes and a circulation magnification of 9 times.
• the neutralized product was hydrolyzed by heating in an autoclave at 170° C. for 1 hour to obtain a liquid containing 55% by mass of potassium internal olefin sulfonate having 16 carbon atoms.
• Example 2 Comparative Example 1 An internal olefin having 16 carbon atoms was produced in the same manner as in Example 1, except that the internal isomerization reaction conditions were changed to those shown in Table 1. Using the obtained internal olefin having 16 carbon atoms, a liquid containing potassium internal olefin sulfonate having 16 carbon atoms was produced in the same manner as in Example 1.
• 1-octadecanol product name: Calcol 8098, manufactured by Kao Corporation
• reaction tube outlet liquid was cooled to 70° C. to recover crude 1-octadecene.
• the obtained crude 1-octadecene was transferred to a distillation flask and distilled at 175-180° C./9 mmHg to obtain 1-octadecene with an olefin purity of 100%.
• An internal isomerization reaction A single-tube fixed-bed reactor was used in which a reaction tube was installed vertically, and the reaction tube was filled with ⁇ -alumina as solid acid catalyst particles to a height of 0.4 m. Note that D/dp is 29.
• An internal isomerization reaction was carried out by supplying at atmospheric pressure from the upper part of the reactor so that the molar amount was doubled.
• the reaction tube outlet liquid was cooled to 70° C. to recover an internal olefin having 18 carbon atoms.
• the resulting internal olefin had an average double bond position of 4.0.
• C18IOS Method for producing C18 internal olefin sulfonate (C18IOS)
• C18IOS C18 internal olefin sulfonate
• the produced internal olefin having 18 carbon atoms is placed in a thin-film sulfonation reactor having an external jacket, and sulfur trioxide gas (1.1 volume %, balance air) was used to carry out the sulfonation reaction.
• the SO 3 /internal olefin molar ratio during the sulfonation reaction was set at 1.005.
• the resulting sulfonated product was mixed with an alkaline aqueous solution (potassium hydroxide 17% by mass, the balance being water) prepared with 1.05 moles of potassium hydroxide (alkaline agent) relative to the theoretical acid value, and subjected to a continuous process (milder Neutralization was carried out at 30° C. using a mixer (product name: Milder MDN303V, manufactured by Matsubo Co., Ltd.) with an average retention time of 30 minutes and a circulation magnification of 9 times.
• the neutralized product was hydrolyzed by heating in an autoclave at 170° C. for 1 hour to obtain a liquid containing 55% by mass of potassium internal olefin sulfonate having 18 carbon atoms.
• Examples 10-12, Comparative Examples 2 and 3 An internal olefin having 18 carbon atoms was produced in the same manner as in Example 9, except that the internal isomerization reaction conditions were changed to those shown in Table 2. Using the obtained internal olefin having 18 carbon atoms, a liquid containing potassium internal olefin sulfonate having 18 carbon atoms was produced in the same manner as in Example 9.
• the particle diameter dp of the solid acid catalyst particles ( ⁇ -alumina) used in the above examples is about 1 to 5 mm, the reaction tubes filled with the solid acid catalyst particles each have a single diameter, and the inner diameter D is It was about 50 to 2000 mm.
• the internal olefin obtained by the production method of the present invention is useful as a base oil for petroleum drilling oil, a raw material for detergents, a raw material for paper sizing agents, a base oil or raw material for lubricating oils, a raw material for chemical products, and the like.
• the internal olefin sulfonate obtained by the production method of the present invention is useful as a base for various detergents.

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