Method for producing an internal olefin

Abstract

Method for producing an internal olefin using a primary aliphatic alcohol having 8 to 24 carbon atoms as a starting material, comprising carrying out the following steps (1) to (3): Step (1): a step to carry out a dehydration reaction of a primary aliphatic alcohol having 8 to 24 carbon atoms in the presence of a solid catalyst; Step (2): a step to control the water content of a water-containing olefin, obtained by the dehydration reaction, to 0.008 wt% or more and 7 wt% or less; and Step (3): a step to internally isomerize the water-containing olefin with a water content adjusted to 0.008 wt% or more and 7 wt% or less, in the presence of a solid catalyst.

Description

Field of invention

[0001] This invention relates to a process for producing an internal olefin using a primary aliphatic alcohol as a starting material and a process for producing an internal olefin sulfonate salt. Background of the invention

[0002] An internal olefin is used as a base oil for an oil drilling fluid, a starting material for a detergent, a starting material for a paper sizing agent, a base oil or a starting material for a lubricant, a starting material for a chemical product, and the like. Examples of the usual process for producing an internal olefin include a process for producing an internal olefin that uses an α-olefin obtained by polymerization of ethylene or the like, and wherein the α-olefin with a reduced water content comes into contact with zeolite and / or montmorrillonite as a catalyst (PTL 1).

[0003] Examples of the process also include a method for obtaining an internal olefin using a crystalline metal silicate as a catalyst in the presence of water (PTL 2).

[0004] Examples of the process for generating an α-olefin as a starting material for an internal olefin include a process for providing an α-olefin by dehydration reaction of a primary aliphatic alcohol (PTL 3 and PTL 4).

[0005] PTL 5 deals with a process for the production of an alpha olefin and in particular a process for the production of a long-chain alpha olefin by a liquid-phase dehydration reaction of a long-chain aliphatic primary alcohol.

[0006] PTL 6 deals with processes for the production of an internal olefin, comprising contacting an α-olefin in the presence of a zeolite catalyst and / or a montmorillonite catalyst.

[0007] PTL 7 deals with the provision of an internal olefin sulfonate suitable as a cleaning component, as well as a detergent composition containing this. List of printed works and patent literature PTL 1: JP-A-2005-239651 PTL 2: JP-A-10-167989 PTL 3: JP-A-2003-95994 PTL 4: WO 2011 / 052732 PTL 5: JP-A-2012-32944 PTL 6: EP 1719747 A1 PTL 7: JP-A-2003-0819335 Summary of the invention

[0008] This invention relates to the following points [1] and [2] [1] Method for producing an internal olefin using a primary aliphatic alcohol having 8 to 24 carbon atoms as a starting material, comprising carrying out the following steps (1) to (3): Step (1): a step to carry out a dehydration reaction of a primary aliphatic alcohol having 8 to 24 carbon atoms in the presence of a solid catalyst; Step (2): a step to control the water content of a water-containing olefin, obtained by the dehydration reaction, to 0.008 wt% or more and 7 wt% or less; and Step (3): a step to internally isomerize the water-containing olefin with water adjusted to 0.008 wt% or more and 7 wt% or less, in the presence of a solid catalyst. [2] A process for producing an internal olefin sulfonate salt, comprising: a step for sulfonating an internal olefin produced by the production process according to point [1] to obtain a sulfonated product; and a step for neutralizing the sulfonated product and subsequently hydrolyzing the neutralized product. Detailed description of the invention

[0009] An internal olefin must have high double bond migration in view of its flowability, and it is required that it exhibits high linearity in view of its biodegradability.

[0010] PTL 1 describes a method for generating an internal olefin by using an α-olefin obtained by polymerization of ethylene or the like, but the yield of the linear internal olefin is not necessarily high, and the double bond migration of the internal olefin has not been investigated.

[0011] PTL 2 describes a process for generating an internal olefin using a crystalline metal osilicate as a catalyst in the presence of water in a large excess amount relative to the α-olefin, but the yield of the internal linear olefin is not necessarily high and the double bond migration of the internal olefin is not described.

[0012] PTL 3 describes a method for generating an α-olefin by dehydration of a primary aliphatic alcohol, but there is no specific investigation regarding the technique for generating an internal olefin. PTL 4 also describes a method for generating an olefin by dehydration of a primary aliphatic alcohol, but there is no investigation regarding a method for efficiently carrying out an isomerization reaction when the dehydration reaction is performed while water is removed from the system.

[0013] When an α-olefin is obtained by dehydration reaction of a primary aliphatic alcohol as a method for generating an α-olefin as a starting material for an internal olefin, there is a problem that the equimolar amount of water is generated simultaneously, increasing the water content of the resulting α-olefin, and the double bond migration of the internal olefin, obtained with the α-olefin as the starting material, is reduced.

[0014] PTL 1 does not suggest the use of a starting material that has a high water content due to the dehydration reaction of an alcohol, and thus it does not examine in detail the water content with respect to the isomerization reaction.

[0015] The procedure described in PTL 2 is the method for carrying out the reaction under conditions with a water content greater than that resulting from the dehydration reaction of an alcohol, and is therefore not practically applicable to the isomerization procedure carried out immediately after the dehydration reaction of an alcohol. Furthermore, there is no specific description regarding the influence of the water content on the isomerization reaction.

[0016] This invention relates to a process capable of adequately providing a linear internal olefin with high double bond migration in high yield even when an olefin with a high water content, obtained by dehydration reaction of a primary aliphatic alcohol, is used as the starting material, and to a process for producing an internal olefin sulfonate salt using the internal olefin obtained by the production process.

[0017] This invention relates to the following points [1] and [2]. [1] Method for producing an internal olefin using a primary aliphatic alcohol having 8 to 24 carbon atoms as a starting material, comprising carrying out the following steps (1) to (3): Step (1): a step to carry out a dehydration reaction of a primary aliphatic alcohol having 8 to 24 carbon atoms in the presence of a solid catalyst; Step (2): a step to control the water content of a water-containing olefin, obtained by the dehydration reaction, to 0.008 wt% or more and 7 wt% or less; and Step (3): a step to internally isomerize the water-containing olefin with a water content adjusted to 0.008 wt% or more and 7 wt% or less, in the presence of a solid catalyst. [2] A process for producing an internal olefin sulfonate salt, comprising: a step for sulfonating the internal olefin produced by the production process according to point [1] to obtain a sulfonated product; and a step for neutralizing the sulfonated product and subsequently hydrolyzing the neutralized product.

[0018] The production process of this invention specifies a process capable of adequately producing an internal linear olefin with high double bond migration in high yield even when using an olefin with a high water content, obtained by dehydration reaction of a primary aliphatic alcohol, as a starting material, and specifies a production process of an internal olefin sulfonate salt using the internal olefin obtained by the production process.

[0019] In the process for producing an internal olefin of this invention, the dehydration reaction of a primary aliphatic alcohol having 8 to 24 carbon atoms is carried out in the presence of a solid catalyst as step (1); water formed in step (1) is separated to control the water content of the hydrated olefin to 0.008 wt% or more and 7 wt% or less as step (2); and the hydrated olefin with a water content adjusted to 0.008 wt% or more and 7 wt% or less is internally isomerized in the presence of a solid catalyst as step (3).

[0020] In this invention, the water content of the olefin with which an internal isomerization reaction is carried out in step (3) is adjusted to 0.008 wt% or more and 7 wt% or less, thereby enabling the internal isomerization reaction to proceed rapidly and suppressing the amount of byproducts, i.e., branched olefin and dimerized olefin. The reason for this effect is not necessarily clear and can be considered as follows.

[0021] The reduction in the reaction rate during the internal isomerization reaction of an olefin is presumably caused by deactivation of the catalyst due to the water contained in the starting material olefin.

[0022] However, it is considered that the catalyst is not deactivated despite the presence of such a large amount of water in the reaction system, which is not normally possible. Instead, the large amount of water is adsorbed at the active sites on the catalyst surface that cause the side reaction, thereby suppressing its occurrence. As a result, it is thought that the reaction rate of the internal isomerization is increased, and the occurrence of the side reaction is suppressed. Step (1)

[0023] In step (1) a dehydration reaction of a primary aliphatic alcohol with 8 to 24 carbon atoms is carried out in the presence of a solid catalyst. Starting material

[0024] In step (1) a primary aliphatic alcohol with 8 to 24 carbon atoms is used as starting material.

[0025] The primary aliphatic alcohol can be any alcohol derived from petroleum or any alcohol derived from a natural material.

[0026] Examples of primary aliphatic alcohols derived from natural materials include those derived from coconut oil, palm oil, palm kernel oil, soybean oil, rapeseed oil, beef tallow, lard, tall oil, and fish oil.

[0027] The number of carbon atoms of the primary aliphatic alcohol is 8 or more, preferably 10 or more, more preferably 12 or more, further preferably 14 or more and still more preferably 16 or more in view of the facilitation of the separation of water in step (2), and is 24 or less, preferably 22 or less and more preferably 18 or less in view of the availability of the starting material.

[0028] Examples of primary aliphatic alcohols derived from natural materials include n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, n-eicosanol, n-docosanol, and n-tetracosanol. catalyst

[0029] Step (1) is carried out in the presence of a solid catalyst.

[0030] The solid catalyst is preferably a solid acidic catalyst given the amplification rate of the dehydration reaction.

[0031] The ratio of the amount of weak acid of the solid acidic catalyst is preferably 70% or more, more preferably 80% or more, further preferably 90% or more and still more preferably 92% or more in view of the suppression of the formation of dimerized olefin and branched olefin, improvement of the yield of the linear olefin and the improvement of the yield of the internal olefin and is preferably 100% or less, more preferably 99% or less, further preferably 95% or less and still more preferably 94% or less in view of the improvement of the average double bond migration.

[0032] The ratio of the amount of weak acid of the solid acid catalyst is preferably 70% or more and 100% or less, more preferably 80% or more and 100% or less, and further preferably 90% or more and 100% or less, in view of the suppression of the formation of the dimerized olefin and the branched olefin, improvement of the yield of the linear olefin, improvement of the yield of the internal olefin, and improvement of the average double bond migration.

[0033] The ratio of the amount of weak acid of the solid acid catalyst is further preferably 92% or more and 100% or less in view of the suppression of the formation of the dimerized olefin and the branched olefin, improvement of the yield of the linear olefin and the improvement of the yield of the internal olefin.

[0034] The ratio of the amount of weak acid of the solid acid catalyst is further preferably 90% or more and 99% or less, more preferably 90% or more and 98% or less, more preferably 90% or more and 95% or less, and more preferably 90% or more and 94% or less, in view of the improvement of the average double bond migration.

[0035] The ratio of the amount of weak acid, as stated herein, signifies the amount of acid calculated from the amount of ammonia desorption at a desorption temperature of 300°C or less, based on the total amount of acid, as measured by an ammonia-programmed desorption method (NH3-TPD).

[0036] The NH3-TPD method involves adsorbing ammonia onto a solid catalyst. The temperature is then increased at a constant, controlled rate, and the amount of desorbed ammonia and the desorption temperature are measured. The amount and strength of the catalyst's acidity can be determined because ammonia adsorbed at weakly acidic sites beneath the acidic sites of the solid catalyst desorbed at a lower temperature, while ammonia adsorbed at strongly acidic sites desorbed at a higher temperature. Measurements using the ammonia-programmed desorption method can be performed, for example, with a catalyst analyzer, such as the "TPD-1AT" automatic temperature-controlled desorption analyzer, manufactured by Bel Japan, Inc.

[0037] The amount of weak acid can be measured as a relative amount with respect to the high peak (i.e., the peak on the side of the higher temperature among the two measured peaks), which is presumed to be 0.99 mmol / g, using ZSM-5 type zeolite, JRCö-Z5-25H, manufactured by ExxonMobil Catalyst Technologies LLC. The peaks are determined by quantitative analysis of ammonia using the ammonia fragment m / e = 17 in the mass spectrum.

[0038] The measurement method used for the NH3-TPD process can be a commonly used one. For example, pretreatment, NH3 adsorption treatment, and vacuum treatment are performed under the following conditions, and then the TPD measurement is carried out.

[0039] Pretreatment: The temperature is increased to 200°C over 20 minutes and maintained in helium for one hour.

[0040] NH3 adsorption treatment: NH3 is adsorbed at 50°C and 2.7 kPa for 10 minutes.

[0041] Vacuum treatment: 50°C for 4 hours and vacuum level: 2.7 kPa

[0042] TPD measurement: Helium gas is supplied at 50 ml / min and the temperature is increased to 600°C at a temperature increase rate of 5°C per minute.

[0043] According to the invention, the amount of weak acid is calculated from the amount of ammonia desorbed in the temperature range from the start of the measurement up to the desorption temperature of 300°C. The amount of strong acid is calculated from the amount of ammonia desorbed in the temperature range from the desorption temperature above 300°C up to the temperature at which ammonia is completely desorbed, and the sum of these amounts is referred to as the total amount of acid. The ratio of the amount of weak acid to the total amount of acid is calculated using the following expression. (Ratio of the amount of weak acid (%)) = ((Amount of weak acid (nmol / g)) / (Amount of total acid (mmol / g))) × 100

[0044] The amount of weak acid in the solid acidic catalyst is preferably 0.01 mmol / g or more, more preferably 0.05 mmol / g or more, and further preferably 0.1 mmol / g or more in view of the suppression of the side reaction.

[0045] The solid acidic catalyst that can be used in step (1) preferably contains at least one element selected from aluminium, iron and gallium, and more preferably contains aluminium in view of the improvement of the reaction rate of the dehydration reaction.

[0046] The solid acid catalyst used in step (1) is particularly specific for aluminium oxide or aluminium phosphate. Reaction temperature

[0047] The reaction temperature in step (1) is preferably 140°C or more, more preferably 200°C or more, further preferably 240°C or more and even more preferably 270°C or more in view of the improvement of the reaction rate.

[0048] The reaction temperature in step (1) is preferably 350°C or less, more preferably 300°C or less and further preferably 290°C or less in view of the suppression of the side reaction. Reaction pressure

[0049] The pressure in a reaction vessel in step (1) is preferably 0.14 MPa or less, considering the absolute pressure with respect to the reaction rate.

[0050] The pressure in the vessel is preferably 0.03 MPa or more, more preferably 0.05 MPa or more and further preferably 0.1 MPa or more, expressed as absolute pressure, with a view to carrying out the reaction with a simple apparatus, and is preferably 0.14 MPa or more, expressed as absolute pressure, for a similar reason.

[0051] The pressure in the reaction vessel in step (1) is preferably 0.03 MPa or more and 0.14 MPa or less and more preferably 0.05 MPa or more and 0.14 MPa or less, expressed as absolute pressure, and is further preferably atmospheric pressure. Inert gas

[0052] The reaction in step (1) is a dehydration reaction of an alcohol, and thus there is a possibility of reducing the reaction rate if water, which is produced as a byproduct, accumulates in the reaction vessel. Therefore, an inert gas is preferably introduced into the reaction vessel in view of the improvement in the reaction rate.

[0053] Examples of inert gases include nitrogen, argon, and helium, with nitrogen being preferred due to its availability.

[0054] The amount of intergas introduced is preferably 0.1 mol or more, and more preferably 0.2 mol or more, per 1 mol of the primary aliphatic alcohol as starting material, considering the amplification rate. The amount of inert gas introduced is preferably 10 mol or less, and more preferably 1 mol or less, considering the improvement in productivity. type of reaction

[0055] Examples of the reaction type in step (1) include a fixed-bed reaction, wherein a starting material is fed to a reaction vessel containing the solid catalyst, and a suspension-bed reaction, wherein the reaction is carried out while the solid catalyst is suspended in a starting material. The reaction type in step (1) is preferably a fixed-bed reaction for reasons of production efficiency. The reaction vessel into which the solid catalyst is loaded in the fixed-bed reaction is preferably a tubular reactor from a similar point of view.

[0056] When step (1) is carried out by the fixed-bed reaction, WHSV (mass of reactant carried per hour with respect to the unit mass of the catalyst) is preferably 0.1 per hour or more, more preferably 0.15 per hour or more and further preferably 0.2 per hour or more, and is preferably 6 per hour or less, more preferably 4 per hour or less, further preferably 2 per hour or less and still more preferably 1 per hour or less in view of the efficient carrying out of the dehydration reaction.

[0057] If step (1) is carried out by a fixed-bed reaction, LHSV (liquid hourly space velocity) is preferably 0.1 per hour or more, more preferably 0.15 per hour or more, and further preferably 0.2 per hour or more, and is preferably 5 per hour or less, more preferably 3.5 per hour or less, further preferably 1.5 per hour or less, and still more preferably 0.5 per hour or less, in view of the efficient execution of the dehydration reaction.

[0058] If step (1) is carried out by a suspension bed reaction, the amount of solid catalyst used is preferably 0.1 wt% or more and 200 wt% or less, more preferably 0.5 wt% or more and 100 wt% or less, and further preferably 1 wt% or more and 50 wt% or less, based on the starting material alcohol, in view of the improvement of the reaction rate.

[0059] The reaction time for the suspension bed reaction is preferably 0.1 hour or more and 20 hours or less, more preferably 0.5 hour or more and 10 hours or less, and further preferably 1 hour or more and 5 hours or less, given the efficient execution of the dehydration reaction.

[0060] The yield of the linear olefin at the time when step (1) is completed is preferably 90 mol% or more, more preferably 93 mol% or more and further preferably 94 mol% or more in view of the improvement in the reaction rate in step (3). Step (2)

[0061] Step (2) is a step to control the water content of the water-containing olefin obtained by the dehydration reaction of the primary aliphatic alcohol with 8 to 24 carbon atoms to 0.008 wt% or more and 7 wt% or less.

[0062] The water content of the hydrous olefin at the time when step (2) is completed is 0.008 wt% or more, given the suppression of the formation of dimerized olefin and branched olefin, the improvement of the linear olefin yield, the improvement of the internal olefin yield and the improvement of the average double bond migration, and is 7 wt% or less, preferably 1 wt% or less, more preferably 0.3 wt% or less, further preferably 0.1 wt% or less, still more preferably 0.07 wt% or less, still more preferably 0.05 wt% or less, still more preferably 0.02 wt% or less and still more preferably 0.01 wt% or less, given the suppression of the formation of dimerized olefin, the improvement of the internal olefin yield and the improvement of the average double bond migration.

[0063] The content of the primary aliphatic alcohol in the water-containing olefin at the time when step (2) is completed is preferably 1 wt% or less, more preferably 0.1 wt% or less and further preferably 0.01 wt% or less, in view of the improvement in the reaction rate in step (3).

[0064] Water in water-containing olefin can be measured using the Karl Fischer method (according to JIS K2275). Methods for controlling water content

[0065] Examples of the process for reducing the water content of the hydrated olefin in step (2) include a process for reducing the pressure in the reaction vessel in step (1), a process for increasing the flow rate of the inert gas therein, a process for reducing the pressure in the reaction vessel and simultaneously increasing the flow rate of the inert gas therein, and a process for separating the water formed in step (1) from the hydrated olefin. The process for reducing the water content of the hydrated olefin in step (2) is preferably a process for separating water formed in step (1) from the hydrated olefin with regard to the loading of the plant.

[0066] Examples of the process for separating water formed in step (1) from the water-containing olefin include a process for separating the water-containing olefin into an aqueous layer and an oily layer and subsequently isolating the aqueous layer from the oily layer, and a process for phase-separating the water-containing olefin obtained in step (1) into a gas phase and a liquid phase by applying the difference in vapor pressure, and subsequently isolating the aqueous layer from a gas phase and an oily layer.

[0067] Among these, a method for separating the water-containing olefin into an aqueous layer and an oily layer and subsequently isolating the aqueous layer from the oily layer, and a method for phase-separating the water-containing olefin obtained in step (1) into a gas phase and a liquid phase by applying the difference in vapor pressure and subsequently isolating the aqueous layer as a gas phase from the oily layer are preferred, and a method for separating the water-containing olefin into an aqueous layer and an oily layer and subsequently isolating the aqueous layer from the oily layer is more preferred in view of the carrying out of step (2) with a simple apparatus.

[0068] Examples of the process for separating the water-containing olefin into an aqueous layer and an oily layer, and the subsequent isolation of the aqueous layer from the oily layer in step (2), include static separation and centrifugal separation. The process for isolating the aqueous layer and the oily layer is preferably a static separation, given that step (2) can be carried out with a simple apparatus.

[0069] The static separation time of the water-containing olefin, when the isolation is carried out by static separation, is preferably 1 minute or more, more preferably 10 minutes or more, further preferably 1 hour or more and even more preferably 3 hours or more, given the reliable isolation of the aqueous and the oily layer.

[0070] The time for static separation is preferably 10 hours or less, and more preferably 5 hours or less, in view of the improvement in production efficiency.

[0071] When insulation is achieved by static separation, the temperature of the water-containing olefin used for static separation is preferably 100°C or less, and more preferably 80°C or less, to reduce the water content of the oily layer. The temperature of the olefin is preferably 0°C or more, and more preferably 20°C or more, to improve production efficiency.

[0072] According to the invention, the water content of the water-containing olefin obtained in step (1) can be controlled by adding water to it before or after the separation of water from the water-containing olefin obtained in step (1).

[0073] If step (1) is carried out by fixed-bed reaction using a tubular reactor, the water formed flows into the reaction vessel in the state where the reaction products and unreacted starting materials are mixed, making it difficult to isolate only the water formed in this way. Therefore, if step (1) is carried out by fixed-bed reaction using a tubular reactor, it is necessary to perform step (1) and then step (2). Step (3)

[0074] In step (3) the water-containing olefin with a water content adjusted to 0.008 wt% or more and 7 wt% or less is internally isomerized in the presence of a solid catalyst. catalyst

[0075] The solid catalyst used in step (3) is preferably an acidic catalyst in view of the improvement in the reaction rate of the isomerization reaction.

[0076] The ratio of the amount of weak acid of the solid catalyst is preferably 70% or more, more preferably 80% or more, further preferably 90% or more and still more preferably 92% or more in view of the suppression of the formation of dimerized olefin and branched olefin, the improvement of the yield of linear olefin and the improvement of the yield of internal olefin and is preferably 100% or less, more preferably 99% or less, further preferably 95% or less and still more preferably 94% or less in view of the improvement of average double bond migration.

[0077] The ratio of the amount of weak acid of the solid acid catalyst is preferably 70% or more and 100% or less, more preferably 80% or more and 100% or less, and further preferably 90% or more and 100% or less, in view of the suppression of the formation of the dimerized olefin and the branched olefin, the improvement of the yield of the linear olefin, the improvement of the yield of the internal olefin, and the improvement of the average double bond migration.

[0078] The ratio of the amount of weak acid of the solid acidic catalyst is further preferably 92% or more and 100% or less, and further preferably 95% or more and 100% or less, in view of the suppression of the formation of the dimerized olefin and the branched olefin, the improvement of the linear olefin yield, and the improvement of the internal olefin yield.

[0079] The ratio of the amount of weak acid of the solid acid catalyst is further preferably 90% or more and 99% or less, even more preferably 90% or more and 98% or less, even more preferably 90% or more and 95% or less, and even more preferably 90% or more and 94% or less, in view of the improvement of the average double bond migration.

[0080] The amount of weak acid in the solid acidic catalyst is preferably 0.01 mmol / g or more, more preferably 0.05 mmol / g or more, and further preferably 0.1 mmol / g or more in view of the suppression of the side reaction.

[0081] The solid acidic catalyst that can be used in step (3) preferably contains at least one element selected from aluminium, iron and gallium, and more preferably aluminium in view of the improvement of the average double bond migration.

[0082] The solid acidic catalyst used in step (3) is preferably γ-aluminum oxide, aluminum phosphate or the like.

[0083] The solid catalyst used in step (3) is preferably the same solid catalyst used in step (1), given the suppression of production costs. Reaction temperature

[0084] The reaction temperature in step (3) is preferably 140°C or more, more preferably 180°C or more, further preferably 200°C or more, still more preferably 230°C or more, still more preferably 240°C or more and still more preferably 270°C or more in view of the enhancement of the average double bond migration and the suppression of the formation of dimerized olefin.

[0085] The reaction temperature in step (3) is preferably 350°C or less, more preferably 300°C or less, further preferably 290°C or less, further preferably 280°C or less and even more preferably 250°C or less in view of the suppression of the formation of the branched olefin and the dimerized olefin, yield of the linear olefin and the yield of the internal olefin.

[0086] The reaction temperature in step (3) is preferably 140°C or more and 350°C or less, more preferably 180°C or more and 300°C or less, further preferably 200°C or more and 300°C or less, and even more preferably 230°C or more and 290°C or less, given the suppression of the formation of the dimerized olefin and the branched olefin, the improvement of the yield of the linear olefin, the improvement of the yield of the internal olefin, and the improvement of the average double bond migration.

[0087] The reaction temperature in step (3) is further preferably 230°C or more and 280°C or less, and even more preferably 230°C or more and 250°C or less, in view of the suppression of the formation of the branched olefin, the enhancement of the yield of the linear olefin and the improvement of the yield of the internal olefin.

[0088] The reaction temperature in step (3) is further preferably 240°C or more and 290°C or less, and even more preferably 270°C or more and 290°C or less, in view of the suppression of the formation of the dimerized olefin and the improvement of the average double bond migration. Reaction pressure

[0089] The pressure in a reaction vessel in step (3) is not particularly limited, and the pressure in step (3) is preferably 0.03 MPa or more, more preferably 0.05 MPa or more and further preferably 0.1 MPa or more, is preferably MPa or less, more preferably 0.5 MPa or less and further preferably 0.2 MPa or less, in each case as absolute pressure, and is specifically preferably atmospheric pressure given that the reaction is carried out with a simple apparatus. Inert gas

[0090] An inert gas can be introduced into a reaction vessel in step (3).

[0091] Examples of inert gases include nitrogen, argon, and helium, with nitrogen being preferred due to its availability.

[0092] The amount of introduced inert gas is preferably 0.1 mol or more, and more preferably 0.2 mol or more, per 1 mol of olefin as starting material, in view of the improvement in the reaction rate. The amount of introduced inert gas is preferably 10 mol or less, and more preferably 1 mol or less, in view of the improvement in productivity. Type of reaction

[0093] Examples of the type of reaction in step (3) include a fixed-bed reaction and a suspension-bed reaction. The type of reaction in step (3) is preferably a fixed-bed reaction due to production efficiency. The reaction vessel into which the solid catalyst is loaded for the fixed-bed reaction is preferably a tubular reactor for a similar reason.

[0094] If both steps (3) and (1) are carried out by fixed bed reaction, the reactions of the steps can be carried out with separate reaction vessels or with the same reaction vessel.

[0095] If step (1) is carried out by fixed-bed reaction, it is necessary to carry out step (2) independently of step (1) as described above. If steps (3) and (1) are carried out using the same reaction vessel, the hydrated olefin obtained in step (1) is subjected to step (2), and then the hydrated olefin from step (1) is transferred to the reaction vessel and subjected to step (3).

[0096] In the fixed-bed reaction, WHSV (mass of reactant carried per hour with respect to the unit mass of the catalyst) is preferably 0.5 per hour or more, more preferably 0.8 per hour or more, and further preferably 1 per hour or more, and is preferably 30 per hour or less, more preferably 20 per hour or less, and further preferably 10 per hour or less, considering the reaction efficiency.

[0097] If step (3) is carried out by fixed-bed reaction, LHSV (liquid hourly space velocity) is preferably 0.5 per hour or more, more preferably 0.8 per hour or more, further preferably 1 per hour or more, and still more preferably 1.2 per hour or more, and is preferably 25 per hour or less, more preferably 18 per hour or less, further preferably 10 per hour or less, and still more preferably 2 per hour or less, in view of the reaction efficiency.

[0098] If step (3) is carried out by suspension bed reaction, the amount of solid acid catalyst used is preferably 0.1 wt% or more and 200 wt% or less, more preferably 0.5 wt% or more and 100 wt% or less, and further preferably 1 wt% or more and 50 wt% or less, based on the starting material alcohol, taking into account the reaction rate.

[0099] The reaction time in the suspension bed reaction is preferably 0.1 hour or more and 20 hours or less, more preferably 0.5 hour or more and 10 hours or less, and further preferably 1 hour or more and 5 hours or less, given the reaction efficiency. yield

[0100] The yield of the linear olefin in step (3) is preferably 90 mol% or more, more preferably 93 mol% or more, further preferably 94 mol% or more and is preferably 100% or less, based on the molar number of the primary aliphatic alcohol as starting material fed into step (1).

[0101] The yield of the branched monomer olefin in step (3) is preferably 5 mol% or less and more preferably 4 mol% or less based on the molar number of the primary aliphatic alcohol as starting material fed to step (1).

[0102] The yield of the dimerized olefin in step (3) is preferably 2 mol% or less and more preferably 1.5 mol% or less, based on the molar number of the primary aliphatic alcohol as starting material which is fed to step (1). Fraction of α-olefin

[0103] The fraction of α-olefin in the olefin obtained in step (3) is preferably 2.0 mol% or less, more preferably 1.5 mol% or less and further preferably 1.0 mol% or less.

[0104] According to the invention, the double bond migration through the internal isomerization reaction is expressed by the average double bond migration, as shown below. n: odd number ∑m=1m=(n−1) / 2(m−1)×(Y / 100) n: even number ∑m=1m=n / 2(m−1)×(Y / 100) where n is the number of carbon atoms of the olefin; m represents the position of the double bond in the olefin and Y represents the percentage of the m-olefin in the olefin with a number of carbon atoms of n at the time when step (3) is completed.

[0105] The average double bond migration of the internal olefin obtained in step (3) is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more.

[0106] According to the invention, only the internal olefin in the form of the monomer can be isolated from the water-containing internal olefin thus obtained by distillation or the like, and thereby the internal olefin can be obtained with high purity. Method for producing an internal olefin sulfonate salt

[0107] The process of an internal olefin sulfonate salt of this invention comprises: a step for sulfonating an internal olefin produced by the production process of this invention to obtain a sulfonated product; and a step for neutralizing the sulfonated product and subsequently hydrolyzing the neutralized product.

[0108] The sulfonation reaction in the step to obtain a sulfonated product can be carried out by reacting the olefin with sulfur trioxide gas in an amount of preferably 0.8 mol or more and 1.2 mol or less per 1 mol of olefin.

[0109] The reaction temperature for the sulfonation reaction is preferably 0°C or higher and 80°C or lower.

[0110] The neutralization of the sulfonated product can be carried out by reaction with an aqueous alkali solution in a simple or larger quantity of 1.5 times or lesser quantity per 1 mol of the theoretical value of the sulfonic acid groups.

[0111] Examples of aqueous alkali solutions that can be used for neutralization include aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous ammonia solution, and aqueous 2-aminoethanol solution.

[0112] The hydrolysis reaction can be carried out by reacting the neutralized product at a temperature of 90°C or more and 200°C or less for a period of 30 minutes or more and 3 hours or less in the presence of water.

[0113] The sulfonation and neutralization reactions can be carried out continuously. After completion of the neutralization reaction, the product can be purified by extraction, rinsing, and similar methods.

[0114] This invention also relates to the following embodiments in addition to those mentioned above. <1> Method for producing an internal olefin using a primary aliphatic alcohol having 8 to 24 carbon atoms as a starting material, comprising carrying out the following steps (1) to (3): Step (1): a step to carry out a dehydration reaction of a primary aliphatic alcohol having 8 to 24 carbon atoms in the presence of a solid catalyst; Step (2): a step to control the water content of a water-containing olefin, obtained by the dehydration reaction, to 0.008 wt% or more and 7 wt% or less; and Step (3): a step to internally isomerize the water-containing olefin with a water content adjusted to 0.008 wt% or more and 7 wt% or less, in the presence of a solid catalyst. <2> Method for producing an internal olefin according to point <1> , wherein the primary aliphatic alcohol with 8 to 24 carbon atoms has a number of carbon atoms of 8 or more, preferably 10 or more, more preferably 12 or more, further preferably 14 or more and more preferably 16 or more and 24 or less, preferably 22 or less and more preferably 18 or less. <3> Method for producing an internal olefin according to point <1> or <2> , wherein the water content of the water-containing olefin at the time when step (2) is completed is 0.008 wt% or more and 7 wt% or less, preferably 1 wt% or less, more preferably 0.3 wt% or less, further preferably 0.1 wt% or less, still more preferably 0.07 wt% or less, still more preferably 0.05 wt% or less, still more preferably 0.02 wt% or less, still more preferably 0.01 wt% or less. <4> Method for producing an internal olefin according to one of the points <1> until <3> , wherein step (2) is a step to separate water from the water-containing olefin obtained in step (1). <5> Method for producing an internal olefin according to one of the points <1> until <4> , wherein the method for separating water in step (2) is preferably a method for isolating the aqueous layer from the oily layer of the water-containing olefin obtained in step (1), a method for evaporating water from the water-containing olefin obtained in step (1) under reduced pressure, or a method for phase-separating the water-containing olefin obtained in step (1) into a gas phase and a liquid phase using the vapor pressure difference and subsequently isolating the aqueous layer as a gas phase from the oily layer, more preferably a method for isolating the aqueous layer from the oily layer of the water-containing olefin obtained in step (1), or a method for phase-separating the water-containing olefin,obtained in step (1) into a gas phase and a liquid phase by using the difference in vapor pressure and subsequently isolating the aqueous layer as a gas phase from the oily layer, and further preferably a method for isolating the aqueous layer from the oily layer of the water-containing olefin obtained in step (1). <6> Method for producing an internal olefin according to point <5> , wherein the method for isolating the aqueous layer from the oily layer of the water-containing olefin is a static separation. <7> Method for generating an internal olefin according to point <6> , wherein the temperature of the water-containing olefin during the static separation is preferably 100°C or less, more preferably 80°C or less, more preferably 0°C or more, and more preferably 20°C or more. <8> Method for producing an internal olefin according to point <6> or <7> , wherein the time for the static separation of the water-containing olefin during the static separation is preferably 1 minute or more, more preferably 10 minutes or more, more preferably 10 hours or less, and more preferably 5 hours or less. <9> Method for generating an internal olefin according to one of the points <1> until <8> , wherein step (1) is carried out by fixed-bed reaction. <10> Method for producing an internal olefin according to one of the points <1> until <9> , wherein step (3) is carried out by fixed-bed reaction. <11> Method for producing an internal olefin according to one of the points <1> until <10> , wherein the solid catalyst in step (1) is a solid acidic catalyst and the amount of weak acid, which is the amount of acid, calculated from the amount of ammonia desorption at a desorption temperature of 300°C or less, based on the total amount of acid measured by the NH3-TPD method, is preferably 70% or more, more preferably 80% or more, further preferably 90% or more and more preferably 92% or more, and preferably 100% or less, more preferably 99% or less and further preferably 95% or less. <12> Method for producing an internal olefin according to one of the points <1> until <10> , wherein the solid catalyst in the step <1> a solid acidic catalyst and the amount of weak acid, which is the amount of acid, calculated from the amount of ammonia desorption at a desorption temperature of 300°C or less, based on the total amount of acid measured by the NH3-TPD method, is preferably 70% or more and 100% or less, more preferably 80% or more and 100% or less and further preferably 90% or more and 100% or less. <13> Method for producing an internal olefin according to one of the points <1> until <10> , wherein the solid catalyst in step (1) is a solid acidic catalyst and the amount of weak acid, which is the amount of acid, calculated from the amount of ammonia desorption at a desorption temperature of 300°C or less, based on the total amount of acid, measured by the NH3-TPD method, is further preferably 92% or more and 100% or less. <14> Method for producing an internal olefin according to one of the points <1> until <10> , wherein the solid catalyst in step (1) is a solid acidic catalyst and the amount of weak acid, which is the amount of acid, calculated from the amount of ammonia desorption at a desorption temperature of 300°C or less, based on the total amount of acid measured by the NH3-TPD method, is further preferably 90% or more and 99% or less, more preferably 90% or more and 98% or less, more preferably 90% or more and 95% or less, and more preferably 90% or more and 94% or less. <15> Method for generating an internal olefin according to one of the points <1> until <14> , wherein the solid catalyst in step (3) is a solid acidic catalyst and the amount of weak acid, which is the amount of acid, calculated from the amount of ammonia desorption at a desorption temperature of 300°C or less, based on the total amount of acid measured by the NH3-TPD method, is preferably 70% or more, more preferably 80% or more, further preferably 90% or more and more preferably 92% or more, and is preferably 100% or less, more preferably 99% or less, further preferably 95% or less and more preferably 94% or less. <16> Method for producing an internal olefin according to one of the points <1> until <14> , wherein the solid catalyst in step (3) is a solid acidic catalyst and the amount of weak acid, which is the amount of acid, calculated from the amount of ammonia desorption at a desorption temperature of 300°C or less, based on the total amount of acid measured by the NH3-TPD method, is preferably 70% or more and 100% or less, more preferably 80% or more and 100% or less, and further preferably 90% or more and 100% or less. <17> Method for producing an internal olefin according to one of the points <1> until <14> , wherein the solid catalyst in step (3) is a solid acidic catalyst and the amount of weak acid, which is the amount of acid, calculated from the amount of ammonia desorption at a desorption temperature of 300°C or less, based on the total amount of acid measured by the NH3-TPD method, is preferably 92% or more and 100% or less, and more preferably 95% or more and 100% or less. <18> Method for producing an internal olefin according to one of the points <1> until <14> , wherein the solid catalyst in step (3) is a solid acidic catalyst and the amount of weak acid, which is the amount of acid, calculated from the amount of ammonia desorption at a desorption temperature of 300°C or less, based on the total amount of acid measured by the NH3-TPD method, is further preferably 90% or more and 99% or less, more preferably 90% or more and 98% or less, more preferably 90% or more and 95% or less, and more preferably 90% or more and 94% or less. <19> Method for generating an internal olefin according to one of the points <1> until <18> , wherein the reaction temperature in step (1) is preferably 140°C or more, more preferably 200°C or more, further preferably 240°C or more and more preferably 270°C or more, and preferably 350°C or less, more preferably 300°C or less and further preferably 290°C or less. <20> Method for generating an internal olefin according to one of the points <1> until <19> , wherein the reaction temperature in step (3) is preferably 140°C or more, more preferably 180°C or more, further preferably 200°C or more, even more preferably 230°C or more, even more preferably 240°C or more and even more preferably 270°C or more, and is preferably 350°C or less, more preferably 300°C or less, further preferably 290°C or less, even more preferably 280°C or less and even more preferably 250°C or less. <21> Method for generating an internal olefin according to one of the points <1> until <19> , wherein the reaction temperature in step (3) is preferably 140°C or more and 350°C or less, more preferably 180°C or more and 300°C or less, further preferably 200°C or more and 300°C or less, and even more preferably 230°C or more and 290°C or less. <22> Method for generating an internal olefin according to one of the points <1> until <19> , wherein the reaction temperature in step (3) is preferably 230°C or more and 280°C or less and more preferably 230°C or more and 250°C or less. <23> Method for generating an internal olefin according to one of the points <1> until <19> , wherein the reaction temperature in step (3) is preferably 240°C or more and 290°C or less and more preferably 270°C or more and 290°C or less. <24> Method for producing an internal olefin according to one of the points <1> until <23> , wherein the reaction pressure in step (1) is preferably 0.03 MPa or more, more preferably 0.05 MPa or more and further preferably 0.1 MPa or more and preferably 0.14 MPa or less and more preferably 0.03 MPa or more and 0.14 MPa or less and further preferably atmospheric pressure. <25> Method for producing an internal olefin according to one of the points <1> until <24> , wherein the reaction pressure in step (3) is preferably 0.03 MPa or more, more preferably 0.05 MPa or more and further preferably 0.1 MPa or more, preferably 1 MPa or less, more preferably 0.5 MPa or less and further preferably 0.2 MPa or less and particularly preferably atmospheric pressure. <26> Method for generating an internal olefin according to one of the points <9> until <25> , wherein WHSV in step (1) is preferably 0.1 per hour or more, more preferably 0.15 per hour or more and further preferably 0.2 per hour or more, and preferably 6 per hour or less, more preferably 4 per hour or less, further preferably 2 per hour or less and still further preferably 1 per hour or less. <27> Method for generating an internal olefin according to one of the points <9> until <26> , wherein the LHSV in step (1) is preferably 0.1 per hour or more, more preferably 0.15 per hour or more and further preferably 0.2 per hour or more, and preferably 5 per hour or less, more preferably 3.5 per hour or less, further preferably 1.5 per hour or less and still more preferably 0.5 per hour or less. <28> Method for generating an internal olefin according to one of the points <10> until <27> , wherein the LHSV in step (3) is preferably 0.5 per hour or more, more preferably 0.8 per hour or more, further preferably 1 per hour or more and more preferably 1.2 per hour or less, and preferably 25 per hour or less, more preferably 18 per hour or less, further preferably 10 per hour or less and more preferably 2 per hour or less. <29> Method for producing an internal olefin according to one of the points <1> until <28> , wherein the average double bond migration of the internal olefin obtained in step (3) is preferably 2 or more, more preferably 3 or more and further preferably 4 or more. Examples of measurement conditions

[0115] The quantitative determination of the olefins in the samples, obtained in the examples and comparison examples below, was carried out as follows. Alcohol conversion, olefin yield and quantitative determination of water

[0116] The sample was diluted with water and then analyzed using a gas chromatography analyzer (HP6890, manufactured by Hewlett-Packard Company, column: Ultra ALLOY-1 capillary column, 30.0 m × 250 µm (manufactured by Frontier Laboratories, Ltd.), detector: hydrogen flame ionization detector (FID)) at an injection temperature of 300°C, a detector temperature of 350°C and a He flow rate of 4.6 ml / min, thereby quantitatively determining the starting material alcohol and the olefin thus formed.

[0117] The alcohol conversion, the product yield, the amount of branched monomeric olefin formed in step (3), the amount of dimerized olefin formed in step (3), and the α-olefin fraction were calculated by the following yield. (Alcohol conversion (mol%)) = 100 − ((remaining amount of alcohol (mol)) / (amount of starting material − alcohol (mol))) × 100 (Yield of linear monomeric olefin (mol%)) = ((Amount of linear monomeric olefin (mol)) / (Amount of starting material − alcohol (mol))) × 100 (Yield of branched monomeric olefin (mol%)) = ((Amount of branched monomeric olefin (mol)) / (Amount of starting material - alcohol added (mol))) × 100 (Yield of dimerized olefin (mol%) = (((amount of dimerized olefin (mol)) × 2) / amount of starting material − alcohol (mol)) × 100 (Amount of branched monomeric olefin formed in step (3) (mol%)) = (Yield of branched monomeric olefin after performing step (3) (mol%) − (Yield of branched monomeric olefin after performing step (2) (mol%)) Amount of dimerized olefin formed in step (3) (mol%) = (Yield of dimerized olefin after performing step (3) (mol%)) − (Yield of dimerized olefin after performing step (2) (mol%)) (Fraction of α−olefin(mol%))=((Amount of α−olefin(mol)) / ((Amount of linear monomeric olefin(mol))+(Amount of branched monomeric olefin(mol))+(Amount of desdimerized olefin(mol))))×100

[0118] The water content in the sample was measured using a Karl Fischer water analyzer (Taitrand 852, manufactured by Metrhom Japan Ltd.). Quantitative determination of the position of the olefinic double bond

[0119] 25 parts by mass of dimethyl disulfide and 1 part by mass of iodine were added to 1 part by mass of the sample, which was then stirred at room temperature for 1 hour. 25 parts by mass of a 30 wt% aqueous sodium thiosulfate solution were then added, followed by vigorous shaking until the mixture became transparent. Subsequently, 25 parts by mass of ethanol and 21 parts by mass of hexane were added in that order, followed by mixing. After separating the mixture into layers by static separation, the resulting hexane layer was subjected to quantitative determination of the position of the olefinic double bond using a gas chromatograph (HP6890, manufactured by Hewlett-Packard Company, column: Ultra ALLOY-1 capillary column, 30.0 m × 250 µm, manufactured by Frontier Laboratories, Ltd.).), Detector: Hydrogen flame ionization detector (FID)) under the conditions of an injection temperature of 300°C, a detector temperature of 350°C and a He flow rate of 4.6 ml / min. Example 1 (Step (1)

[0120] A reaction tube with an inner diameter of 35 mm and a length of 500 mm was positioned vertically. A γ-aluminium catalyst, Neobead GB13 (manufactured by Mizusawa Industrial Chemicals, Ltd., amount of weak acid: 0.28 mmol / g, ratio of the amount of weak acid: 92.5%, 335 g) was placed in the reaction tube.

[0121] At a catalyst layer temperature of 280°C, stearyl alcohol, Kalcol 8098 (manufactured by Kao Corporation, density at 20°C: 0.83 g / cm³) was used. 3Stearyl alcohol was added as a primary aliphatic alcohol at a rate of 0.15 L per hour (LHSV: 0.30 L per hour, WHSV: 0.37 L per hour), and nitrogen was introduced at a rate of 3.2 L per hour, given the volume under standard conditions (amount of nitrogen introduced: 0.3 mol per 1 mol of stearyl alcohol), from the upper part of the reaction tube under atmospheric pressure for 72 hours. The liquid drained from the outlet of the reaction tube was cooled to 80°C, and the hydrated olefin was collected. The alcohol conversion of 100 mol%, the yield of the linear monomeric olefin was 98.5 mol%, the yield of the branched monomeric olefin was 0.33 mol%, the yield of the dimerized olefin was 1.22 mol%, the yield of 1-octadecene was 4.9 mol%, and the average double bond migration was 2.1. Step (2)

[0122] The water-containing olefin obtained in step (1) was separated into an oily layer and an aqueous layer by static separation at a temperature of 40°C for 4 hours. The resulting oily layer was used as the starting material in step (3), and the aqueous layer was discarded. The water content of the oily layer was 0.0044 wt%. Step (3)

[0123] A reaction tube with an inner diameter of 35 mm and a length of 500 mm was arranged vertically and 0.5 l (335 g) of γ-alumina of the same type and batch as the catalyst used in step (1) was filled into the reaction tube.

[0124] At a catalyst layer temperature of 280°C, the oily layer obtained in step (2) was fed at a rate of 0.75 l per hour (LHSV: 1.50 l per hour), and nitrogen was supplied at a rate of 3.2 l per hour, expressed as volume, under standard conditions from the upper part of the reaction tube at atmospheric pressure for 14 hours. The liquid drained from the outlet of the reaction tube was cooled to 40°C and collected.

[0125] The yield of the linear monomeric olefin was 94.2 mol%, the amount of the branched monomeric olefin formed in step (3) was 4.17 mol%, and the amount of the dimerized olefin formed therein was 0.11 mol%. The yield of 1-octadecene was 1.63 mol%, and the average double bond migration was 4.1. The results are shown in Table 1. Example 2

[0126] The same procedure as in Example 1 was carried out under the same conditions, except that the temperature during the static separation in step (2) was changed to 80°C in Example 1. The water content of the oily layer obtained in step (2) was 0.0090 wt%, and the yield of the linear monomeric olefin obtained in step (3) was 94.9 mol%. The amount of branched monomeric olefin formed in step (3) was 3.58 mol%, and the dimerized olefin was not formed in step (3). The yield of 1-octadecene was 0.88 mol%, and the average double bond migration was 4.3. The results are shown in Table 1. Example 3

[0127] The same procedure as in Example 1 was carried out under the same conditions, except that deionized water was added to the oily layer obtained in step (2) in Example 1, obtaining an oily component with a water content controlled to 0.1481 wt%, and the oily component was used in step (3).

[0128] The yield of the linear monomeric olefin obtained in step (3) was 96.1 mol%. The amount of the branched monomeric olefin formed in step (3) was 1.97 mol%. The yield of 1-octadecene was 2.00 mol%, and the average double bond migration was 3.7. The results are shown in Table 1. Example 4

[0129] The same procedures were carried out under the same conditions as in Example 1, except that palmityl alcohol (Kalcol 8098, manufactured by Kao Corporation) was used as the primary aliphatic alcohol in step (1) of Example 1, and deionized water was added to the oily layer obtained in step (2), obtaining an oily component with a water content adjusted to 0.0570 wt%, and the oily component was used in step (3).

[0130] The alcohol conversion of the hydrated olefin obtained in step (1) was 100 mol%, the yield of the linear monomeric olefin was 98.8 mol%, the yield of the branched monomeric olefin was 0.25 mol%, and the yield of the dimerized olefin was 0.93 mol%. The yield of 1-hexadecene was 3.41 mol%, and the average double bond migration was 2.2.

[0131] The yield of the linear monomeric olefin obtained in step (3) was 96.0 mol%. The amount of the branched monomeric olefin formed in step (3) was 2.47 mol%, and the amount of the dimerized olefin formed in step (3) was 0.35 mol%. The yield of 1-hexadecene was 0.70 mol%, and the average double bond migration was 4.4. The results are shown in Table 1. Example 5

[0132] The same process was carried out under the same conditions as in Example 1, except that a mixed alcohol comprising palmityl alcohol and stearyl alcohol in a mass ratio of 80 / 20 was used as the primary aliphatic alcohol in step (1) in Example 1, and deionized water was added to the oily layer obtained in step (2), obtaining an oily component with a water content adjusted to 0.0570 wt%, and the oily component was used in step (3).

[0133] The alcohol conversion of the hydrated olefin obtained in step (1) was 100 mol%, the yield of the linear monomeric olefin was 98.7 mol%, the yield of the branched monomeric olefin was 0.27 mol%, and the yield of the dimerized olefin was 0.94 mol%. The yield of 1-olefin was 3.54 mol%, and the average double bond migration was 1.97.

[0134] The yield of the linear monomeric olefin obtained in step (3) was 95.6 mol%. The amount of the branched monomeric olefin formed in step (3) was 2.85 mol%, and the amount of the dimerized olefin formed in step (3) was 0.31 mol%. The yield of 1-olefin was 0.80 mol%, and the average double bond migration was 4.3. The results are shown in Table 1. Example 6: Catalyst Manufacturing Example 1

[0135] 9.9 g of ethylphosphonic acid, 27.7 g of 85% orthophosphoric acid, and 112.5 g of aluminum nitrate (nonahydrate) were dissolved in 1000 g of water. An aqueous ammonia solution was added dropwise to the resulting mixture at room temperature, and the pH was raised to 5 beforehand, yielding a white precipitate in the form of a gel. The precipitate was filtered and rinsed with water, then dried at 110°C for 15 hours and pulverized to 60 mesh or less. 10 parts by mass of Aluminasol were added to 100 parts by mass of the pulverized catalyst, and the mixture was extruded to a diameter of 2.5 mm. The formed mixture was baked at 250°C for 3 hours, yielding a formed catalyst from a solid acidic catalyst (hereinafter referred to as Catalyst 1). The resulting catalyst had a weak acid content of 1 mmol / g and a weak acid ratio of 96%. reaction

[0136] The same procedures were carried out under the same conditions as in Example 1, except that 0.5 l (270 g) of the catalyst obtained in catalyst preparation Example 1 was placed as catalyst into the reaction tube in step (3) of Example 1, the temperature of the catalyst layer was 240°C, and deionized water was added to the oily layer obtained in step (2), obtaining an oily component with a water content adjusted to 0.0570 wt%, and the oily component was used in step (3).

[0137] The amount of linear monomeric olefin obtained in step (3) was 95.8 mol%. The amount of branched monomeric olefin formed in step (3) was 2.47 mol%, and the amount of dimerized olefin formed in step (3) was 0.24 mol%. The yield of 1-octadecene was 0.24 mol%, and the average double bond migration was 3.1. The results are shown in Table 1. Comparative example 1

[0138] The same procedures were carried out under the same conditions as in Example 1, except that deionized water was added to the oily layer obtained in step (2) in Example 1, obtaining an oil-water suspension with a water content adjusted to 7.1 wt%, and step (3) was carried out with the suspension supplied at a rate of 0.42 l per hour, and nitrogen supplied at a rate of 1.8 l per hour, expressed as volume, under standard conditions.

[0139] The yield of the linear monomeric olefin obtained in step (3) was 98.4 mol%. The branched monomeric olefin and the dimerized olefin were not found in step (3). The yield of 1-octadecene was 2.53 mol%, and the average double bond migration was 2.9. The results are shown in Table 1. Example 7: Production of internal sodium olefin sulfonate

[0140] A thin-film sulfonation reactor with an external jacket was used. The internal olefin, obtained in step (3) of Example 7, was introduced into the reactor, and the sulfonation reaction was carried out by passing sulfur trioxide gas (SO3) through it. Cooling water at 20°C was passed through the reactor's external jacket during the reaction. The molar ratio of sulfur trioxide gas to the internal olefin (SO3 / internal olefin) established during the sulfonation reaction was 1.01.

[0141] The sulfonated product obtained by the sulfonation reaction was added to an aqueous alkali solution prepared using sodium hydroxide at 1.5 times the theoretical acid value, followed by stirring at 30°C for one hour to neutralize the solution. The neutralized product was hydrolyzed by heating in an autoclave at 160°C for one hour, yielding a crude product of internal sodium olefin sulfonate. The concentration of sodium olefin sulfonate in the crude product of internal sodium olefin sulfonate was 35 wt%. The concentration of sodium olefin sulfonate was measured by a potentiometric titration using a benzethonium chloride solution (Test Procedure for Synthetic Detergents, JIS K3362). Table 1 Example See e.g. 1 2 3 4 5 6 1 Condition catalyst γ-Alumina γ-Alumina γ-Alumina γ-Alumina γ-Alumina Catalyst manufacturing example 1 γ-Alumina Number of carbon atoms of the starting material alcohol 18 18 18 16 16 / 18 (mixture) 18 18 Water content after completion of step (2) (mass%) 0,0044 0,0090 0,1481 0,0570 0,0570 0,0570 7,1000 Fluid space velocity (per hour) 1,50 1,50 1,50 1,50 1,50 1,50 0,83 Selectivity in step (3) Amount of branched olefin formed (mol%) 4,17 3,58 1,97 2,47 2,85 2,47 0,00 Amount of dimerized olefins (mol%) 0,11 0,00 0,40 0,35 0,31 0,24 0,00 Table 1 (continued) Example See e.g. 1 2 3 4 5 6 1 Internal olefin Yield of deslinear olefin (mol%) 94,2 94,9 96,1 96,0 95,6 95,8 98,4 yield of 1-olefin (mol%) 1,63 0,88 2,00 0,70 0,80 0,24 2,53 Average double bond migration 4, 1 4, 3 3, 7 4, 4 4, 3 3, 1 2, 9

[0142] According to this invention, a linear internal olefin with high double bond migration can be adequately prepared in high yield by using an olefin obtained by dehydration reaction of a primary aliphatic alcohol.

Claims

[1] Method for producing an internal olefin using a primary aliphatic alcohol having 8 to 24 carbon atoms as a starting material, comprising carrying out the following steps (1) to (3): Step (1): a step to carry out a dehydration reaction of a primary aliphatic alcohol having 8 to 24 carbon atoms in the presence of a solid catalyst; Step (2): a step to control the water content of a water-containing olefin, obtained by the dehydration reaction, to 0.008 wt% or more and 7 wt% or less; and Step (3): a step to internally isomerize the water-containing olefin with a water content adjusted to 0.008 wt% or more and 7 wt% or less, in the presence of a solid catalyst. [2] Method for producing an internal olefin according to claim 1, wherein the internal olefin obtained in step (3) has an average double bond migration of 2 or more. [3] Method for producing an internal olefin according to claim 1 or 2, wherein the water content in step (2) is adjusted by separating water from the water-containing olefin. [4] Method for producing an internal olefin according to any one of claims 1 to 3, wherein step (1) is carried out by fixed bed reaction. [5] Method for producing an internal olefin according to any one of claims 1 to 4, wherein step (3) is carried out by fixed bed reaction. [6] Method for producing an internal olefin according to any one of claims 1 to 5, wherein the reaction temperature in step (1) is 140°C or more and 350°C or less. [7] Method for producing an internal olefin according to any one of claims 1 to 6, wherein the reaction temperature in step (3) is 140°C or more and 350°C or less. [8] Method for producing an internal olefin according to any one of claims 1 to 7, wherein the solid catalyst in step (1) is a solid acid catalyst. [9] Method for producing an internal olefin according to any one of claims 1 to 8, wherein the solid catalyst in step (3) is a solid acid catalyst. [10] Method for producing an internal olefin according to claim 8, wherein the solid catalyst in step (1) has an amount of the weak acid of 70% or more. [11] Method for producing an internal olefin according to claim 9, wherein the solid catalyst in step (1) has an amount of the weak acid of 70% or more. [12] Method for producing an internal olefin according to claim 10, wherein the solid catalyst in step (1) contains at least one element selected from aluminium, iron and gallium. [13] Method for producing an internal olefin according to claim 11, wherein the solid catalyst in step (3) contains at least one element selected from aluminium, iron and gallium. [14] Method for producing an internal olefin according to any one of claims 1 to 13, wherein the solid catalyst used in step (3) is the same solid catalyst used in step (1). [15] Method for producing an internal olefin according to any one of claims 4 to 14, wherein a reaction vessel into which the solid catalyst is filled is a tubular reactor. [16] Method for producing an internal olefin according to any one of claims 4 to 15, wherein the LHSV in step (1) is 0.1 per hour or more and 5 per hour or less. [17] Method for producing an internal olefin according to any one of claims 5 to 16, wherein an LHSV in step (3) is 0.5 per hour or more and 25 per hour or less. [18] Method for producing an internal olefin according to any one of claims 1 to 17, wherein an inert gas is introduced into a reaction vessel in step (1). [19] Method for producing an internal olefin according to any one of claims 1 to 18, wherein an inert gas is introduced into a reaction vessel in step (3). [20] Method for producing an internal olefin sulfonate salt, comprising: a step for sulfonating the internal olefin produced by the production process according to any one of claims 1 to 19, to obtain a sulfonated product; and a step for neutralizing the sulfonated product and subsequently hydrolyzing the neutralized product.