DE112014000437T5 - Process for producing an internal olefin - Google Patents

Abstract

A process for producing an internal olefin using a primary aliphatic alcohol having 8 to 24 carbon atoms as a starting material comprises carrying out the following steps (1) to (3): Step (1): a step of carrying out a dehydration reaction of a primary aliphatic alcohol 8 to 24 carbon atoms in the presence of a solid catalyst; Step (2): a step of controlling a water content of a water-containing olefin obtained by the dehydration reaction to 0.001 mass% or more and 7 mass% or less; and Step (3): a step of internally isomerizing the water-containing olefin having a hydrogen content of 0.001 mass% or more and 7 mass% or less, in the presence of a solid catalyst.

Description

Field of the invention

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

An internal olefin is used as a base oil for an oil drilling fluid, a detergent raw material, a paper sizing raw material, a base oil or a lubricant oil raw material, a chemical product raw material, and the like. Examples of the conventional process for producing an internal olefin include a process for producing an internal olefin using an α-olefin obtained by polymerizing ethylene or the like, and wherein the α-olefin having a reduced water content with zeolite and / or montmorillonite as Catalyst comes in contact (PTL 1).

Examples of the method also include a method of obtaining an internal olefin using a crystalline metallosilicate as a catalyst in the presence of water (PTL 2).

Examples of the method of producing an α-olefin as a starting material of an internal olefin include a method of providing an α-olefin by dehydration reaction of a primary aliphatic alcohol (PTL 3 and PTL 4).

List of pamphlets

Patent literatures

• PTL 1: JP-A-2005-239651
• PTL 2: JP-A-10-167989
• PTL 3: JP-A-2,003 to 95,994
• PTL 4: WO 2011/052732

Summary of the invention

• [1] Verfahren zur Erzeugung eines internen Olefins unter Verwendung eines primären aliphatischen Alkohols mit 8 bis 24 Kohlenstoffatomen als Ausgangsmaterial, umfassend die Durchführung der folgenden Schritte (1) bis (3): Schritt (1): ein Schritt zum Durchführen einer Dehydratisierungsreaktion eines primären aliphatischen Alkohols mit 8 bis 24 Kohlenstoffatomen in der Gegenwart eines festen Katalysators; Schritt (2): ein Schritt zum Steuern eines Wassergehaltes eines Wasser-haltigen Olefins, erhalten durch die Dehydratisierungsreaktion, auf 0,001 Massen% oder mehr und 7 Massen% oder weniger; und Schritt (3): ein Schritt zum internen Isomerisieren des Wasser-haltigen Olefins mit einem Wasserstoffgehalt, der auf 0,001 Massen% oder mehr und 7 Massen% oder weniger eingestellt ist, in der Gegenwart eines festen Katalysators.
• [2] Verfahren zur Erzeugung eines internen Olefinsulfonatsalzes, umfassend: einen Schritt zum Sulfonieren eines internen Olefins, das durch das Produktionsverfahren gemäß Punkt [1] erzeugt ist, unter Erhalt eines sulfonierten Produktes; und einen Schritt zum Neutralisieren des sulfonierten Produktes und anschließendes Hydrolysieren des neutralisierten Produktes.

This invention relates to the following items [1] and [2]

• [1] A process for producing an internal olefin using a primary aliphatic alcohol having 8 to 24 carbon atoms as the starting material, which comprises carrying out the following steps (1) to (3): Step (1): a step of carrying 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 of controlling a water content of a water-containing olefin obtained by the dehydration reaction to 0.001 mass% or more and 7 mass% or less; and step (3): a step of internally isomerizing the water-containing olefin having a hydrogen content adjusted to 0.001 mass% or more and 7 mass% or less in the presence of a solid catalyst.
• [2] A process for producing an internal olefin sulfonate salt, comprising: a step of sulfonating an internal olefin produced by the production method of the item [1] to obtain a sulfonated product; and a step of neutralizing the sulfonated product and then hydrolyzing the neutralized product.

Detailed description of the invention

An internal olefin must have a high double-bond migration in view of the flowability thereof and is required to have a high linearity in view of the biodegradability thereof.

PTL 1 describes a process for producing 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 studied.

PTL 2 describes a process for producing an internal olefin with a crystalline metallosilicate as a catalyst in the presence of water in a large excess amount with respect 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.

PTL 3 describes a method for producing an α-olefin by dehydration reaction of a primary aliphatic alcohol, but there is no specific study on the technique for producing an internal olefin. PTL 4 also describes a process for producing an olefin by dehydration reaction of a primary aliphatic alcohol, but there is no study on a process for efficiently carrying out an isomerization reaction when the dehydration reaction is carried out while removing water from the system.

When an α-olefin is obtained by dehydration reaction of a primary aliphatic alcohol as a process for producing 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-olefins, and the double bond migration of the internal olefin, obtained with the α-olefin as the starting material, decreases.

PTL 1 does not suggest the use of a starting material having a large 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.

The method described in PTL 2 is the method of carrying out the reaction under condition having a water content higher than the water content resulting from the dehydration reaction of an alcohol, and thus is not practically applicable to the isomerization process which occurs immediately after the dehydration reaction Alcohol is carried out. Furthermore, there is no specific description regarding the influence of the water content on the isomerization reaction.

This invention relates to a process capable of adequately yielding a linear internal olefin having a high double bond migration in high yield even when using an olefin having a large water content obtained by dehydration reaction of a primary aliphatic alcohol as a starting material and to provide a process for producing an internal olefin sulfonate salt using the internal olefin obtained by the production process.

• [1] Verfahren zur Erzeugung eines internen Olefins unter Verwendung eines primären aliphatischen Alkohols mit 8 bis 24 Kohlenstoffatomen als Ausgangsmaterial, umfassend die Durchführung der folgenden Schritte (1) bis (3): Schritt (1): ein Schritt zum Durchführen einer Dehydratisierungsreaktion eines primären aliphatischen Alkohols mit 8 bis 24 Kohlenstoffatomen in der Gegenwart eines festen Katalysators; Schritt (2): ein Schritt zum Steuern eines Wassergehaltes eines Wasser-haltigen Olefins, erhalten durch die Dehydratisierungsreaktion, auf 0,001 Massen% oder mehr und 7 Massen% oder weniger; und Schritt (3): einen Schritt zum internen Isomerisieren des Wasser-haltigen Olefins mit einem Wassergehalt, der auf 0,001 Massen% oder mehr und 7 Massen% oder weniger eingestellt ist, in der Gegenwart eines festen Katalysators.
• [2] Verfahren zur Erzeugung eines internen Olefinsulfonatsalzes, umfassend: einen Schritt zum Sulfonieren des internen Olefins, das durch das Produktionsverfahren gemäß Punkt [1] erzeugt ist, unter Erhalt eines sulfonierten Produktes; und einen Schritt zum Neutralisieren des sulfonierten Produktes und anschließendes Hydrolysieren des neutralisierten Produktes.

This invention relates to the following items [1] and [2].

• [1] A process for producing an internal olefin using a primary aliphatic alcohol having 8 to 24 carbon atoms as the starting material, which comprises carrying out the following steps (1) to (3): Step (1): a step of carrying 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 of controlling a water content of a water-containing olefin obtained by the dehydration reaction to 0.001 mass% or more and 7 mass% or less; and Step (3): a step of internally isomerizing the water-containing olefin having a water content adjusted to 0.001 mass% or more and 7 mass% or less in the presence of a solid catalyst.
• [2] A process for producing an internal olefin sulfonate salt, comprising: a step of sulfonating the internal olefin produced by the production method of the item [1] to obtain a sulfonated product; and a step of neutralizing the sulfonated product and then hydrolyzing the neutralized product.

The production method of this invention provides a method capable of adequately indicating an internal linear olefin having a high double-bond migration in a high yield even when an olefin having a large water content obtained by dehydration reaction of a primary aliphatic alcohol, is used as a starting material and to indicate a production process of an internal olefin sulfonate salt using the internal olefin obtained by the production process.

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 the step (1) is separated to control the water content of the water-containing olefin to be 0.001 mass% or more and 7 mass% or less as the step (2); and the water-containing olefin having a water content set to 0.001 mass% or more and 7 mass% or less is isomerized internally in the presence of a solid catalyst as step (3).

In this invention, the water content of the olefin with which an internal isomerization reaction is carried out in the step (3) is set to 0.001 mass% or more and 7 mass% or less, whereby the internal isomerization reaction can be carried out quickly and the amount of by-products That is, a branched olefin and a dimerized olefin can be suppressed. The cause of the effect is not necessarily clear and can be considered as follows.

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

However, it is considered that the catalyst is not deactivated although such a large amount of water is present in the reaction system, which is not normally possible, but that the large amount of water is adsorbed on the active sites on the surface of the catalyst cause the side reaction, whereby the occurrence of a side reaction is suppressed. As a result, it is considered that the reaction rate of the internal isomerization is increased, and the occurrence of the side reaction is suppressed.

Step 1)

In step (1), a dehydration reaction of a primary aliphatic alcohol having 8 to 24 carbon atoms is carried out in the presence of a solid catalyst.

starting material

In step (1), a primary aliphatic alcohol having 8 to 24 carbon atoms is used as a starting material.

The primary aliphatic alcohol may be any of alcohol derived from petrol and an alcohol derived from a natural material.

Examples of the primary aliphatic alcohol derived from a natural material include those derived from a coconut oil, palm oil, palm kernel oil, soybean oil, rapeseed oil, beef tallow, lard, tall oil and fish oil.

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 facilitating the separation of water in the 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.

Examples of the primary aliphatic alcohol derived from a natural material include n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, n-eicosanol, n -docosanol and n-tetracosanol.

catalyst

The step (1) is carried out in the presence of a solid catalyst.

The solid catalyst is preferably a solid acid catalyst in view of the amplification reaction rate of the dehydration reaction.

The ratio of the amount of the weak acid of the solid acidic catalyst is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more and still more preferably 92% or more in view of suppressing the formation of dimerized olefin and branched olefin . Improving the yield of the linear olefin and improving 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.

The ratio of the amount of the weak acid of the solid acidic catalyst is preferably 70% or more and 100% or less, more preferably 80% or more and 100% or less, and more preferably 90% or more and 100% or less in view of the suppression of 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.

The ratio of the amount of the weak acid of the solid acidic catalyst is more preferably 92% or more and 100% or less in view of suppressing the formation of the dimerized olefin and the branched olefin, improving the yield of the linear olefin, and improving the yield of the internal olefins ,

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

The ratio of the amount of the weak acid as stated herein means 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 determined by an ammonia-programmed desorption process (US Pat. NH ₃ -TPD) is measured.

The NH ₃ -TPD method is such a method that ammonia is adsorbed on a solid catalyst, the temperature is then raised at a constant controlled rate of temperature increase, and the amount of ammonia desorbed and the desorption temperature are measured. The acid amount and the acid strength of the catalyst can be measured thereby, because ammonia adsorbed at weakly acidic sites among the acid sites of the solid catalyst is desorbed at a lower temperature, while ammonia adsorbed at strongly acidic sites is desorbed Desorbed higher temperature. The measurement by the ammonia-programmed desorption method may be performed, for example, with a catalyst analyzer, an automatic temperature-controlled desorption analyzer "TPD-1AT" produced by Bel Japan, Inc.

The amount of the weak acid may be expressed as a relative amount with respect to the high peak (ie, the peak on the higher temperature side among the two measured peaks), which is presumed to be 0.99 mmol / g with ZSM-5 type zeolite , JRC6-Z5-25H, produced by ExxonMobil Catalyst Technologies LLC. The peaks are determined by quantitative determination of ammonia with the fragment of ammonia m / e = 17 in the mass spectrum.

The measuring method which becomes the NH ₃ -TPD method may be a measuring method which is usually performed. For example, the pretreatment, the NH ₃ adsorption treatment and the vacuum treatment are carried out under the following conditions, and then the TPD measurement is performed.

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

NH ₃ adsorption treatment: NH ₃ is adsorbed at 50 ° C and 2.7 kPa for 10 minutes.
Vacuum treatment: 50 ° C for 4 hours and vacuum level: 2.7 kPa

TPD measurement: Helium gas is passed at 50 ml / min and the temperature is raised to 600 ° C at a temperature increase rate of 5 ° C per minute.

According to the invention, the amount of weak acid from the ammonia desorption amount in the temperature range from the beginning of the measurement to the desorption temperature of 300 ° C is calculated, the amount of strong acid is from the ammonia desorption in the temperature range from the desorption temperature of more than 300 ° C calculated to the temperature at which ammonia is completely desorbed, and the Total is called the total amount of acid. The ratio of the amount of the weak acid with respect to the total amount of acid is calculated by the following expression. (Ratio of the amount of weak acid (%)) = ((amount of weak acid (mmol / g)) / (amount of total acid (mmol / g))) × 100

The amount of the weak acid in the solid acid 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.

The solid acid catalyst which can be used in the step (1) preferably contains at least one element selected from aluminum, iron and gallium, and more preferably contains aluminum in view of the improvement of the reaction rate of the dehydration reaction.

The solid acid catalyst used in step (1) is particularly specific for alumina or aluminum phosphate.

reaction temperature

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

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

reaction pressure

The pressure in a reaction vessel in the step (1) is preferably 0.14 MPa or less in view of the absolute pressure in terms of the reaction rate.

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 in terms of absolute pressure in terms of conducting the reaction with a simple plant, and is preferably 0.14 MPa or more in terms of absolute pressure, for a similar reason.

The pressure in the reaction vessel in the 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 in terms of absolute pressure, and is more preferably more atmospheric Print.

inert gas

The reaction in the step (1) is a dehydration reaction of an alcohol, and thus there is a possibility of reducing the reaction rate when water generated as a by-product is accumulated in the reaction vessel. Accordingly, an inert gas is preferably introduced in the reaction vessel in view of the improvement of the reaction rate.

Examples of the inert gas include nitrogen, argon and helium, and nitrogen is preferable in view of availability.

The amount of the interstituted gas is preferably 0.1 mol or more, and more preferably 0.2 mol or more, per 1 mol of the primary aliphatic alcohol as a starting material in view of the amplification reaction rate. The amount of the introduced inert gas is preferably 10 mol or less, and more preferably 1 mol or less, in view of the improvement in productivity.

of reaction

Examples of the reaction manner in the step (1) include a fixed bed reaction in which a raw material is supplied to a reaction tank having the solid catalyst filled therein, and a suspension bed reaction in which the reaction is carried out while the solid catalyst is in a starting material is suspended. The reaction mode in step (1) is preferably a fixed bed reaction in view of production efficiency. The reaction vessel into which the solid catalyst is filled in the fixed bed reaction is preferably a tubular reactor from a similar standpoint.

When the step (1) is carried out by the fixed bed reaction, WHSV (mass of the reactant fed per one 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 more preferably 0.2 per hour or more, and is preferably 6 per hour or less, more preferably 4 per hour or less, more preferably 2 per hour or less, and still more preferably 1 hour or less, in view of the efficient performance of the dehydration reaction.

When the 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 or more hour, and is preferable 5 per hour or less, more preferably 3.5 per hour or less, more preferably 1.5 per hour or less, and still more preferably 0.5 hour or less in view of the efficient performance of the dehydration reaction.

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

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 in view of the efficient performance of the dehydration reaction ,

The yield of the linear olefin at the time when the 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 of the reaction rate in the step (3 ).

Step 2)

The step (2) is a step of controlling the water content of the water-containing olefin obtained by the dehydration reaction of the primary aliphatic alcohol having 8 to 24 carbon atoms to 0.001 mass% or more and 7 mass% or less.

The water content of the water-containing olefin at the time when the step (2) is completed is 0.001 mass% or more, preferably 0.005 mass% or more, and more preferably 0.008 mass% or more in view of suppressing the formation of dimerized olefin and the branched olefin, improving the yield of the linear olefin, improving the yield of the internal olefin and improving the average double bond migration, and is 7 mass% or less, preferably 1 mass% or less, more preferably 0.3 mass% or less, more preferably 0.1% or less by mass, even more preferably 0.07% by mass or less, even more preferably 0.05% by mass or less, more preferably 0.02% by mass or less and still more preferably 0.01 Mass% or less in view of suppressing the formation of the dimerized olefin, improving the yield of the internal olefin, and improving the average double-bond migrati on.

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

Water in the water-containing olefin can be measured by the Karl Fischer method (according to JIS K2275).

Method for controlling the water content

Examples of the method for reducing the water content of the water-containing olefin in the step (2) include a method of reducing the pressure in the reaction vessel in the step (1), a method of Increasing the flow amount of the inert gas therein, a method for reducing the pressure in the reaction vessel and timely increasing the flow amount of the inert gas therein, and a method for separating the water formed in step (1) from the water-containing olefin. The method of reducing the water content of the water-containing olefin in the step (2) is preferably a method of separating water formed in the step (1) from the water-containing olefin with respect to the loading of the plant.

Examples of the method for separating water formed in the step (1) from the water-containing olefin include a method for separating the water-containing olefin into an aqueous layer and an oily layer, and then 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 then isolating the aqueous layer of a gaseous phase of the oily layer.

Among them, a method for separating the water-containing olefin into an aqueous layer and an oily layer and then isolating the aqueous layer from the oily layer and a method for phase separation of the water-containing olefin obtained in step (1), in a gas phase and a liquid phase by applying the difference in vapor pressure, and then isolating the aqueous layer as a gaseous phase from the oily layer, and a method of separating the water-containing olefin into an aqueous layer and an oily layer, and then isolating the aqueous layer from the oily layer is more preferable in view of performing step (2) with a simple plant.

Examples of the method of separating the water-containing olefin into an aqueous layer and an oily layer and then isolating the aqueous layer from the oily layer in step (2) include static separation and centrifugal separation. The method for insulating the aqueous layer and the oily layer is preferably static separation in view of performing step (2) with a simple equipment.

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 still more preferably 3 hours or more in view of the reliable insulation aqueous and oily layers.

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

When the isolation is performed by static separation, the temperature of the water-containing olefin with which the static separation is conducted is preferably 100 ° C or less, and more preferably 80 ° C or less, in view of the reduction of the water content of the oily layer. The temperature thereof is preferably 0 ° C or more, and more preferably 20 ° C or more in view of the improvement in production efficiency.

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

Thus, when the step (1) is carried out by a fixed bed reaction using a tubular reactor, water formed flows into the reaction tank in the state where the reaction products and unreacted raw materials are mixed, and thus it is difficult to isolate only water thus formed , When the step (1) is carried out by a fixed bed reaction using a tubular reactor, it is necessary to carry out the step (1) and then the step (2).

Step 3)

In step (3), the water-containing olefin having a water content adjusted to 0.001 mass% or more and 7 mass% or less is internally isomerized in the presence of a solid catalyst.

catalyst

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

The ratio of the amount of the 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 suppressing the formation of dimerized olefin and the branched olefin , the improvement in the yield of the linear olefin and the improvement in 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.

The ratio of the amount of the weak acid of the solid acidic catalyst is preferably 70% or more and 100% or less, more preferably 80% or more and 100% or less, and more preferably 90% or more and 100% or less in view of the suppression of 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.

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

The ratio of the amount of the weak acid of the solid acidic catalyst is more preferably 90% or more and 99% or less, still more preferably 90% or more and 98% or less, still 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 in the average double-bond migration.

The amount of the weak acid in the solid acid 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.

The solid acid catalyst which can be used in the step (3) preferably contains at least one element selected from aluminum, iron and gallium, and more preferably aluminum in view of the improvement of the average double bond migration.

The solid acid catalyst used in the step (3) is preferably γ-alumina, aluminum phosphate or the like.

The solid catalyst used in the step (3) is preferably the same solid catalyst used in the step (1) in view of the suppression of the production cost.

reaction temperature

The reaction temperature in the 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.

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

The reaction temperature in the step (3) is preferably 140 ° C or more and 350 ° C or less, more preferably 180 ° C or more and 300 ° C or less, more preferably 200 ° C or more and 300 ° C or less and still more preferably 230 ° C or more and 290 ° C or less in view of the suppression of the formation of the dimerized olefin and the branched one Olefins, improving the yield of the linear olefin, improving the yield of the internal olefin and improving the average double bond migration.

The reaction temperature in the step (3) is more preferably 230 ° C or more and 280 ° C or less and still more preferably 230 ° C or more and 250 ° C or less in view of suppressing the formation of the branched olefin, enhancing the yield of the linear olefin and improving the yield of the internal olefin.

The reaction temperature in the step (3) is more preferably 240 ° C or more and 290 ° C or less, more preferably 270 ° C or more and 290 ° C or less in view of suppressing the formation of the dimerized olefin and improving the average double bond Migration.

reaction pressure

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 more preferably 0.2 MPa or less, in each case as absolute pressure, and is specifically preferably atmospheric pressure in view of carrying out the reaction with a simple plant.

inert gas

An inert gas may be introduced into a reaction vessel in step (3).

Examples of the inert gas include nitrogen, argon and helium, and nitrogen is preferable in view of availability.

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

Examples of the kind of the reaction in the step (3) include a fixed bed reaction and a suspension bed reaction. The kind of the reaction in the step (3) is preferably a fixed bed reaction in view of the production efficiency. The reaction vessel into which the solid catalyst is filled for the fixed bed reaction is preferably a tubular reactor for a similar reason.

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.

When the step (1) is carried out by a fixed bed reaction, it is necessary to perform the step (2) independently of the step (1) as described above. When steps (3) and (1) are carried out with the same reaction vessel, the water-containing olefin obtained in step (1) is subjected to step (2), and then the water-containing olefin is added to the reaction vessel of step ( 1) and subjected to step (3).

In the fixed bed reaction, WHSV (mass of the reactant fed per one hour with respect to the unit mass of the catalyst) is preferably 0.5 hour or more, more preferably 0.8 hour or more, and further preferably 1 hour or more and preferably 30 per hour or less, more preferably 20 per hour or less, more preferably 10 per hour or less in view of the reaction efficiency.

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

When the step (3) is carried out by suspension bed reaction, the amount of the solid acidic catalyst used is preferably 0.1 mass% or more and 200 mass% or less, more preferably 0.5 mass% or more and 100 mass% or less and more preferably 1 mass% or more and 50 mass% or less, based on the starting material alcohol in view of the reaction rate.

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 in view of the reaction efficiency.

yield

The yield of the linear olefin in the 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 the starting material, which is passed into step (1).

The yield of the branched monomer olefin in the 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 the starting material, which is fed to the step (1).

The yield of the dimerized olefin in the 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 the starting material, which is supplied to the step (1).

Fraction of α-olefin

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

In the present invention, the double bond migration by the internal isomerization reaction is expressed by the average double bond migration, as shown below.
n: odd number (average double bond migration) = Σm = (n-1) / 2 / m = 1 (m-1) × (Y / 100) (1-1) n: even number (average double bond migration) = Σm = n / 2 / m = 1 (m-1) × (Y / 100) (1-2) wherein n is the number of carbon atoms of the olefin; m is the position of the double bond in the olefin and Y is the percentage of the m-olefin in the olefin having a number of carbon atoms of n at the time when step (3) is completed.

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

According to the invention, only the internal olefin in the form of the monomer can be isolated by distillation or the like from the water-containing internal olefin thus obtained, and thereby the internal olefin can be obtained with high purity.

Process for producing an internal olefinsulfonate salt

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

The sulfonation reaction in the step of obtaining a sulfonated product may 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.

The reaction temperature in the sulfonation reaction is preferably 0 ° C or more and 80 ° C or less.

The neutralization of the sulfonated product can be carried out by reaction with an aqueous alkali solution in a simple or larger amount of 1.5 times or less per 1 mole of the theoretical value of the sulfonic acid groups.

Examples of the aqueous alkali solution which can be used for the neutralization include an aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, aqueous ammonia solution and an aqueous 2-aminoethanol solution.

The hydrolysis reaction may 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.

The sulfonation reaction and the neutralization reaction can be carried out continuously. After completion of the neutralization reaction, the product may be purified by extraction, rinsing and the like.

• <1> Verfahren zur Erzeugung eines internen Olefins unter Verwendung eines primären aliphatischen Alkohols mit 8 bis 24 Kohlenstoffatomen als Ausgangsmaterial, umfassend die Durchführung der folgenden Schritte (1) bis (3): Schritt (1): ein Schritt zum Durchführen einer Dehydratisierungsreaktion eines primären aliphatischen Alkohols mit 8 bis 24 Kohlenstoffatomen in der Gegenwart eines festen Katalysators; Schritt (2): ein Schritt zum Steuern eines Wassergehaltes eines Wasser-haltigen Olefins, erhalten durch die Dehydratisierungsreaktion, auf 0,001 Massen% oder mehr und 7 Massen% oder weniger; und Schritt (3): ein Schritt zum internen Isomerisieren des Wasser-haltigen Olefins mit einem Wasserstoffgehalt, der auf 0,001 Massen% oder mehr und 7 Massen% oder weniger eingestellt ist, in der Gegenwart eines festen Katalysators.
• <2> Verfahren zur Erzeugung eines internen Olefins gemäß Punkt <1>, worin der primäre aliphatische Alkohol mit 8 bis 24 Kohlenstoffatomen eine Zahl von Kohlenstoffatomen von 8 oder mehr, bevorzugt 10 oder mehr, mehr bevorzugt 12 oder mehr, weiter bevorzugt 14 oder mehr und noch weiter bevorzugt 16 oder mehr und 24 oder weniger, bevorzugt 22 oder weniger und mehr bevorzugt 18 oder weniger aufweist.
• <3> Verfahren zur Erzeugung eines internen Olefins gemäß Punkt <1> oder <2>, worin der Wassergehalt des Wasserhaltigen Olefins zum Zeitpunkt, wenn der Schritt (2) vollendet ist, 0,001 Massen% oder mehr bevorzugt 0,005 Massen% oder mehr und mehr bevorzugt 0,008 Massen% oder mehr ist und 7 Massen% oder weniger, bevorzugt 1 Massen% oder weniger, mehr bevorzugt 0,3 Massen% oder weniger, weiter bevorzugt 0,1 Massen% oder weniger, noch weiter bevorzugt 0,07 Massen% oder weniger, noch weiter bevorzugt 0,05 Massen% oder weniger, weiterhin bevorzugt 0,02 Massen% oder weniger noch weiter bevorzugt 0,01 Massen% oder weniger ist.
• <4> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <3>, worin der Schritt (2) ein Schritt zum Trennen von Wasser von dem Wasserhaltigen Olefin, erhalten im Schritt (1) ist.
• <5> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <4>, worin das Verfahren zum Trennen von Wasser in Schritt (2) bevorzugt ein Verfahren zum Isolieren der wäßrigen Schicht aus der öligen Schicht von dem Wasser-haltigen Olefin, erhalten im Schritt (1) ist, ein Verfahren zum Verdampfen von Wasser aus dem Wasser-haltigen Olefin, erhalten im Schritt (1) unter vermindertem Druck oder ein Verfahren zum Phasentrennen des Wasser-haltigen Olefins, erhalten im Schritt (1) in eine Gasphase und eine flüssige Phase unter Verwendung des Unterschiedes des Dampfdruckes und anschließendes Isolieren der wäßrigen Schicht als Gasphase von der öligen Schicht, mehr bevorzugt ein Verfahren zum Isolieren der wäßrigen Schicht von der öligen Schicht des Wasser-haltigen Olefins, erhalten im Schritt (1), oder ein Verfahren zum Phasentrennen des Wasser-haltigen Olefins, erhalten im Schritt (1) in eine Gasphase und eine flüssige Phase durch Verwendung des Unterschiedes des Dampfdruckes und anschließendes Isolieren der wäßrigen Schicht als Gasphase von der öligen Schicht, und weiter bevorzugt ein Verfahren zum Isolieren der wäßrigen Schicht von der öligen Schicht des Wasser-haltigen Olefins, erhalten im Schritt (1) ist.
• <6> Verfahren zum Erzeugen eines internen Olefins gemäß Punkt <5>, worin das Verfahren zum Isolieren der wäßrigen Schicht von der öligen Schicht des Wasser-haltigen Olefins eine statische Trennung ist.
• <7> Verfahren zum Erzeugen eines internen Olefins nach Punkt <6>, worin die Temperatur des Wasser-haltigen Olefins bei der Durchführung der statischen Trennung bevorzugt 100°C oder weniger und mehr bevorzugt 80°C oder weniger und bevorzugt 0°C oder mehr und mehr bevorzugt 20°C oder mehr ist.
• <8> Verfahren zur Erzeugung eines internen Olefins gemäß Punkt <6> oder <7>, worin die Zeit für die statische Trennung des Wasser-haltigen Olefins bei der statischen Trennung bevorzugt 1 Minute oder mehr und mehr bevorzugt 10 Minuten oder mehr und bevorzugt 10 Stunden oder weniger und mehr bevorzugt 5 Stunden oder weniger ist.
• <9> Verfahren zur Erzeugung eines internen Olefins nach einem der Punkte <1> bis <8>, worin der Schritt (1) durch Festbettreaktion durchgeführt wird.
• <10> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <9>, worin der Schritt (3) durch Festbettreaktion durchgeführt wird.
• <11> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <10>, worin der feste Katalysator im Schritt (1) ein fester saurer Katalysator ist und die Menge der schwachen Säure, die die Säuremenge ist, berechnet von der Ammoniak-Desorptionsmenge bei einer Desorptionstemperatur von 300°C oder weniger, bezogen auf die gesamte Säuremenge, gemessen durch das NH₃-TPD-Verfahren, bevorzugt 70% oder mehr, mehr bevorzugt 80% oder mehr, weiter bevorzugt 90% oder mehr und noch weiter bevorzugt 92% oder mehr ist und bevorzugt 100% oder weniger, mehr bevorzugt 99% oder weniger und weiter bevorzugt 95% oder weniger ist.
• <12> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <10>, worin der feste Katalysator im Schritt <1> ein fester saurer Katalysator ist und die Menge der schwachen Säure, die die Säuremenge ist, berechnet von der Ammoniak-Desorptionsmenge bei einer Desorptionstemperatur von 300°C oder weniger, bezogen auf die gesamte Säuremenge, gemessen durch das NH₃-TPD-Verfahren, bevorzugt 70% oder mehr und 100% oder weniger, mehr bevorzugt 80% oder mehr und 100% oder weniger und weiter bevorzugt 90% oder mehr und 100% oder weniger ist.
• <13> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <10>, worin der feste Katalysator im Schritt (1) ein fester saurer Katalysator ist und die Menge der schwachen Säure, die die Säuremenge ist, berechnet von der Ammoniak-Desorptionsmenge bei einer Desorptionstemperatur von 300°C oder weniger, bezogen auf die gesamte Säuremenge, gemessen durch das NH₃-TPD-Verfahren, weiter bevorzugt 92% oder mehr und 100% oder weniger ist.
• <14> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <10>, worin der feste Katalysator im Schritt (1) ein fester saurer Katalysator ist und die Menge der schwachen Säure, die die Säuremenge ist, berechnet von der Ammoniak-Desorptionsmenge bei einer Desorptionstemperatur von 300°C oder weniger bezogen auf die gesamte Säuremenge, gemessen durch das NH₃-TPD-Verfahren, weiter bevorzugt 90% oder mehr und 99% oder weniger, noch weiter bevorzugt 90% oder mehr und 98% oder weniger, noch weiter bevorzugt 90% oder mehr und 95% oder weniger und noch weiter bevorzugt 90% oder mehr und 94% oder weniger ist.
• <15> Verfahren zur Erzeugung eines internen Olefins nach einem der Punkte <1> bis <14>, worin der feste Katalysator im Schritt (3) ein fester saurer Katalysator ist und die Menge der schwachen Säure, die die Säuremenge ist, berechnet von der Ammoniak-Desorptionsmenge bei einer Desorptionstemperatur von 300°C oder weniger bezogen auf die gesamte Säuremenge, gemessen durch das NH₃-TPD-Verfahren, bevorzugt 70% oder mehr, mehr bevorzugt 80% oder mehr, weiter bevorzugt 90% oder mehr und noch weiter bevorzugt 92'% oder mehr und ist bevorzugt 100%% oder weniger, mehr bevorzugt 99% oder weniger, weiter bevorzugt 95% oder weniger und noch weiter bevorzugt 94% oder weniger ist.
• <16> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <14>, worin der feste Katalysator im Schritt (3) ein fester saurer Katalysator ist und die Menge der schwachen Säure, die die Säuremenge ist, berechnet von der Ammoniak-Desorptionsmenge bei einer Desorptionstemperatur von 300°C oder weniger bezogen auf die gesamte Säuremenge, gemessen durch das NH₃-TPD-Verfahren, bevorzugt 70% oder mehr und 100%& oder weniger, mehr bevorzugt 80% oder mehr und 100% oder weniger und weiter bevorzugt 90% oder mehr und 100% oder weniger ist.
• <17> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <14>, worin der feste Katalysator im Schritt (3) ein fester saurer Katalysator ist und die Menge der schwachen Säure, die die Säuremenge ist, berechnet von der Ammoniak-Desorptionsmenge bei einer Desorptionstemperatur von 300°C oder weniger bezogen auf die gesamte Säuremenge, gemessen durch das NH₃-TPD-Verfahren, bevorzugt 92% oder mehr und 100% oder weniger und noch weiter bevorzugt 95% oder mehr und 100% oder weniger ist.
• <18> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <14>, worin der feste Katalysator im Schritt (3) ein fester saurer Katalysator ist und die Menge der schwachen Säure, die die Säuremenge ist, berechnet von der Ammoniak-Desorptionsmenge bei einer Desorptionstemperatur von 300°C oder weniger bezogen auf die gesamte Säuremenge, gemessen durch das NH₃-TPD-Verfahren, weiter bevorzugt 90% oder mehr und 99% oder weniger, noch weiter bevorzugt 90% oder mehr und 98% oder weniger, noch weiter bevorzugt 90% oder mehr und 95% oder weniger und noch weiter bevorzugt 90% oder mehr und 94% oder weniger ist.
• <19> Verfahren zur Erzeugung eines internen Olefins nach einem der Punkte <1> bis <18>, worin die Reaktionstemperatur im Schritt (1) bevorzugt 140°C oder mehr, mehr bevorzugt 200°C oder mehr, weiter bevorzugt 240°C oder mehr und noch weiter bevorzugt 270°C oder mehr ist und bevorzugt 350°C oder weniger, mehr bevorzugt 300°C oder weniger und weiter bevorzugt 290°C oder weniger ist.
• <20> Verfahren zur Erzeugung eines internen Olefins nach einem der Punkte <1> bis <19>, worin die Reaktionstemperatur im Schritt (3) bevorzugt 140°C oder mehr, mehr bevorzugt 180°C oder mehr, weiter bevorzugt 200°C oder mehr, noch weiter bevorzugt 230°C oder mehr, noch weiter bevorzugt 240°C oder mehr und noch weiter bevorzugt 270°C oder mehr ist, und ist vorzugsweise 350°C oder weniger, mehr bevorzugt 300°C oder weniger, weiter bevorzugt 290°C oder weniger noch weiter bevorzugt 280°C oder weniger und noch weiter bevorzugt 250°C oder weniger ist.
• <21> Verfahren zur Erzeugung eines internen Olefins nach einem der Punkte <1> bis <19>, worin die Reaktionstemperatur im Schritt (3) bevorzugt 140°C oder mehr und 350°C oder weniger mehr bevorzugt 180°C oder mehr und 300°C oder weniger, weiter bevorzugt 200°C oder mehr und 300°C oder weniger und noch weiter bevorzugt 230°C oder mehr und 290°C oder weniger ist.
• <22> Verfahren zur Erzeugung eines internen Olefins nach einem der Punkte <1> bis <19>, worin die Reaktionstemperatur im Schritt (3) bevorzugt 230°C oder mehr und 280°C oder weniger und mehr bevorzugt 230°C oder mehr und 250°C oder weniger ist.
• <23> Verfahren zur Erzeugung eines internen Olefins nach einem der Punkte <1> bis <19>, worin die Reaktionstemperatur im Schritt (3) bevorzugt 240°C oder mehr und 290°C oder weniger und mehr bevorzugt 270°C oder mehr und 290°C oder weniger ist.
• <24> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <23>, worin der Reaktionsdruck in Schritt (1) bevorzugt 0,03 MPa oder mehr, mehr bevorzugt 0,05 MPa oder mehr und weiter bevorzugt 0,1 MPa oder mehr ist und bevorzugt 0,14 MPa oder weniger und mehr bevorzugt 0,03 MPa oder mehr und 0,14 MPa oder weniger und weiter bevorzugt atmosphärischer Druck ist.
• <25> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <24>, worin der Reaktionsdruck in Schritt (3) bevorzugt 0,03 MPa oder mehr, mehr bevorzugt 0,05 MPa oder mehr und weiter bevorzugt 0,1 MPa oder mehr ist, bevorzugt 1 MPa oder weniger, mehr bevorzugt 0,5 MPa oder weniger und weiter bevorzugt 0,2 MPa oder weniger und speziell bevorzugt atmosphärischer Druck ist.
• <26> Verfahren zur Erzeugung eines internen Olefins nach einem der Punkte <9> bis <25>, worin WHSV im Schritt (1) bevorzugt 0,1 pro Stunde oder mehr, mehr bevorzugt 0,15 pro Stunde oder mehr und weiter bevorzugt 0,2 pro Stunde oder mehr ist, und bevorzugt 6 pro Stunde oder weniger, mehr bevorzugt 4 pro Stunde oder weniger, weiter bevorzugt 2 pro Stunde oder weniger und noch weiter bevorzugt 1 pro Stunde oder weniger ist.
• <27> Verfahren zur Erzeugung eines internen Olefins nach einem der Punkte <9> bis <26>, worin die LHSV im Schritt (1) bevorzugt 0,1 pro Stunde oder mehr, mehr bevorzugt 0,15 pro Stunde oder mehr und weiter bevorzugt 0,2 pro Stunde oder mehr ist, und bevorzugt 5 pro Stunde oder weniger, mehr bevorzugt 3,5 pro Stunde oder weniger, weiter bevorzugt 1,5 pro Stunde oder weniger und noch weiter bevorzugt 0,5 pro Stunde oder weniger ist.
• <28> Verfahren zur Erzeugung eines internen Olefins nach einem der Punkte <10> bis <27>, worin die LHSV im Schritt (3) bevorzugt 0,5 pro Stunde oder mehr, mehr bevorzugt 0,8 pro Stunde oder mehr, weiter bevorzugt 1 pro Stunde oder mehr und noch mehr bevorzugt 1,2 pro Stunde oder weniger ist und bevorzugt 25 pro Stunde oder weniger, mehr bevorzugt 18 pro Stunde oder weniger, weiter bevorzugt 10 pro Stunde oder weniger und noch weiter bevorzugt 2 pro Stunde oder weniger ist.
• <29> Verfahren zur Erzeugung eines internen Olefins gemäß einem der Punkte <1> bis <28>, worin die durchschnittliche Doppelbindungs-Migration des internen Olefins, erhalten im Schritt (3), bevorzugt 2 oder mehr, mehr bevorzugt 3 oder mehr und weiter bevorzugt 4 oder mehr ist.

This invention also relates to the following embodiments in addition to the above.

• <1> A process 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 of carrying 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 of controlling a water content of a water-containing olefin obtained by the dehydration reaction to 0.001 mass% or more and 7 mass% or less; and step (3): a step of internally isomerizing the water-containing olefin having a hydrogen content adjusted to 0.001 mass% or more and 7 mass% or less in the presence of a solid catalyst.
• <2> A method of producing an internal olefin according to item <1>, wherein the primary aliphatic alcohol having 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> A method of producing an internal olefin according to item <1> or <2>, wherein the water content of the water-containing olefin at the time when the step (2) is completed is 0.001 mass% or more preferably 0.005 mass% or more and more preferably 0.008 mass% or more and 7 mass% or less, preferably 1 mass% or less, more preferably 0.3 mass% or less, further preferably 0.1 mass% or less, still more preferably 0.07 mass% or less, more preferably 0.05 mass% or less, further preferably 0.02 mass% or less, even more preferably 0.01 mass% or less.
• <4> A process for producing an internal olefin according to any one of <1> to <3>, wherein the step (2) is a step of separating water from the hydrous olefin obtained in the step (1).
• <5> A process for producing an internal olefin according to any one of <1> to <4>, wherein the process for separating water in step (2) is preferably one A process for isolating the aqueous layer from the oily layer of the water-containing olefin obtained in the step (1) is a process for evaporating water from the water-containing olefin obtained in the step (1) under reduced pressure or a process for phase separation of the water-containing olefin obtained in the step (1) into a gas phase and a liquid phase using the difference of the vapor pressure and then isolating the aqueous layer as a gaseous phase from the oily layer, more preferably a method of isolating the aqueous layer of the oily layer of the water-containing olefin obtained in the step (1), or a process for phase separating the water-containing olefin obtained in the step (1) into a gas phase and a liquid phase by using the difference of the vapor pressure and then isolating the aqueous layer as gaseous phase of the oily layer, and more preferably a method of isolating the aqueous layer of the oily layer of the water-containing olefin obtained in the step (1).
• <6> A method of producing an internal olefin according to item <5>, wherein the method of isolating the aqueous layer from the oily layer of the water-containing olefin is a static separation.
• <7> A method of producing an internal olefin according to item <6>, wherein the temperature of the water-containing olefin in carrying out the static separation is preferably 100 ° C or less, and more preferably 80 ° C or less, and preferably 0 ° C or more and more preferably 20 ° C or more.
• <8> A process for producing an internal olefin according to item <6> or <7>, wherein the time for the static separation of the water-containing olefin in the static separation is preferably 1 minute or more, and more preferably 10 minutes or more and preferably 10 Hours or less and more preferably 5 hours or less.
• <9> A process for producing an internal olefin according to any one of the items <1> to <8>, wherein the step (1) is carried out by a fixed bed reaction.
• <10> A process for producing an internal olefin according to any of the items <1> to <9>, wherein the step (3) is carried out by a fixed bed reaction.
• <11> A process for producing an internal olefin according to any of the items <1> to <10>, wherein the solid catalyst in the step (1) is a solid acid catalyst and the amount of the weak acid which is the acid amount calculated from Ammonia desorption amount at a desorption temperature of 300 ° C or less, based on the total amount of acid, measured by the NH ₃ -TPD method, preferably 70% or more, more preferably 80% or more, further preferably 90% or more and still more preferably 92% or more, and preferably 100% or less, more preferably 99% or less, and further preferably 95% or less.
• <12> A process for producing an internal olefin according to any of the items <1> to <10>, wherein the solid catalyst in the step <1> is a solid acidic catalyst and the amount of the weak acid, which is the amount of acid calculated from Ammonia desorption amount at a desorption temperature of 300 ° C or less, based on the total amount of acid, measured by the NH ₃ -TPD method, preferably 70% or more and 100% or less, more preferably 80% or more and 100% or less and more preferably 90% or more and 100% or less.
• <13> A process for producing an internal olefin according to any of the items <1> to <10>, wherein the solid catalyst in the step (1) is a solid acid catalyst and the amount of the weak acid which is the acid amount calculated from Ammonia desorption amount at a desorption temperature of 300 ° C or less, based on the total amount of acid measured by the NH ₃ -TPD method, more preferably 92% or more and 100% or less.
• <14> A process for producing an internal olefin according to any one of the items <1> to <10>, wherein the solid catalyst in the step (1) is a solid acid catalyst and the amount of the weak acid which is the acid amount calculated from Ammonia desorption amount at a desorption temperature of 300 ° C or less based on the total amount of acid measured by the NH ₃ -TPD method, more preferably 90% or more and 99% or less, still more preferably 90% or more and 98% or less, more preferably 90% or more and 95% or less, and even more preferably 90% or more and 94% or less.
• <15> A process for producing an internal olefin according to any one of <1> to <14>, wherein the solid catalyst in the step (3) is a solid acid catalyst and the amount of the weak acid which is the acid amount calculated from Ammonia desorption amount at a desorption temperature of 300 ° C or less based on the total amount of acid measured by the NH ₃ -TPD method, preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and still more preferably 92% or more, and is preferably 100% or less, more preferably 99% or less, still more preferably 95% or less, and still more preferably 94% or less.
• <16> A process for producing an internal olefin according to any of the items <1> to <14>, wherein the solid catalyst in the step (3) is a solid acidic catalyst and the amount of the weak acid which is the acid amount calculated from Ammonia desorption amount at a desorption temperature of 300 ° C or less based on the total amount of acid measured by the NH ₃ -TPD method, preferably 70% or more and 100% & or less, more preferably 80% or more and 100% or less and more preferably 90% or more and 100% or less.
• <17> A process for producing an internal olefin according to any one of the items <1> to <14>, wherein the solid catalyst in the step (3) is a solid acid catalyst and the amount of the weak acid which is the acid amount calculated from Ammonia desorption amount at a desorption temperature of 300 ° C or less based on the total amount of acid measured by the NH ₃ -TPD method, preferably 92% or more and 100% or less, and more preferably 95% or more and 100% or less is.
• <18> A process for producing an internal olefin according to any of the items <1> to <14>, wherein the solid catalyst in the step (3) is a solid acid catalyst and the amount of the weak acid which is the acid amount calculated from Ammonia desorption amount at a desorption temperature of 300 ° C or less based on the total amount of acid measured by the NH ₃ -TPD method, more preferably 90% or more and 99% or less, still more preferably 90% or more and 98% or less, more preferably 90% or more and 95% or less, and even more preferably 90% or more and 94% or less.
• <19> A process for producing an internal olefin according to any one of <1> to <18>, wherein the reaction temperature in the 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 more preferably 290 ° C or less.
• <20> A process for producing an internal olefin according to any of the items <1> to <19>, wherein the reaction temperature in the step (3) is preferably 140 ° C or more, more preferably 180 ° C or more, further preferably 200 ° C or more, more preferably 230 ° C or more, still more preferably 240 ° C or more and still 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, more preferably 280 ° C or less, and even more preferably 250 ° C or less.
• <21> A process for producing an internal olefin according to any of the items <1> to <19>, wherein the reaction temperature in the step (3) is preferably 140 ° C or more and 350 ° C or less, more preferably 180 ° C or more and 300 Is C or less, more preferably 200 ° C or more and 300 ° C or less, and even more preferably 230 ° C or more and 290 ° C or less.
• <22> A process for producing an internal olefin according to any one of <1> to <19>, wherein the reaction temperature in the 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> A process for producing an internal olefin according to any one of <1> to <19>, wherein the reaction temperature in the 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> A process for producing an internal olefin according to any of the items <1> to <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, Is 1 MPa or more, and is preferably 0.14 MPa or less, and more preferably 0.03 MPa or more and 0.14 MPa or less, and more preferably atmospheric pressure.
• <25> A process for producing an internal olefin according to any one of <1> to <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 more preferably 0.2 MPa or less, and especially preferably atmospheric pressure.
• <26> A process for producing an internal olefin according to any one of <9> to <25>, wherein WHSV in the step (1) is preferably 0.1 per hour or more, more preferably 0.15 per hour or more, and further preferably 0 Is 2 per hour or more, and is preferably 6 per hour or less, more preferably 4 per hour or less, more preferably 2 per hour or less, and still more preferably 1 hour or less.
• <27> A process for producing an internal olefin according to any one of <9> to <26>, wherein the LHSV in the step (1) is preferably 0.1 per hour or more, more preferably 0.15 per hour or more, and further preferably Is 0.2 per hour or more, and is preferably 5 per hour or less, more preferably 3.5 per hour or less, more preferably 1.5 per hour or less, and still more preferably 0.5 hour or less.
• <28> A process for producing an internal olefin according to any one of <10> to <27>, wherein the LHSV in the step (3) is preferably 0.5 hour or more, more preferably 0.8 hour or more, more preferably 1 per hour or more and even more preferably 1.2 per hour or less, and preferably 25 per hour or less, more preferably 18 per hour or less, more preferably 10 per hour or less, and still more preferably 2 per hour or less ,
• <29> A process for producing an internal olefin according to any one of <1> to <28>, wherein the average double bond migration of the internal olefin obtained in the step (3) is preferably 2 or more, more preferably 3 or more and further preferably 4 or more.

Examples

measurement conditions

The quantitative determination of the olefins in the samples obtained in Examples and Comparative Examples below as samples was carried out as follows.

Alcohol conversion, yield of olefins and quantitative determination of water

The sample was diluted with water and then with a gas chromatography analyzer (HP6890, produced by Hewlett-Packard Company, column: Ultra ALLOY-1 capillary column, 30.0 m × 250 μm (produced by Frontier Laboratories, Ltd.), Detector: Hydrogen flame ionization detector (FID)) was analyzed 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.

The alcohol conversion, the yield of the product, the amount of the branched monomeric olefin formed in the step (3), the amount of the dimerized olefin formed in the step (3), and the fraction of the α-olefin were calculated by the following yield. (Alcohol conversion (mol%)) = 100 - ((residual alcohol amount (mol)) / (Feed amount of the 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)) / (Feed amount of starting material alcohol (mol)) × 100) (Yield of dimerized olefin (mol%) = (((dimerized olefin amount (mol)) × 2) / amount of starting material alcohol (mol) fed) × 100 (Amount of the branched monomeric olefin formed in the step (3) (mol%)) = (yield of the branched monomeric olefin after performing step (3) (mol%)) - (yield of the branched monomeric olefin after performing step (2 ) (mol%)) Amount of the dimerized olefin formed in the step (3) (mol%)) = (yield of the dimerized olefin after performing step (3) (mol%)) - (yield of the 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 dimerized olefin (mol)))) × 100

The water content in the sample was measured by a Karl Fischer water analyzer (Taitrand 852, produced by Metrhom Japan Ltd.).

Quantitative determination of the position of the olefinic double bond

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 normal temperature for 1 hour, and 25 parts by mass of a 30 mass% aqueous sodium thiosulfate solution was added, followed by vigorous shaking until the mixture became transparent , Thereafter, 25 parts by mass of ethanol and 21 parts by mass of hexane were added in this 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 olefinic double bond with a gas chromatography analyzer (HP6890, produced by Hewlett-Packard Company, column: Ultra ALLOY-1 capillary column, 30.0 m × 250 μm (produced 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 subjected.

example 1

(Step 1)

A reaction tube having an inner diameter of 35 mm and a length of 500 mm was placed vertically. A γ-alumina 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) as a catalyst was used in filled the reaction tube.

At a temperature of the catalyst layer of 280 ° C, stearyl alcohol, Kalcol 8098 (manufactured by Kao Corporation, density at 20 ° C: 0.83 g / cm ³ ) as a primary aliphatic alcohol in an amount of 0.15 l per hour (LHSV 0.30 per hour, WHSV: 0.37 per hour) and nitrogen was added in an amount of 3.2 l per hour in view of the volume under standard conditions (amount of nitrogen introduced: 0.3 mol per 1 mol of stearyl alcohol) the upper part of the reaction tube was introduced under atmospheric pressure for 72 hours. The liquid discharged from the outlet of the reaction tube was cooled to 80 ° C and the water-containing 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%, the average double bond migration was 2.1.

Step 2)

The water-containing olefin obtained in the 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 mass%.

Step 3)

A reaction tube having an inner diameter of 35 mm and a length of 500 mm was placed vertically, and 0.5 liter (335 g) of γ-alumina of the same kind and charge as the catalyst used in step (1) was used filled in the reaction tube.

At a temperature of the catalyst layer of 280 ° C, the oily layer obtained in the step (2) was fed in an amount of 0.75 l per hour (LHSV: 1.50 per hour), and nitrogen was added in an amount of 3.2 l per hour, expressed as volume, under standard condition from the top of the reaction tube at atmospheric pressure for 14 hours. The liquid discharged from the outlet of the reaction tube was cooled to 40 ° C and collected.

The yield of the linear monomeric olefin was 94.2 mol%, the amount of the branched monomeric olefin formed in the 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

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

Example 3

The same procedure as in Example 1 was conducted under the same conditions except that deionized water was added to the oily layer obtained in the step (2) in Example 1 to obtain an oily component having a water content on 0.1481 mass%, and the oily component was used in step (3).

The yield of the linear monomeric olefin obtained in the step (3) was 96.1 mol%. The amount of the branched monomeric olefin formed in the 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

The same operations 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 the step (1) of Example 1, and deionized water became the oily one Layer obtained in the step (2) was added to obtain an oily component having a water content adjusted to 0.0570 mass%, and the oily component was used in the step (3).

The alcohol conversion of the water-containing olefin obtained in the 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 dimerized Olefin was 0.93 mol%. The yield of 1-hexadecene was 3.41 mol% and the average double bond migration was 2.2.

The yield of the linear monomeric olefin obtained in the step (3) was 96.0 mol%. The amount of the branched monomeric olefin formed in the step (3) was 2.47 mol%, and the amount of the dimerized olefin formed in the 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

The same operation 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 the step (1) in Example 1, and deionized water was added to the oily layer obtained in step (2) to obtain an oily component having a water content adjusted to 0.0570 mass%, and the oily component was used in step (3).

The alcohol conversion of the water-containing olefin obtained in the 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 dimerized Olefin was 0.94 mol%. The yield of 1-olefin was 3.54 mol% and the average double bond migration was 1.97.

The yield of the linear monomeric olefin obtained in the step (3) was 95.6 mol%. The amount of the branched monomeric olefin formed in the step (3) was 2.85 mol%, and the amount of the dimerized olefin formed in the 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 Preparation Example 1

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 mixed solution at room temperature, and the pH thereof was raised to 5 to obtain a white precipitate in the form of a gel. The precipitate was filtered and rinsed with water and then dried at 110 ° C for 15 hours and pulverized to 60 mesh or less. Ten parts by mass of aluminasol was added to 100 parts by mass of the pulverized catalyst, and the mixture was extrusion-molded into a diameter of 2.5 mm. The molded mixture was baked at 250 ° C for 3 hours to obtain a solid catalyst shaped catalyst (hereinafter referred to as Catalyst 1). The catalyst thus obtained had an amount of weak acid of 1 mmol / g and a ratio of the weak acid of 96%.

reaction

The same operations were carried out under the same conditions as in Example 1, except that 0.5 liter (270 g) of the catalyst obtained in Catalyst Preparation Example 1 as a catalyst was filled in the reaction tube in Step (3) of Example 1 That is, the temperature of the catalyst was not 240 ° C, and deionized water was added to the oily layer obtained in step (2) to obtain an oily component having a water content adjusted to 0.0570 mass%, and the oily component became the step (3) used.

The amount of the linear monomeric olefin obtained in the step (3) was 95.8 mol%. The amount of the branched monomeric olefin formed in the step (3) was 2.47 mol%, and the amount of the dimerized olefin formed in the 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

The same operations 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 to obtain an oil-water suspension having a water content which was set at 7.1 mass%, and the step (3) was carried out with the suspension supplied in an amount of 0.42 liter per hour and nitrogen in an amount of 1.8 liter per Hour, expressed as volume, under the standard condition.

The yield of the linear monomeric olefin obtained in the 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

Preparation of the internal sodium olefin sulfonate

A thin-film sulfonation reactor with an external jacket was used as the reactor. The internal olefin obtained in the step (3) of Example 7 was added to the reactor, and the sulfonation reaction was carried out by passing sulfur trioxide gas (SO ₃ ). Cooling water at 20 ° C was passed through the external jacket of the reactor during the reaction. The molar ratio of sulfur trioxide gas and the internal olefin (SO ₃ / internal olefin) set in the sulfonation reaction was 1.01.

The sulfonated product obtained by the sulfonation reaction was added to an aqueous alkali solution prepared by using sodium hydroxide in an amount of 1.5 times the theoretical acid value, followed by stirring at 30 ° C for one hour for neutralization. The neutralized product was hydrolyzed by heating in an autoclave for one hour at 160 ° C to give a crude product of internal sodium olefinsulfonate. The concentration of sodium olefinsulfonate in the crude product of the internal sodium olefin sulfonate was 35% by mass. The concentration of sodium olefinsulfonate was measured by a potentiometric titration method using a benzethonium chloride solution (synthetic detergent testing method, JIS K3362).

According to this invention, a linear internal olefin having high double-bond migration can be suitably produced in high yield by using an olefin obtained by dehydration reaction of a primary aliphatic alcohol.

Claims (20)

A process 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 of carrying 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 of controlling a water content of a water-containing olefin obtained by the dehydration reaction to 0.001 mass% or more and 7 mass% or less; and Step (3): a step of internally isomerizing the water-containing olefin having a hydrogen content set to 0.001 mass% or more and 7 mass% or less in the presence of a solid catalyst. A process for producing an internal olefin according to claim 1, wherein the internal olefin obtained in the step (3) has an average double bond migration of 2 or more. A process for producing an internal olefin according to claim 1 or 2, wherein the water content in the step (2) is adjusted by separating water from the water-containing olefin. A process for producing an internal olefin according to any one of claims 1 to 3, wherein the step (1) is carried out by a fixed bed reaction. A process for producing an internal olefin according to any one of claims 1 to 4, wherein the step (3) is carried out by a fixed bed reaction. A process for producing an internal olefin according to any one of claims 1 to 5, wherein a reaction temperature in the step (1) is 140 ° C or more and 350 ° C or less. A process for producing an internal olefin according to any one of claims 1 to 6, wherein a reaction temperature in step (3) is 140 ° C or more and 350 ° C or less. A process for producing an internal olefin according to any one of claims 1 to 7, wherein the solid catalyst in step (1) is a solid acidic catalyst. A process for producing an internal olefin according to any one of claims 1 to 8, wherein the solid catalyst in step (3) is a solid acidic catalyst. A process 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. A process 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. A process for producing an internal olefin according to claim 10, wherein the solid catalyst in step (1) contains at least one element selected from aluminum, iron and gallium. A process for producing an internal olefin according to claim 11, wherein the solid catalyst in step (3) contains at least one element selected from aluminum, iron and gallium. A process for producing an internal olefin according to any one of claims 1 to 13, wherein the solid catalyst used in the step (3) is the same solid catalyst used in the step (1). A process 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. A process for producing an internal olefin according to any one of claims 4 to 15, wherein an LHSV in the step (1) is 0.1 per hour or more and 5 per hour or less. A process 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. A process 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). A process 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). A process for producing an internal olefin sulfonate salt, comprising: a step of sulfonating the internal olefin produced by the production process of any one of claims 1 to 19 to obtain a sulfonated product; and a step of neutralizing the sulfonated product and then hydrolyzing the neutralized product.