JP2013245281A - Method for producing desulfurized fatty acid or fatty acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a desulfurized fatty acid or fatty acid ester.SOLUTION: A method for producing a desulfurized fatty acid or fatty acid ester includes steps 1 and 2, in which the step 2 is performed successively to the step 1, or the step 1 and step 2 are simultaneously performed. Step 1: A bromine-based oxidizing agent is brought into contact with raw material oil and fat containing one or more selected from fatty acids and fatty acid esters and a sulfur component in liquid phase. Step 2: (a) A washing treatment by a polar solvent or (b) an adsorption treatment by an adsorbent is performed.

Description

  The present invention relates to a method for producing a desulfurized fatty acid or fatty acid ester, and a method for producing an alcohol using a desulfurized fatty acid or fatty acid ester obtained by the production method as a raw material.

  Fatty acids or fatty acid esters derived from fats and oils such as coconut oil and palm oil are useful as a natural long-chain hydrocarbon source, a raw material for functional materials, a biofuel, and the like. In particular, higher alcohols obtained by hydrogenating them are useful as raw materials for surfactants and the like. Since fatty acids or fatty acid esters derived from natural fats and oils contain sulfur-containing compounds that poison the hydrogenation catalyst as trace components (hereinafter also referred to as sulfur components), sulfur components are required for use in alcohol production. It is necessary to exclude.

In a conventional method for producing an alcohol via a methyl ester, sulfur components can be removed to some extent by performing distillation at the methyl ester stage. And the methyl ester with little sulfur content can be obtained by processing the methyl ester after distillation with an adsorption agent (patent document 1).
On the other hand, for the purpose of cost and environmental load reduction, alcohol production by a direct hydrogenation method from fats and oils or fatty acids, which does not undergo methyl ester and does not undergo distillation in the previous stage of hydrogenation, has been proposed, Along with this, development of new desulfurization technology is desired.

Patent Document 2 discloses a method of desulfurizing a fuel oil by treating it with hydrogen peroxide, a carboxylic acid, and an acid catalyst or an oxidizing agent containing an acid, and then bringing the fuel oil into contact with an adsorbent. Yes. In patent document 2, as a target fuel oil, only kerosene has actually been confirmed to be effective.
As described above, various desulfurization means such as hydrodesulfurization methods have been proposed in the petrochemical field in order to prevent environmental impacts, odors, and hue deterioration. It cannot be applied as a desulfurization method for fats and oils.
・ The main sulfur component is an aromatic sulfur component such as benzothiophene ・ The reaction temperature is 300 ° C. or higher ・ The initial value of sulfur component concentration and the reduction target value are high

  As a method for removing a sulfur component in the gas phase, Patent Document 3 discloses that a gas containing substantially only alkyl sulfide as a sulfur component at a concentration of 10 ppm or less is brought into contact with activated carbon adsorbed with bromine to obtain alkyl sulfide. A method of removal is disclosed. Here, the alkyl sulfide existing in the gas phase is removed, and no particular mention is made of application in the liquid phase. Furthermore, although it is not necessarily clear about the composition of the sulfur component in fats and oils, it is not only alkyl sulfide.

JP 2007-224272 A Japanese Patent Application Laid-Open No. 2002-322483 JP 54-132470 A

  The present invention provides a new method for desulfurization of fatty acids or fatty acid esters, and in particular, a method for producing desulfurized fatty acids or fatty acid esters that do not require methyl ester or distillation, and a method for producing the same. Provided is a method for producing an alcohol using the resulting fatty acid or fatty acid ester as a raw material.

The inventors of the present invention have made it possible to produce a desulfurized fatty acid or fatty acid ester by bringing a raw material fat containing a sulfur component into contact with a bromine-based oxidant and performing washing or adsorption treatment at the same time or subsequently. I found it.
That is, the present invention relates to the following [1] and [2].
[1] A method for producing a desulfurized fatty acid or fatty acid ester, comprising the following step 1 and step 2, and performing step 2 after step 1 or simultaneously with step 1 and step 2.
Step 1: A step of bringing a bromine-based oxidant into contact with a raw material fat containing one or more selected from fatty acids and fatty acid esters and a sulfur component in a liquid phase Step 2: (a) With a polar solvent For the desulfurized fatty acid or fatty acid ester obtained by the production method of [2] [1], in which washing treatment or (b) adsorption treatment with an adsorbent is performed, Periodic Table Groups 8 and 9; A method for producing an alcohol, wherein a hydrogenation reaction is carried out using a catalyst containing one or more metals selected from Group 10.

According to the present invention, desulfurized fatty acid or fatty acid ester can be easily obtained. In particular, a fatty acid or a fatty acid ester having a low sulfur component content can be efficiently obtained without passing through a methyl ester or distillation.
Furthermore, alcohol can be efficiently produced by the hydrogenation method using the obtained fatty acid or fatty acid ester as a raw material.

The method for producing a desulfurized fatty acid or fatty acid ester of the present invention includes the following step 1 and step 2, and is a method in which step 2 is followed by step 2 or simultaneously with step 1 and step 2.
Step 1: A step of bringing a bromine-based oxidant into contact with a raw material fat containing one or more selected from fatty acids and fatty acid esters and a sulfur component in a liquid phase Step 2: (a) With a polar solvent Cleaning process or (b) Adsorption process with adsorbent

[Raw oil]
The raw material fat used in the production method of the present invention contains one or more selected from fatty acids and fatty acid esters (hereinafter also simply referred to as “fatty acids”) and a sulfur component.
Although it does not restrict | limit especially as a fatty acid, The fatty acid obtained by hydrolyzing fats and oils is mention | raise | lifted.
Although it does not restrict | limit especially as a fatty acid ester, The lower alkyl ester obtained by transesterifying fats and oils and fats and oils with a C1-C5 lower alcohol, and obtained by transesterifying fats and oils with C6-C25 higher alcohols A wax etc. are mentioned.
Here, the above fats and oils refer to a composition containing a glycerin ester of a long chain fatty acid mainly composed of triglyceride, and may contain diglyceride, monoglyceride, fatty acid and the like. Here, the main component means a component occupying 50% by mass or more of the total amount.
Examples of oils and fats include vegetable oils such as palm oil, palm kernel oil, palm oil, soybean oil, corn oil, algae oil, and Jatropha oil, and animal oils such as beef tallow, lard, and fish oil. Among these, vegetable oil is more preferable from the viewpoint of stable supply, and palm oil and palm kernel from the viewpoint of containing many alkyl chain lengths of 12 and 14 carbon atoms that are useful as raw materials for high value-added products such as surfactants. Oil is more preferred.
The number of carbon atoms of the fatty acid or fatty acid residue of the fatty acid ester contained in the raw material fat is preferably 8-24, more preferably 10-22, and still more preferably 12-18.
Fatty acids or fatty acid esters may be used alone or in combination of two or more.
Although content in particular of the fatty acid or fatty acid ester contained in raw material fats and oils is not restrict | limited, For example, 80 mass% or more is preferable, 90 mass% is more preferable, 95 mass% or more is still more preferable. The upper limit of the content is, for example, 100% by mass.
Although the method of this invention can be used suitably for any raw material fats and oils, by applying to fats and oils and fatty acids, it can provide a low-cost and low environmental load process including subsequent alcohol production.

Although it does not restrict | limit especially as a sulfur component, For example, aromatic sulfur components, such as thiols, sulfides, disulfides, thiocarboxylic acids, and thiophene, are illustrated. These components can be efficiently removed in the present invention.
The sulfur content of the raw oil (before treatment) is preferably such that it is usually contained in the crude palm kernel oil or crude palm oil, but is preferably 5 mg / kg or less, more preferably 3 to 5 mg / kg. is there. Here, in this specification, sulfur content shall be measured by the method of an Example description.

  Specifically, the raw material fats and oils used in the present invention are, for example, crude vegetable oils such as crude palm oil, crude palm kernel oil, crude palm oil, crude soybean oil, crude corn oil, crude algal oil, and crude jatropha oil, and crude beef tallow , One or more selected from crude animal oils such as crude pork fat and crude fish oil.

[Brominated oxidizer]
Examples of the bromine-based oxidizing agent used in the present invention include bromine (Br ₂ ), hypobromous acid or a salt thereof, bromic acid or a salt thereof, and the like. Among these brominated oxidants, bromine, hypobromous acid or a salt thereof is preferable, and bromine is more preferable from the viewpoints of cost, handleability, and desulfurization efficiency.
Although it does not restrict | limit especially as a form of a bromine type oxidizing agent, It is preferable that it is a liquid phase state from a viewpoint of improving contact efficiency with the sulfur component in raw material fats and oils. For example, a raw material, an aqueous solution, an organic solution, and the like are preferably used. Among these, an aqueous solution is preferable from the viewpoint of being inexpensive and easy to handle.
Although the density | concentration of the bromine type oxidizing agent in aqueous solution is not restrict | limited in particular, 0.1-3 mass% is preferable, 0.5-2 mass% is more preferable, 0.8-1.5 mass% is still more preferable.
In addition, you may use the bromine carry | supported by activated carbon etc. as a form of a bromine type oxidizing agent.

[Step 1]
Step 1 is a step of bringing a bromine-based oxidant into contact with a raw material fat containing one or more selected from fatty acids and fatty acid esters and a sulfur component in a liquid phase.
The contact with the bromine-based oxidant is performed, for example, by adding the bromine-based oxidant to the liquid-phase raw material fat under stirring.
Here, the liquid phase state refers to a state in which a liquid exists at a temperature not lower than the melting point and not higher than the boiling point of fatty acids in the raw material fat. However, it is allowed to contain a small amount of gas phase or solid.
By making the state at the time of contact a liquid phase, the sulfur component in the raw material fat and the bromine-based oxidant are efficiently contacted without consuming excessive energy for evaporating the raw material.
For the contact, a batch type reaction vessel may be used, or a continuous type device may be used.
The temperature at the time of contact is not particularly limited as long as the fatty acids are in a liquid phase range. In the case of using a solid fat at normal temperature, it is also suitable to use a supercooled liquid that has been cooled to a liquid state at a temperature equal to or higher than the melting point and then cooled. From the viewpoint of operational stability, 20 to 200 ° C is preferable, 30 to 120 ° C is more preferable, and 40 to 80 ° C is still more preferable.
Although the pressure at the time of a contact is not restrict | limited in particular, the range of 0.01-1000 kPa is suitable.
The contact time varies depending on the conditions such as the amount of sulfur component, the amount of bromine-based oxidant added, and the temperature, but it is usually suitably performed in the range of 0.1 to 600 minutes.
Although the atmosphere at the time of contact is not particularly limited, it is preferably carried out in an inert gas atmosphere such as nitrogen or argon from the viewpoint of preventing quality deterioration such as coloring of fatty acids.
Fatty acids are subjected to contact as they are, but a solvent may be used from the viewpoint of maintaining a liquid phase and maintaining fluidity. Examples of the solvent include alcohols and hydrocarbons.

The amount of bromine-based oxidizing agent used is preferably in the range of 0.01 to 120% by mass, more preferably in the range of 0.05 to 50% by mass, and further in the range of 0.1 to 12% by mass with respect to the raw material fat. preferable. By setting the content to 0.01% by mass or more, oxidation can be performed in a sufficiently acceptable short time. On the other hand, by setting it as 120 mass% or less, the load of a subsequent washing | cleaning or adsorption | suction process can be reduced.
Moreover, the usage-amount of a bromine type | system | group oxidizing agent uses 5-5000 mass parts suitably per 1 mass part of sulfur elements contained in raw material fats and oils, 50-1000 mass parts is more preferable, and 100-500 mass parts is further. preferable.

[Step 2]
Step 2 is a step including either (a) a cleaning treatment with a polar solvent or (b) an adsorption treatment with an adsorbent.

<(A) Cleaning treatment with polar solvent>
Although it does not restrict | limit especially as a polar solvent used at the washing | cleaning process of this invention, The aqueous solution containing an organic solvent is used in the range which carries out liquid-liquid phase separation with water or fatty acids. As specific examples of the solvent, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and the like are preferably used. From the viewpoint of washing efficiency, water or a water-methanol mixed solvent is preferable. From the viewpoint of layer separation, it is more preferable to use a combination of methanol and water (95: 5) or water alone.
The temperature at the time of washing is not particularly limited, but a range in which the fatty acids maintain a liquid phase is preferable. As long as the fatty acids are kept in a liquid phase state, the washing step can be suitably performed even if the fatty acid is cooled to room temperature after being in the liquid phase state in Step 1. Specifically, 20-200 degreeC is preferable from a viewpoint of stability of operation, 30-120 degreeC is more preferable, and 40-80 degreeC is still more preferable.
Washing is performed by adding a solvent to the fatty acids, sufficiently stirring and then separating the layers, and removing the solvent layer. It can also be carried out continuously using a countercurrent absorption tower.
The amount of the solvent used for washing is preferably 10 to 1000 parts, more preferably 20 to 500 parts, and even more preferably 50 to 200 parts with respect to 100 parts of the raw oil and fat. When washing is carried out batchwise, it is preferably carried out in several steps.
The end point of washing can be determined by analyzing the sulfur component.

[(B) Adsorption treatment]
(Adsorbent)
The adsorbent used for the raw material fat after Step 1 of the present invention is not particularly limited, and known adsorbents such as activated carbon, activated clay, silica, zeolite, ion exchange resin can be used. Among these, activated carbon, silica, and activated clay are preferable, and activated clay and silica are more preferable from the viewpoint that they are suitable for removing highly polar components.
In addition, impregnated coal (GS2X4 / 6G) sold by Nippon Enviro Chemicals Co., which has bromine attached on activated carbon, can perform the oxidation treatment and the adsorption treatment at the same time.
0.1-10 mass% is preferable with respect to raw material fats and oils, and, as for the usage-amount of adsorbent, 0.3-5 mass% is preferable, and 0.5-2 mass% is more preferable.
The adsorption treatment is performed by adding the adsorbent to the fatty acids and stirring for a predetermined time.
The adsorption treatment can also be performed by passing the above fatty acids through a column packed with an adsorbent.
When using a column, the liquid space velocity is preferably 1 to 100 / h, more preferably 10 to 50 / h.
The adsorption temperature is preferably in the range where the fatty acids maintain a liquid phase. Even if it is cooled to room temperature after being in the liquid phase state in step 1, it can be carried out suitably. Specifically, from the viewpoint of operational stability, 20 to 200 ° C is preferable, 30 to 160 ° C is more preferable, and 40 to 120 ° C is still more preferable.
Moreover, the pressure at the time of adsorption | suction is although it does not restrict | limit in particular, The range of 1-1000 kPa is preferable, 5-300 kPa is more preferable, The range of 8-100 kPa is still more preferable.
The adsorption time is preferably 5 to 300 minutes, more preferably 10 to 180 minutes, and still more preferably 20 to 150 minutes.
After the adsorption treatment, the fatty acids and the adsorbent can be separated by means such as filtration and centrifugation.
The product is obtained by normal post-treatment. When a solvent is used, the solvent is distilled off to obtain the desired product.
Step 2 can be performed simultaneously with step 1 or subsequent to step 1.

  The sulfur content contained in the desulfurized fatty acid or fatty acid ester (hereinafter simply referred to as “desulfurized raw oil and fat”) obtained as a result of Steps 1 and 2 is 3 mg / kg or less, more preferably 1 mg / kg or less, still more preferably It is 0.8 mg / kg or less, and is suitably used as an intermediate raw material for various reactions such as a hydrogenation reaction.

[Step 3]
In this invention, the process which makes the desulfurization raw material fat and oil contact with the adsorption agent containing 1 or more types of metals chosen from Ni and Cu by the process 1 and the process 2 as the process 3 can be performed.
The adsorbent used in Step 3 is not particularly limited, but contains 10 to 85% by mass (content as a metal oxide in the total amount of adsorbent) of at least one metal selected from Ni and Cu, and is fine. The pore volume in the range of 20 to 200 nm in pore diameter is preferably 0.15 to 1.0 mL / g, and at least one metal selected from Ni and Cu is supported on the support.
The carrier is not particularly limited. For example, known carriers such as silica, alumina, silica alumina, zeolite, diatomaceous earth, activated clay, titania, zirconia, and activated carbon can be used, but silica, alumina, silica alumina, titania, zirconia are used. Silica and silica alumina are particularly preferable.

The adsorption treatment method is not particularly limited, and any commonly used method such as a suspension method or a fixed bed method can be used. When processing in large quantities, a continuous fixed bed system is advantageous.
When continuously performing the adsorption treatment in a fixed bed system, it is preferable to carry out under the following conditions. The atmosphere gas is preferably hydrogen, and an inert gas may coexist. Inert gases include nitrogen, argon and helium. The flow rate of the atmospheric gas is preferably in the range of 0.1 to 300 times the molar ratio of hydrogen to the number of moles of the desulfurized raw material fat to be treated. The pressure of the atmospheric gas is preferably 0.01 to 50 MPa, and more preferably 0.1 to 30 MPa.

From the viewpoint of obtaining a sufficient adsorption rate, the treatment temperature is preferably 40 ° C. or higher, and more preferably 50 ° C. or higher. Moreover, from a viewpoint of suppressing side reactions, such as hydrocracking, 200 degrees C or less is preferable and 180 degrees C or less is still more preferable.
The flow rate of the raw material desulfurized raw oil and fat is appropriately set from the viewpoints of productivity, catalyst life, suppression of hydrocracking, etc., but the liquid space velocity (LHSV) per hour is preferably 0.1 or more. Also, from the viewpoint of obtaining sufficient adsorption performance, LHSV is preferably 5 or less.

  As a result of Step 3, the content of the sulfur component contained in the fatty acid or the like is 0.8 mg / kg or less, more preferably 0.5 mg / kg or less, still more preferably 0.2 mg / kg or less. It is suitably used for the addition reaction.

[Method for producing alcohol]
As described above, the present invention is a desulfurized raw oil obtained through Steps 1 and 2, and optionally Step 3 as described above, and is selected from Group 8, Group 9 and Group 10 of the Periodic Table. Alternatively, the present invention also provides a method for producing alcohol, in which a hydrogenation reaction is performed using a catalyst containing two or more metals.
Examples of the catalyst include Co-based catalysts such as Co / Mo and Co / Zr, Cu-based catalysts such as Cu / Cr and Cu / Zn, and other noble metal-based catalysts such as Re-based, Ru-based, Rh-based and platinum. Can be used. Among these catalysts, a Co-based catalyst is preferable because of high alcohol selectivity and high durability against by-product fatty acids. In the presence of any of the above catalysts, the hydrogenation reaction can be carried out by any commonly used reaction method such as a liquid phase suspension bed or a fixed bed method.
When the reaction is carried out in the liquid phase suspension bed system, the catalyst amount is preferably 0.1 to 20% by mass relative to the fatty acids, but a practical reaction yield can be obtained depending on the reaction temperature or reaction pressure. Can be arbitrarily selected. The reaction temperature is preferably 160 to 350 ° C, more preferably 200 to 280 ° C. The reaction pressure is preferably 0.1 to 35 MPa, more preferably 3 to 30 MPa.
When the reaction is carried out continuously in a fixed bed system, it is preferable to use a catalyst formed into a columnar shape, a pellet shape, a spherical shape or the like. The reaction temperature is preferably 130 to 300 ° C, more preferably 150 to 270 ° C, and the reaction pressure is preferably 0.1 to 30 MPa. LHSV is arbitrarily determined according to reaction conditions in consideration of productivity and reactivity.

The desulfurized fatty acids obtained by the method of the present invention are suitably used for the production of alcohol by hydrogenation because the catalyst poison is removed.
In addition, lower alkyl esters such as methyl ester are also suitably used as biodiesel fuel with less SOx generation.
The alcohol obtained by the production method of the present invention is useful as a raw material for various functional materials such as surfactants.
In application to the direct hydrogenation reaction to fats and oils, glycerin can be recovered in high yield together with the aliphatic alcohol.
In particular, if it is applied to fats and oils or fatty acids, alcohol can be obtained without passing through an ester, so that the production method is lower in cost and less in environmental burden.
Even when applied to ordinary lower alkyl esters, the life of the catalyst is extended, resulting in an environmentally friendly process.

The present invention discloses the following desulfurized fatty acid or fatty acid ester production method and alcohol production method with respect to the above-described embodiments.
<1> A method for producing a desulfurized fatty acid or fatty acid ester, comprising the following step 1 and step 2 and performing step 2 after step 1 or simultaneously with step 1 and step 2.
Step 1: A step of bringing a bromine-based oxidant into contact with a raw material fat containing one or more selected from fatty acids and fatty acid esters and a sulfur component in a liquid phase Step 2: (a) With a polar solvent Step <2> for performing washing treatment or (b) adsorption treatment with adsorbent <1> The production method according to <1>, wherein the sulfur content in the desulfurized fatty acid or fatty acid ester is 1 mg / kg or less.
<3> The production method according to <1> or <2>, wherein the sulfur content in the raw material fat is 3 to 5 mg / kg.
<4> The production method according to any one of <1> to <3>, wherein the bromine-based oxidant is one or more compounds selected from bromine, hypobromite and salts thereof.
<5> The amount of the bromine-based oxidant used relative to the raw oil and fat is 0.01 to 120% by mass, more preferably 0.05 to 50% by mass, and still more preferably 0.1 to 12% by mass, <1 >-<4> The manufacturing method in any one of.
<6> The amount of bromine oxidizing agent used for the raw material fat is 5 to 5000 parts by mass, more preferably 50 to 1000 parts by mass, and even more preferably 100 to 500 parts by mass, per 1 part by mass of sulfur element contained in the raw material fats and oils. The production method according to any one of <1> to <5>.
<7> The production method according to any one of <1> to <6>, wherein the bromine oxidizing agent is an aqueous bromine solution.
<8> The concentration of bromine in the aqueous bromine solution is 0.1 to 3% by mass, preferably 0.5 to 2% by mass, more preferably 0.8 to 1.5% by mass, according to <7>. Production method.
<9> Step 2 is a step of performing adsorption treatment with (b) an adsorbent, and the adsorbent is one or more adsorbents selected from activated carbon, activated clay, silica, zeolite, and ion exchange resin. The production method according to any one of <1> to <8>.
<10> The amount of the adsorbent used in step 2 is 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, and still more preferably 0.5 to 2% by mass with respect to the raw oil and fat. The manufacturing method in any one of <1>-<9>.
<11> The production method according to any one of <1> to <10>, wherein the adsorption temperature in step 2 is 20 to 200 ° C, more preferably 30 to 160 ° C, and still more preferably 40 to 120 ° C.
<12> The pressure during adsorption in the step 2 is in the range of 1 to 1000 kPa, more preferably in the range of 5 to 300 kPa, and still more preferably in the range of 8 to 100 kPa, according to any one of <1> to <11>. Manufacturing method.
<13> The production method according to any one of <1> to <12>, wherein the adsorption time is 5 to 300 minutes, more preferably 10 to 180 minutes, and still more preferably 20 to 150 minutes.
<14> The production method according to any one of <1> to <13>, wherein Step 2 is performed after Step 1.
<15> The production method according to any one of <1> to <14>, further comprising the following step 3.
Step 3: Step of bringing the fatty acid or fatty acid ester desulfurized in Step 1 and Step 2 into contact with an adsorbent containing one or more metals selected from Ni and Cu <16> The adsorbent in Step 3 is made of Ni and Cu. 10 to 85% by mass (content as metal oxide in the total amount of the adsorbent) of at least one selected metal is contained, and the pore volume in the range of the pore diameter of 20 to 200 nm is 0.15 to 1. <15> The production method according to <15>, wherein the production is 0 mL / g, and at least one metal selected from Ni and Cu is supported on a carrier.
<17> The production method according to <15> or <16>, wherein step 3 is continuously performed in a fixed bed system.
<18> The production method according to <15> to <17>, wherein the atmospheric gas in step 3 contains at least hydrogen, and the pressure of the atmospheric gas is 0.01 to 50 MPa, more preferably 0.1 to 30 MPa.
<19> The production according to any one of <15> to <18>, wherein the treatment temperature in step 3 is 40 ° C. or higher, more preferably 50 ° C. or higher and 200 ° C. or lower, and still more preferably 50 ° C. or higher and 180 ° C. or lower. Method.
<20> For desulfurized fatty acid or fatty acid ester obtained by the production method according to any one of <1> to <19>, selected from Group 8, Group 9, and Group 10 of the Periodic Table A method for producing an alcohol, wherein a hydrogenation reaction is carried out using a catalyst containing one or more metals.
<21> The method for producing an alcohol according to <20>, wherein the hydrogenation reaction is performed in a liquid phase suspension bed system.
<22> The method for producing an alcohol according to <21>, wherein the reaction temperature is 160 to 350 ° C, more preferably 200 to 280 ° C.
<23> The method for producing an alcohol according to <21> or <22>, wherein the reaction pressure of the hydrogenation reaction is 0.1 to 35 MPa, more preferably 3 to 30 MPa.
<24> The method for producing an alcohol according to <20>, wherein the hydrogenation reaction is continuously performed in a fixed bed system.
<25> The method for producing alcohol according to <24>, wherein the catalyst is formed into a columnar shape, a pellet shape, a spherical shape, or the like.
<26> The method for producing an alcohol according to <24> or <25>, wherein the reaction temperature is 130 to 300 ° C, more preferably 150 to 270 ° C.
<27> The method for producing an alcohol according to any one of <24> to <26>, wherein the reaction pressure is 0.1 to 30 MPa.

[Measurement method of sulfur content]
In the following examples, the sulfur content was measured with a low concentration sulfur analyzer 9000 LLS manufactured by ANTEK. Details are as follows.
(Preparation of standard solution)
0.228 g of dibutyl sulfide is dissolved in 500 mL of a solvent (calcol 1098, manufactured by Kao Corporation, decyl alcohol), and 2 mL of this solution is added to a 100 mL volumetric flask. To this, 98 mL of Calcoal 1098 was added to prepare a 2 ng / μL standard solution. In addition, standard solutions of 1 ng / μL and 5 ng / μL were also prepared in the same manner.
(Sample preparation)
A measurement sample was added to a 4 g vial, and 5 mL of isooctane was added thereto to prepare a sample.
(Measurement of sulfur content)
The sulfur content was measured by introducing a measurement sample into a capillary, burning it with oxygen gas, and measuring the concentration of the generated SO ₂ gas with an ultraviolet fluorescent concentration sensor.

(Example 1: Oxidation / adsorption treatment of fats and oils)
50 g of crude palm kernel oil (sulfur content: 4.7 mg / kg) was placed in a 200 mL four-necked flask with a lower neck. After the temperature was raised to 50 ° C., 6 g of bromine water (bromine content 1% by mass) was added thereto (bromine content 250 times as much as Br _{2 with} respect to the sulfur element contained in the raw oil). The reaction was carried out in the liquid phase, 40 ° C., and normal pressure for 30 minutes (Step 1). Then, 1 mass% (0.5g) of adsorbent was added with respect to crude palm kernel oil as it was, and it reacted at 120 degreeC and 8 kPa for 25 minutes (process 2). As the adsorbent, activated carbon (Calboraphin (manufactured by Nippon Enviro Chemicals)) was used.
The conversion rates of the above examples are shown in Table 1 below.

(Examples 2 to 5)
Oxidation and adsorption treatment of fats and oils was performed in the same manner as in Example 1. However, as an adsorbent, instead of activated carbon (carborafin), activated carbon (Shirakaba A, (manufactured by Nippon Enviro Chemicals)), activated carbon (MHS 40/80 (manufactured by Nippon Enviro Chemicals)), activated clay (Galleon Earth V2 ( Mizusawa Chemical Co., Ltd.)) and silica (Trisyl300 (Grace Davison Discovery Sciences))) were used.
The results are shown in Table 1.

(Comparative Example 1)
The contact process with the bromine of the process 1 was not performed, but only the process 2 was performed by the method similar to Example 1, and the desulfurized palm kernel oil was manufactured. The results are shown in Table 1.

  As can be seen from Table 1, bromine water was added dropwise under mild conditions of 40 ° C. and normal pressure, and a high desulfurization effect was obtained by subjecting this to adsorption treatment with a commercially available adsorbent.

(Example 6: Bromine treatment and cleaning treatment of fats and oils)
The raw crude palm kernel oil (sulfur content: 4.7 mg / kg) was contacted with bromine in step 1 as in Example 1, and then the brominated fatty acids were washed 3 times with 500 mL of water. Extraction and washing were performed (step 2). Extraction was carried out by adding water, stirring for 1 minute at room temperature (25 ° C.), separating the layers, and allowing to stand until the upper and lower phases were almost transparent (about 3 to 5 minutes), and then draining the water.
The results are shown in Table 2.

(Comparative Example 2)
A washed palm kernel oil was produced in the same manner as in Example 6 except that the contact with bromine in Step 1 was not performed. The results are shown in Table 2.

(Example 7)
A deodorized palm kernel oil was obtained in the same manner as in Example 1 except that 0.5 g of a 9% by mass sodium bromate aqueous solution was used instead of 1% by mass bromine water. The sulfur content in the obtained palm kernel oil was 1.5 mg / kg.

(Example 8) Oxidation / adsorption treatment of fats and oils 20 kg of crude palm kernel oil (sulfur content: 4.7 mg / kg) is added to a 30 lSUS container, and coking coal (GS2X4 / 6G, bromine loading amount of 800 mg / kg) is used as a raw material. 1 mass% (200g) was added with respect to fats and oils (the process 1 and the process 2 were performed simultaneously). The contact was performed at 40 ° C. and normal pressure for 1 hour. After contact, the adsorbent was filtered off. The sulfur content of the palm kernel oil after the treatment was 0.90 (mg / kg).

Example 9
Steps 1 and 2 were performed in the same manner as in Example 1 to obtain desulfurized palm kernel oil. Furthermore, the following operation was performed as process 3 with respect to the obtained desulfurized fats and oils.

<Step 3>
(Activation and reaction of adsorbent)
A 500 mL autoclave was charged with 2.0 g of an Ni-containing adsorbent synthesized by the method described in Patent Document 1 (Japanese Patent Laid-Open No. 2007-224272) and 200 g of lauryl alcohol, and after replacing the system with hydrogen, 1 MPa The pressure was increased to 200 ° C. for 2 hours. Step 3 was performed using the adsorbent obtained by cooling and depressurization.
(Adsorption treatment)
After desulfurization, 200 g of palm kernel oil (sulfur content: 0.90 mg / kg) was charged into the above vessel, and the system was replaced with hydrogen. Then, the pressure was increased to 24.5 MPa and treated at 135 ° C. for 3 hours. After cooling and depressurization, the sulfur content of the treated palm kernel oil was measured and found to be 0.05 (mg / kg) or less.

(Example 10)
Ni-catalyzed desulfurization treatment of palm kernel oil after desulfurization Steps 1 and 2 were performed in the same manner as in Example 1 to obtain desulfurized palm kernel oil. The desulfurized palm kernel oil was desulfurized with an adsorbent containing Ni.
(Preparation of adsorbent)
An adsorbent containing Ni was produced by the method described in Patent Document 1 (Japanese Patent Laid-Open No. 2007-224272), and the obtained adsorbent was used as a fixed bed reactor (made by SUS, inner diameter 13 mmφ, height 833 mm). ). The fatty acid methyl ester from which sulfur content has been removed in advance is passed through LHSV 1.74 / h together with hydrogen (pressure 20 MPa, introduction amount 44.2 NL / h) from the top of the fixed bed reactor adjusted to 155 ° C. for 24 hours. And activated.
(Adsorption treatment)
In the fixed bed reactor prepared as described above, the desulfurized palm kernel oil obtained in Example 8 was reacted under the conditions of LHSV = 5 and hydrogen of 131.7 NL / h under the reaction conditions of 20 MPa and 155 ° C. (Condition A) was supplied from the upper part of the reactor, and an adsorption treatment was performed. The time when the reactor temperature reaches a predetermined temperature is set to 0 h, sampling is performed every 4 hours, and the residual sulfur content in the desulfurized palm kernel oil and the desulfurization activity when the desulfurized palm kernel oil is circulated for 24 hours. It is shown in Table 3. The reaction temperature and LHSV were measured under the conditions B to D shown in Table 3, and the residual sulfur content and desulfurization activity were similarly measured and shown in Table 3. The desulfurization activity was calculated by the following formula.
Desulfurization activity = log (sulfur content before adsorption treatment / sulfur content after adsorption treatment)
Here, “log” represents a natural logarithm.

(Example 11)
(Manufacture of alcohol)
Using the desulfurized palm kernel oil obtained in Example 10 as a raw material, alcohol is obtained according to the method described in JP-A-2008-221199.
In addition, since the sulfur content which is a catalyst toxicity component is as very small as about 0.1 (mg / kg), deterioration of the catalyst for alcohol production can be suppressed. For this reason, a highly efficient means for producing alcohol can be provided, and its industrial value is great.

  Since the desulfurized fatty acid or fatty acid ester obtained by the method of the invention has the catalyst poison removed, it can be suitably used as a production of alcohol by hydrogenation or a biodiesel fuel with less SOx generation. The alcohol obtained by the production method of the present invention is useful as a raw material for various functional materials such as surfactants.

Claims (9)

The manufacturing method of the desulfurized fatty acid or fatty acid ester which includes the following process 1 and process 2, performs process 2 after process 1, or performs simultaneously with process 1 and process 2.
Step 1: A step of bringing a bromine-based oxidant into contact with a raw material fat containing one or more selected from fatty acids and fatty acid esters and a sulfur component in a liquid phase Step 2: (a) With a polar solvent Cleaning process or (b) Adsorption process with adsorbent   The manufacturing method of Claim 1 whose sulfur content in raw material fats and oils is 3-5 mg / kg.   The manufacturing method of Claim 1 or 2 whose bromine-type oxidizing agent is a 1 type, or 2 or more types of compound chosen from a bromine, hypobromous acid, and its salt.   The manufacturing method of any one of Claims 1-3 whose usage-amount with respect to raw material fats and oils of a bromine type oxidizing agent is 0.01-120 mass%.   Step 2 is a step of performing an adsorption treatment with (b) an adsorbent, and the adsorbent is one or more adsorbents selected from activated carbon, activated clay, silica, zeolite, and ion exchange resin. Item 5. The production method according to any one of Items 1 to 4.   The manufacturing method according to claim 1, wherein Step 2 is performed after Step 1. Furthermore, the manufacturing method of any one of Claims 1-6 which performs the following process 3. FIG.
Step 3: The step of bringing the fatty acid or fatty acid ester desulfurized by Step 1 and Step 2 into contact with an adsorbent containing one or more metals selected from Ni and Cu   The manufacturing method of any one of Claims 1-7 whose sulfur content in the desulfurized fatty acid or fatty acid ester is 1 mg / kg or less.   One type selected from Group 8, Group 9, and Group 10 of the periodic table for the desulfurized fatty acid or fatty acid ester obtained by the production method according to any one of claims 1 to 8. Or the manufacturing method of alcohol which performs hydrogenation reaction using the catalyst containing 2 or more types of metals.