JP2014005370A - Oil and fat purification method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil and fat-purification method where a sulfur-containing compound in an oil and fat is reduced using a certain adsorbent reusable by reproduction; an adsorbent of a sulfur-containing compound in an oil and fat; and an oil and fat-production method where the content of a sulfur-containing compound is reduced.SOLUTION: Provided are: [1] an oil and fat-purification method where a sulfur-containing compound in an oil and fat is adsorbed using an adsorbent consisting of a carrier having a group represented by the general formula (1) and having a volume change rate of 50% or less, and thereafter the oil and fat and the adsorbent are separated; [2] an adsorbent of a sulfur-containing compound in an oil and fat; and [3] an oil and fat-production method where the content of a sulfur-containing compound is reduced. -R-SOM(1) (In the formula, Rrepresents a saturated or unsaturated hydrocarbon group having a carbon number of 1 to 15, and M represents a cation of at least one kind of atoms selected from Group 10 and Group 11 in the periodic table.)

Description

  TECHNICAL FIELD The present invention relates to a method for purifying fats and oils, and more particularly, to a method for purifying fats and oils for reducing sulfur-containing compounds in fats and oils, a sulfur-containing compound adsorbent in fats and oils, and a method for producing fats and oils with reduced sulfur-containing compound contents. .

  Oils and fats, fatty acids derived from fats and oils, and fatty acid esters usually contain several to several tens of mg / kg of sulfur. When these fats and oils or fatty acids derived from fats and oils and fatty acid esters are used as raw materials to produce an alcohol by performing a hydrogenation reaction in the presence of an ester reduction catalyst, the sulfur content contained in the raw materials is used as a catalyst poison for the hydrogenation catalyst. Acts and significantly reduces the catalytic activity. In particular, in the case of a fixed bed continuous reaction, the catalyst life becomes very short, so that the catalyst needs to be replaced frequently, and the operating rate of the equipment is inevitably lowered. Moreover, a sulfur-containing compound produces an odor when heating natural fats and oils. Therefore, fats and oils or fatty acid esters derived from fats and oils with a low sulfur content are required.

In Patent Document 1, as a method for removing sulfur-containing compounds from oil-and-fat materials derived from natural fats and oils such as glyceride oil, oil-and-fat materials having a step of bringing oil-and-fat material into contact with hydrosilica gel and adsorbing sulfur onto the hydrosilica gel are disclosed. A method for removing the sulfur-containing compound is disclosed.
Patent Document 2 discloses a fuel oil that is not oil and fat, but has silver supported on a carrier such as silica, and further supports nickel, ruthenium, etc., if necessary, to reduce the sulfur content in the fuel oil. A desulfurizing agent is disclosed.
Patent Document 3 discloses a cation exchange resin having a SO ₃ ^- group as a liquid chromatography column filler suitable for separation of saccharides, and Ag ^{+ and} alkali metal ions and / or alkaline earth metal ions as counter ions. Metal-supported cation exchange resins having the following have been proposed.

JP-A-6-33086 JP 2002-316043 A JP-A-61-86654

However, the hydrosilica gel described in Patent Document 1 has a problem that the reduction performance of the sulfur-containing compound is not sufficient, and the used hydrosilica gel cannot be regenerated and reused, so that the cost of the adsorption treatment is high.
The metal adsorbing carrier of Patent Document 2 is reused as a desulfurizing agent because metal components such as silver are also desorbed from the carrier during the regeneration operation to remove the sulfur-containing compound adsorbed using a high-polarity solvent. Proved difficult.
Since the metal-supported ion exchange resin of Patent Document 3 can be used in a high-polarity solvent, it can be regenerated and reused, but the metal cation of the metal-supported ion exchange resin of Patent Document 3 It was revealed that the adsorption efficiency of sulfur-containing compounds is low when the oil is replaced with those described in Patent Document 2 and applied to oils and fats.
The present invention relates to a method for refining fats and oils that reduces sulfur-containing compounds in fats and oils, using specific adsorbents that can be reused by regeneration, sulfur-containing compound adsorbents in fats and oils, and reduced sulfur-containing compound contents. It aims at providing the manufacturing method of fats and oils.

That is, the present invention provides the following [1] to [3].
[1] A sulfur-containing compound in an oil or fat is adsorbed by using an adsorbent having a volume change rate of 50% or less, comprising a carrier to which a group represented by the following general formula (1) is bonded. Oil and fat purification method for separating the agent.
_{^{-R 1 -SO 3 - M + (}} 1)
(In the formula, R ¹ represents a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, and M represents a cation of at least one atom selected from Groups 10 and 11 of the periodic table. .)
[2] A sulfur-containing compound adsorbent in fats and oils comprising a carrier to which the group represented by the general formula (1) is bonded, and having a volume change rate of 50% or less.
[3] A sulfur-containing compound in fats and oils is made by contacting an adsorbent comprising a fat and oil and a carrier to which the group represented by the general formula (1) is bonded, and having a volume change rate of 50% or less. A method for producing fats and oils with a reduced content of sulfur-containing compounds, comprising a step of purifying fats and oils after separating the adsorbents from the fats and oils.

  According to the purification method of the present invention, sulfur-containing compounds in fats and oils can be efficiently reduced using a specific adsorbent that can be regenerated and reused. Moreover, according to this invention, the manufacturing method of the fat and oil in which the sulfur containing compound adsorption agent in fats and oils and the sulfur containing compound content were reduced can be provided.

[Oil and fat refining method]
The method for purifying fats and oils of the present invention comprises an adsorbent comprising a carrier bonded with a group represented by the following general formula (1) and having a volume change rate of 50% or less (hereinafter also referred to as “adsorbent of the present invention”). Is used to adsorb sulfur-containing compounds in fats and oils, and then separate the fats and fats and the adsorbent.
_{^{-R 1 -SO 3 - M + (}} 1)
(In the formula, R ¹ represents a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, and M represents a cation of at least one atom selected from Groups 10 and 11 of the periodic table. .)

<Oil and fat>
The fats and oils mean natural fats and oils derived from natural resources such as vegetable fats, animal fats and marine fats and oils, and derivatives derived from natural fats and oils such as diglycerides and monoglycerides obtained by transesterification of natural fats and oils. Examples of vegetable oils include corn oil, cottonseed oil, olive oil, peanut oil, rapeseed oil, sunflower oil, sesame oil, soybean oil, sunflower oil, coconut oil, palm oil, palm kernel oil and the like. Pork fat etc. are mentioned, and fish oil etc. are mentioned as marine oil and fat. Moreover, fatty acid, fatty acid ester, etc. are mentioned as a derivative derived from natural fats and oils.
Among these, vegetable oils such as rapeseed oil, coconut oil, palm oil, and palm kernel oil, and animal fats such as beef tallow are preferable, and vegetable oils such as coconut oil and palm kernel oil are more preferable.

In oils and fats, for example, vegetable oils such as coconut oil and palm oil, since organic pigments such as sterols, carotenoids, and chlorophyll are present, it is preferable to carry out a conventional purification treatment in advance.
Moreover, in fats and oils, although it changes with kinds of fats and oils, several to several dozen ppm sulfur containing compound is normally contained.
According to the method for purifying fats and oils of the present invention, the concentration of the sulfur-containing compound in the fats and oils can be reduced to preferably 2.5 ppm or less, more preferably 1 ppm or less.
Sulfur-containing compounds present in fats and oils include aromatic sulfur-containing compounds such as thiols, sulfides, disulfides, thiocarboxylic acids, thiophenes, sulfoxides, episulfides, isothiocyanates, thiocyanates, oxazolidinethiones And sulfur-containing amino acids. There are a wide variety of sulfur-containing compounds present in fats and oils, from low to high polar ones. By using the adsorbent of the present invention, sulfur-containing compounds can be efficiently removed from fats and oils. It becomes.
The adsorbent of the present invention can remove sulfur-containing compounds more efficiently when the oxidation number of sulfur of the sulfur-containing compound in fats and oils is divalent or tetravalent, and the oxidation number is divalent. In some cases, sulfur-containing compounds can be removed more efficiently.

<Adsorbent>
The adsorbent of the present invention may be an adsorbent that is composed of a carrier to which the group represented by the general formula (1) is bonded and has a volume change rate of 50% or less.
Here, “bond” refers to a covalent bond and does not include other bonds such as ionic bond and physical adsorption.
The adsorbent of the present invention comprises a carrier to which the group represented by the general formula (1) is bound (hereinafter also referred to as “the carrier of the present invention”).
The carrier to which the group represented by the general formula (1) is bonded is not limited to one obtained by bonding the group represented by the general formula (1) to the carrier, and the adsorbent is represented by the general formula. What is necessary is just to have group represented by (1). For example, after sulfonating the crosslinked organic polymer compound, the counter ion of the sulfonic acid group is exchanged with silver ion, as long as it has a group represented by the general formula (1), In the present invention, the carrier represented by the general formula (1) is included.
The carrier of the present invention may be an inorganic compound or an organic compound, but from the viewpoint of use cost, one or more selected from an inorganic compound and a crosslinked organic polymer compound are preferable.
The shape of the adsorbent of the present invention is not particularly limited and may be any of a spherical shape, a pellet shape, and a crushed shape, but a spherical shape is preferable from the viewpoint of the adsorption efficiency of the sulfur-containing compound.
From the viewpoint of the adsorption efficiency of the sulfur-containing compound contained in the fat and oil, the adsorbent of the present invention preferably has a number average particle size in the fat and oil of 10 to 1200 μm, more preferably 20 to 800 μm, and still more preferably 30 to 30 μm. 600 μm. Specifically, the average particle size is measured by the method described in the examples.
The adsorbent of the present invention is preferably porous from the viewpoint of the adsorption efficiency of the sulfur-containing compound contained in the oil and fat, and the average pore diameter in the oil and fat is a value measured by a mercury intrusion method, preferably 10 to 10. 300 tons, more preferably 40 to 150 tons. The average pore diameter of the adsorbent in fats and oils is specifically evaluated by the method described in the examples.

If the volume change rate is 50% or less, the adsorbent of the present invention has a high adsorption capacity for sulfur-containing compounds in fats and oils. The volume change rate of the adsorbent is preferably 30% or less, more preferably 15% or less, and still more preferably 10% or less, from the viewpoint of the adsorption capacity for the sulfur-containing compound.
In the present invention, the volume change rate refers to the difference between the volume of the adsorbent in water and the volume of the adsorbent in fats and oils divided by the volume of the adsorbent in water, specifically, the method described in the examples. Measured in Here, the volume of the adsorbent refers to the volume containing water or fat after swelling when the adsorbent swells with water or fat. When the adsorbent is completely dissolved in water or fat under the measurement conditions described in the examples, the volume change rate is not measured.
The volume change rate depends on the properties of the carrier of the present invention.For example, when an inorganic compound described later is used as the carrier of the present invention, swelling due to water or oil is not seen, and no volume change is seen. The rate can be considered as 0%. On the other hand, when the carrier of the present invention is cross-linked as described later, the adsorbent of the present invention may swell due to water or fat, in which case the group represented by the general formula (1) Since it has high polarity, normally, the degree of swelling in water is larger than the degree of swelling in fats and oils, and the volume change rate shows a value of 0% or more.

(Carrier)
Specific examples of the inorganic compound that is the carrier of the present invention include silica, alumina, silica alumina, zeolite, diatomaceous earth, activated clay, titania, zirconia, activated carbon and the like.
Specific examples of the crosslinked organic polymer compound that is the carrier of the present invention include crosslinked synthetic polymers such as crosslinked polystyrene, crosslinked polyvinyl alcohol, and crosslinked polymethacrylate, crosslinked starch, crosslinked pullulan, crosslinked And cross-linked polysaccharides such as cross-linked hydroxyethyl cellulose, cross-linked methyl cellulose, and cross-linked carboxymethyl cellulose.
When the carrier of the present invention is a crosslinked synthetic polymer or a crosslinked polysaccharide, the volume change rate of the adsorbent can be controlled by the degree of crosslinking of the crosslinked synthetic polymer or crosslinked polysaccharide, and the degree of crosslinking It is possible to reduce the volume change rate of the adsorbent by increasing the.
There is no limitation in particular as a crosslinking agent used for crosslinking. Specifically, a crosslinking agent having two or more vinyl groups in the molecule, such as divinylbenzene, methylenebisacrylamide, polyethylene glycol diacrylate, trimethylolpropane triacrylate, or the like, or glycidyl in the molecule such as polyethylene glycol diglycidyl ether. Examples thereof include a crosslinking agent having two or more groups.

  From the viewpoint of ease of production of the adsorbent of the present invention and cost, the support of the present invention is preferably silica, alumina, silica alumina or cross-linked polystyrene, more preferably cross-linked polystyrene, More preferably, it is a cross-linked polystyrene cross-linked with divinylbenzene.

(Group represented by general formula (1))
_{^{-R 1 -SO 3 - M + (}} 1)
In general formula (1), R ¹ represents a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, and M represents a positive atom of at least one atom selected from Groups 10 and 11 of the periodic table. Indicates ions.
The hydrocarbon group represented by R ¹ in the general formula (1) may be linear, branched or cyclic. R ¹ is represented by the following general formula (2) because of the ease of ionic bond formation between the cation represented by M ⁺ and the sulfonate group (—SO ₃ ⁻ ) in the general formula (1). It is preferably a hydrocarbon group. In the general formula (2), the sulfonate group in the general formula (1) is bonded to the terminal on the benzene ring side.
_{- (CH 2) n -C 6} H 4 - (2)
In general formula (2), n is an integer of 0 to 9, more preferably an integer of 0 to 5, and still more preferably an integer of 0 to 3.

If M ⁺ is a cation of at least one atom selected from Groups 10 and 11 of the periodic table, it can efficiently adsorb sulfur-containing compounds in fats and oils. From the viewpoint of adsorption efficiency, the cation is preferably a silver ion and / or a palladium ion, and more preferably a silver ion.
Since the sulfonate group in the general formula (1) and the cation represented by M ⁺ are strongly bonded by ionic bonds, the sulfonate group is washed with a highly polar solvent in oils and fats or during regeneration. However, there is an advantage that the cation represented by M ⁺ in the general formula (1) is difficult to desorb from the adsorbent of the present invention. For this reason, the adsorbent of the present invention can be used in fats and oils, and after adsorbing sulfur-containing compounds in fats and oils, it is possible to selectively remove sulfur-containing compounds using a highly polar solvent. Yes, it can be reused. From the viewpoint of the refining cost of the fats and oils of the present invention, the adsorbent of the present invention is preferably regenerated and reused.

The amount of M ^{+ in} the adsorbent is preferably 0.1 mmol / g or more, more preferably 0.3 mmol / g or more, and still more preferably 0.5 mmol / g or more from the viewpoint of adsorption efficiency. The amount of M ⁺ in the adsorbent is preferably 3.0 mmol / g or less, more preferably 2.5 mmol / g or less, and still more preferably 1.5 mmol / g or less from the viewpoint of availability.
The SO ₃ ⁻ amount in the adsorbent is preferably 0.1 mol / g or more, more preferably 0.3 mol / g or more, from the viewpoint of immobilizing a suitable amount of M ^{+ in} the adsorbent, / g or more is more preferable. The amount of SO ₃ ⁻ in the adsorbent is preferably 3.0 mmol / g or less, more preferably 2.5 mmol / g or less, and still more preferably 1.5 mmol / g or less from the viewpoint of availability.
The amount of M ⁺ in the adsorbent can be determined by ICP (radio frequency inductively coupled plasma) emission spectroscopic analysis, and the amount of SO ₃ ⁻ in the adsorbent can be determined by atomic absorption analysis. Specifically, it can be carried out by the method described in the examples.

<Method for producing adsorbent>
There is no limitation in particular in the manufacturing method of the adsorption agent of this invention. When the carrier of the present invention is an inorganic compound such as silica, it can be obtained by reacting (i) silica with an agent represented by the following general formula (3), or (ii) silica and the following general formula ( 4) After the agent represented by 4) is reacted, by contacting with an aqueous solution of at least one metal salt selected from Group 10 and Group 11 of the periodic table such as silver nitrate, the counter ion of the sulfonate group is exchanged. Can be obtained.
_{^{X-R 2 -SO 3 - Y}} + (3)
_{^{X-R 2 -SO 3 - Z}} + (4)
In the general formulas (3) and (4), X represents a functional group capable of forming a bond with the carrier of the present invention. Specifically, a hydroxyl group, an amino group, a halogen atom, a trihydroxysilano group, a trialkoxy (C1 -3) A silano group, an epoxy group, etc. are mentioned. R ² represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms. Y ⁺ represents a cation of an atom selected from Groups 10 and 11 of the periodic table, and Z ⁺ represents a cation of an atom excluding a cation of an atom selected from Groups 10 and 11 of the periodic table. .

When the carrier of the present invention is a cross-linked organic polymer compound, (iii) after polymerization and cross-linking of the raw material monomer or after cross-linking to polysaccharide, the above (i) or (ii ) In the same manner as in the case of), and (iv) represented by the general formula (1) except that the counter ion is not M ^+. A commercially available strongly acidic ion exchange resin having a group to be exchanged with an aqueous solution of at least one metal salt selected from Group 10 and Group 11 of the periodic table such as silver nitrate, to exchange the counter ion of the sulfonate group You can also. In the production method (iii), the crosslinking and the reaction with the agent of the general formula (3) or (4) may be performed simultaneously.

<Method for adsorption / separation of sulfur-containing compounds>
The method for purifying fats and oils of the present invention includes a step of adsorbing a sulfur-containing compound in fats and oils to the adsorbent of the present invention and then separating the fats and oils and the adsorbent.
The method for adsorbing sulfur-containing compounds in fats and oils using the adsorbent of the present invention is not particularly limited as long as it is a method for bringing the adsorbent of the present invention into contact with the target fats and oils, but (i) the present invention. (2) A method of adding the adsorbent of the present invention to a fat or oil, or a method of adding a fat to the adsorbent of the present invention (hereinafter also referred to as “column method”) (Hereinafter also referred to as “addition method”) can be suitably employed.
In the case of the column method, adsorption of the sulfur-containing compound by the adsorbent of the present invention and separation of the adsorbent can be performed simultaneously. In the case of the addition method, after the adsorption of the sulfur-containing compound in the fat and oil by the adsorbent of the present invention, the fat and oil and the adsorbent are separated by a known method such as filtration. Among these, the column method is more preferable from the viewpoint of adsorption efficiency.
In the case of the column method, the liquid space velocity is preferably 0.12 to 120 h ⁻¹ , more preferably 1.2 to 30 h ⁻¹ , from the viewpoint of the adsorption efficiency of the adsorption efficiency of the sulfur-containing compound to the adsorbent. 2 to 12 h ⁻¹ is more preferable.

In the case of the addition method, the amount of the adsorbent used in the present invention is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the fat and oil, from the viewpoint of adsorption efficiency.
The contact time between the oil and fat and the adsorbent of the present invention is preferably 0.1 to 12 hours, more preferably 0.5 to 2 hours. From the viewpoint of the adsorption rate of the sulfur-containing compound, it is preferable to mix the oil after addition of the adsorbent with shaking or stirring.
In the column method or the addition method, the temperature at which the sulfur-containing compound in the fat or oil is adsorbed by the adsorbent of the present invention is preferably from 5 to 80 ° C., more preferably from the viewpoint of preventing decomposition of the sulfur-containing compound and adsorption efficiency. Is 15-30 ° C.

In both the column method and the addition method, a solvent can be used for the purpose of reducing the viscosity of the oil.
Although there is no limitation in particular in the solvent used, from a viewpoint of the adsorption | suction efficiency of the sulfur containing compound in fats and oils by the adsorption agent of this invention, a medium-low polarity solvent is preferable and a low polarity solvent is more preferable. Specifically, hydrocarbon solvents such as hexane, octane, isooctane, and toluene; ester solvents such as ethyl acetate are preferable, hydrocarbon solvents such as hexane, octane, isooctane, and toluene are more preferable, and separation from oils and fats is easy after purification. From the viewpoint of properties, hexane is more preferable.

<Regeneration treatment of adsorbent>
The adsorbent of the present invention is adsorbable by adsorbing sulfur-containing compounds in fats and oils because the amount of sulfur-containing compounds that can be adsorbed is determined by the amount of M ⁺ supported in the adsorbent. The amount drops. Thus, although the adsorbable amount of the adsorbent after use in the method for purifying fats and oils of the present invention (hereinafter also referred to as “adsorbent after use”) is lower than before use, the adsorbent after use is reduced. By removing the sulfur-containing compound from the adsorbent by bringing the agent into contact with the highly polar solvent, the adsorbable amount of the sulfur-containing compound can be recovered again (hereinafter also referred to as “regeneration treatment”). The adsorbent of the present invention that has been regenerated can be reused in the method for purifying fats and oils of the present invention.

Examples of the highly polar solvent used for the regeneration treatment include lower alcohols having 1 to 3 carbon atoms, acetonitrile, and the like, but they have high solubility in fats and oils and sulfur-containing compounds, and are easy to remove from the adsorbent. Therefore, ethanol or isopropanol is preferable.
The amount of the highly polar solvent used is preferably 1 to 100 times by volume, more preferably 5 to 50 times by volume with respect to the adsorbent after use, from the viewpoint of the removal rate of the migration compound from the adsorbent and from the viewpoint of cost. 10-30 volume times is still more preferable.
The method for contacting the adsorbent after use with the highly polar solvent is not particularly limited, but it is preferable from the viewpoint of the removal efficiency of the sulfur-containing compound that the adsorbent is packed in a column and then the highly polar solvent is circulated. .
The adsorbent after the regeneration treatment is preferably brought into contact with the hydrocarbon solvent before reuse, and the highly polar solvent adhering to the adsorbent is replaced with the solvent.

[Sulfur-containing compound adsorbent]
The sulfur-containing compound adsorbent in the fats and oils of the present invention is an adsorbent comprising a carrier to which the group represented by the general formula (1) is bonded and having a volume change rate of 50% or less.
As described above, sulfur-containing compounds in fats and oils are aromatic sulfur-containing compounds such as thiols, sulfides, disulfides, thiocarboxylic acids, thiophenes, sulfoxides, episulfides, isothiocyanates, thiocyanates, oxazolidinethiones. And low-polarity to high-polarity amino acids such as sulfur-containing amino acids, but by using the adsorbent of the present invention, it becomes possible to efficiently remove sulfur-containing compounds from fats and oils. .
The adsorbent of the present invention can remove sulfur compounds more efficiently when the sulfur oxidation number of the sulfur-containing compound in the fat is divalent or tetravalent, and the oxidation number is divalent. In this case, the sulfur-containing compound can be removed more efficiently.

[Oil production method]
The method for producing a fat with reduced sulfur-containing compound content according to the present invention comprises an adsorbent comprising a fat and fat and a carrier to which a group represented by the general formula (1) is bound, and having a volume change rate of 50% or less. After making it contact and adsorb | suck the sulfur containing compound in fats and oils to this adsorbent, the refinement | purification process of the fats and oils which isolate | separates fats and oils and this adsorbent is included.
According to the method for producing fats and oils of the present invention, fats and oils having a reduced sulfur-containing compound content can be efficiently produced.

In relation to the above-described embodiment, the present invention further discloses the following oil and fat purification method, production method, and adsorbent.
<1>
It consists of a carrier bonded with a group represented by the following general formula (1), adsorbs sulfur-containing compounds in fats and oils using an adsorbent whose volume change rate is 50% or less, and then separates the fats and fats and the adsorbents. A method for purifying oils and fats.
_{^{-R 1 -SO 3 - M + (}} 1)
(In the formula, R ¹ represents a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, and M represents a cation of at least one atom selected from Groups 10 and 11 of the periodic table. .)

<2>
The method for purifying fats and oils according to <1>, wherein R ¹ in the general formula (1) is a hydrocarbon group represented by the following general formula (2).
_{- (CH 2) n -C 6} H 4 - (2)
(In the formula, n is an integer of 0 to 9, preferably 0 to 5, more preferably 0 to 3.)
<3>
The method for purifying fats and oils according to <1> or <2>, wherein M ⁺ in the general formula (1) is silver ion or palladium ion.
<4>
The method for purifying fats and oils according to any one of <1> to <3>, wherein the carrier is one or more selected from an inorganic compound and a crosslinked organic polymer compound.
<5>
The method for purifying fats and oils according to any one of <1> to <4>, wherein the volume change rate is 30% or less, preferably 15% or less, more preferably 10% or less.

<6>
A sulfur-containing compound adsorbent in fats and oils, comprising a carrier to which a group represented by the following general formula (1) is bonded, and having a volume change rate of 50% or less.
_{^{-R 1 -SO 3 - M + (}} 1)
(In the formula, R ¹ represents a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, and M represents a cation of at least one atom selected from Groups 10 and 11 of the periodic table. .)
<7>
The sulfur-containing compound adsorbent according to <6>, wherein R ¹ in the general formula (1) is a hydrocarbon group represented by the following general formula (2).
_{- (CH 2) n -C 6} H 4 - (2)
(In the formula, n is an integer of 0 to 9, preferably 0 to 5, more preferably 0 to 3, more preferably 3.)
<8>
The sulfur-containing compound adsorbent according to <6> or <7>, wherein M ⁺ in the general formula (1) is silver ion or palladium ion.
<9>
The sulfur-containing compound adsorbent according to any one of <6> to <8>, wherein the carrier is one or more selected from an inorganic compound and a crosslinked organic polymer compound.
<10>
The sulfur-containing compound adsorbent according to any one of <6> to <9>, which is used for removing sulfur-containing compounds in fats and oils.

<11>
An oil and fat and a carrier to which the group represented by the general formula (1) described in <1> is bonded, and an adsorbent having a volume change rate of 50% or less are brought into contact with the adsorbent. A method for producing fats and oils with a reduced content of sulfur-containing compounds, comprising a step of purifying fats and oils after separating the sulfur-containing compounds and separating the adsorbents from the fats and oils.

Specific operations of each measurement in the following examples are shown below.
<Measurement of sulfur concentration in fats and oils>
The sulfur concentration in the fat was measured by combustion oxidation / UV fluorescence method (Antek Instruments, low concentration sulfur analyzer 9000 LLS). Using isooctane as a diluent solvent, a 50% by mass solution was prepared, and measurement was performed at a combustion tube temperature of 1050 ° C. and a sample introduction amount of 60 μL.

<Measurement method of volume change rate>
Fill a graduated cylinder (20 mm in diameter) with a filler swollen in a large excess of water for 24 hours so that the top surface after filling the graduated cylinder is as flat as possible and parallel to the bottom of the graduated cylinder. While filling up to 10 mL scale. The filler is washed with 100 mL of ethanol and 100 mL of hexane in this order, and then left for 1 hour in a large excess of hexane with respect to the filler. Then, the graduated cylinder is refilled with the same method as described above, and then filled. The scale of the upper surface position (A (mL)) was read.
The volume change rate was calculated from the following calculation formula.
Volume change rate (%) = {10 (mL) −A (mL)} / 10 (mL) × 100

<Method for measuring the amount of M ^{+ in} the adsorbent>
(I) Method for measuring the amount of M ⁺ when the carrier of the present invention is a cross-linked organic polymer compound An adsorbent (hereinafter also referred to as “dry adsorbent”) dried at 80 ° C. for 10 hours under a nitrogen stream is 0. 0.1 g was collected and subjected to thermal decomposition treatment with 1 mL of concentrated sulfuric acid (98% by mass) and 5 mL of concentrated nitric acid (60% by mass). Subsequently, decomposition treatment is performed while adding hydrogen peroxide (30% by mass) and concentrated nitric acid as appropriate. After cooling, 1 mL of concentrated nitric acid is added, and then the sample solution is dissolved in 20 mL with ultrapure water. It was. ICP (high frequency inductively coupled plasma) emission spectrometer (Perkin Elmer, Optima 5300 DV, high frequency output: 1.3 kW, sample introduction amount: 1 mL / min, sample flash time: 20 seconds, measurement height: 15 mm, measurement wavelength (Ag: 328.068 nm, Pd: 340.458 mm), the amount of M ⁺ was calculated.
(Ii) Method for measuring the amount of M ⁺ when the carrier of the present invention is silica After collecting 0.01 g of the dry adsorbent in a platinum crucible, an alkali flux (sodium carbonate: boric acid = 5: 2 (mass ratio)) ) Add 2g and melt at 950 ° C. After cooling, the sample solution was dissolved in 4 mL of hydrochloric acid (13.5% by mass) and diluted with water to 100 mL. The amount of M ⁺ was calculated by ICP emission spectroscopic analysis in the same manner as in “(i) Method for measuring the amount of M ⁺ when the carrier of the present invention is a crosslinked organic polymer compound”.

<Measurement method of Na ⁺ amount in comparative adsorbent A>
0.1 g of the dried adsorbent was sampled and subjected to thermal decomposition treatment with 1 mL of concentrated sulfuric acid and 5 mL of concentrated nitric acid. Thereafter, decomposition treatment is performed while appropriately adding hydrogen peroxide (30% by mass) and concentrated nitric acid, and after standing to cool, 1 mL of concentrated nitric acid is added, and then dissolved in 20 mL with ultrapure water as a sample solution. did. Atomic absorption spectrometer (Varian Co., Spectra AA220, measurement wavelength: 589 nm, Frame Type: Air / acetylene, air flow rate: 13.5 L / min, acetylene flow: 2 L / min) of the M ⁺ by measuring the The amount was calculated.

<SO ₃ in the adsorbent ^- the amount of measurement methods>
After passing 20 g of 1M-NaCl aqueous solution through 5 g of the dry adsorbent packed in the column to exchange the counter ion of SO ₃ ⁻ in the adsorbent with Na ⁺ , 100 mL of ion-exchanged water was passed through the surplus adsorbent. Na ⁺ removal was performed. Thereafter, 20 g of a 1M-KCl aqueous solution was passed through to exchange the SO ₃ ⁻ counter ion in the adsorbent with K ⁺ , and the amount of Na ⁺ contained in the effluent at that time was analyzed by atomic absorption spectrometry (manufactured by Varian, (Spectra AA220, measurement wavelength: 589 nm, frame type: air / acetylene, air flow rate: 13.5 L / min, acetylene flow rate: 2 L / min). SO ₃ in the Na ⁺ amount in the effluent sorbent ^- amount is regarded as substantially the same, SO ₃ in the adsorbent ^- was calculated quantities.

<Method for measuring the amount of trilaurin and didodecyl sulfide>
Trirallin and didodecyl sulfide were quantified by gas chromatography (GC-FID). The measurement conditions are as follows.
Gas chromatograph measuring device: 6890 manufactured by Agilent
Column: HP-1 (30 m × 0.32 mm × 0.25 μm)
Oven temperature rising condition: 40 ° C (0 min) → 10 ° C / min → 300 ° C (15 min)
Carrier gas: He (column flow rate: 1.0 mL / min)
Injection method: split 10: 1, inlet temperature: 300 ° C., sample injection volume: 1 μL
Detector: FID (300 ° C)
As a measurement sample, a solution prepared by adding 1 mL of hexane to each solution containing trilaurin and didodecyl sulfide in Reference Example 1 below, which was dried at 80 ° C. under a nitrogen stream, was used.

<Evaluation method of average pore diameter>
The average pore diameter of the adsorbent at the time of drying was measured by a mercury intrusion method (Micromeritics, PoreSizer 9320). The maximum pressure of mercury intrusion was 207 MPa. Since the adsorbent in the examples of the present invention can be regarded as having almost no volume change in the dry state and in the fats and oils, the value obtained by the above method was regarded as the value of the average pore diameter of the adsorbent of the present invention in the fats and oils. .

<Measurement method of average particle diameter of adsorbent>
(1) When support | carrier is a silica The average particle diameter at the time of drying was measured by the following method.
Combine the test sieve (see JIS-Z8801-1) from the top in the order of openings 106 μm, 90 μm, 53 μm, 32 μm, and saucer, put about 50 g of water-absorbing resin in the top sieve, and roll tap type automatic sieve shaker And shaken for 10 minutes.
After measuring the weight of the adsorbent remaining on each sieve, the mass ratio (residual percentage) R to the whole adsorbent remaining on each sieve is a semi-logarithmic graph (horizontal axis: particle size (logarithmic scale), vertical axis : Residual percentage), and the particle diameter corresponding to R = 50% was determined to obtain the average particle diameter.
Since the adsorbents in the examples can be regarded as having almost no volume change in the dry state and in the fats and oils, the value obtained by the above method was regarded as the value of the average particle diameter of the adsorbents in the fats and oils.
(2) When the carrier is a crosslinked organic polymer compound The average particle size during drying was measured by the following method.
In the method (1) above, the test sieve was measured in the same manner as (1) above except that the test sieves were combined in the order of 850 μm, 600 μm, 500 μm, 355 μm, 106 μm, and pan from the top.
Since the adsorbents in the examples can be regarded as having almost no volume change in the dry state and in the fats and oils, the value obtained by the above method was regarded as the value of the average particle diameter of the adsorbents in the fats and oils.

Example 1 (Preparation of adsorbent 1)
(1) Preparation of silver nitrate solution 1.5 g of silver nitrate was weighed and dissolved while gradually adding to 1.5 mL of ultrapure water.
(2) Preparation of adsorbent 1 5 g of strong cation exchange silica having a benzenesulfonic acid group dried at 80 ° C. for 10 hours under a nitrogen stream (manufactured by Varian, trade name; cartridge bond elute for solid phase extraction, benzenesulfone) The acid SCX) was filled with 3.0 g of the silver nitrate solution prepared in the above (1), and silver ions were supported on the carrier. Thereafter, 100 ml of each was poured in the order of ultrapure water, ethanol, chloroform, and hexane for washing.
The obtained adsorbent has an average particle size of 45 μm, a volume change rate of 0%, the average pore size of the adsorbent in fats and oils is 60 mm, the Ag ⁺ amount in the adsorbent is 0.64 mmol / g, and the SO ₃ ⁻ amount is It was 0.79 mmol / g.

Example 2 (Preparation of adsorbent 2)
(1) Preparation of silver nitrate solution 1.5 g of silver nitrate was weighed and dissolved while gradually adding to 1.5 mL of ultrapure water.
(2) Preparation of adsorbent 2 7.5 g of a strong cation exchange resin having a benzenesulfonic acid group dried at 80 ° C. for 10 hours under a nitrogen stream (manufactured by Mitsubishi Chemical Corporation, styrene-divinylbenzene synthetic polymer, high A porous type strongly acidic cation exchange resin RCP160) was filled with 3.0 g of the silver nitrate solution prepared in (1), and silver ions were supported on the carrier. Thereafter, 100 ml of each was poured in the order of ultrapure water, ethanol, chloroform, and hexane for washing.
The obtained adsorbent has an average particle size of 519 μm, a volume change rate of 10%, the average pore size of the adsorbent in fats and oils is 100 kg, the Ag ⁺ amount in the adsorbent is 1.2 mmol / g, and the SO ₃ ⁻ amount is It was 1.5 mmol / g.

Preparation Example 1 (Preparation of Comparative Adsorbent A)
Comparative Adsorbent A was obtained in the same manner as Adsorbent 2 except that 1M aqueous sodium acetate solution was used instead of the silver nitrate solution.
The obtained adsorbent has an average particle size of 519 μm, a volume change rate of 10%, the average pore size of the adsorbent in fats and oils is 100 mm, the Na ⁺ amount in the adsorbent is 1.2 mmol / g, and the SO ₃ ⁻ amount is It was 1.5 mmol / g.

Preparation Example 2 (Preparation of comparative adsorbent B)
A commercially available silica gel adsorbing 10% by mass of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 10% silver nitrate silica gel) was used.

Preparation Example 3 (Preparation of comparative adsorbent C)
As a strong cation exchange resin, a styrene-divinylbenzene synthetic polymer manufactured by Mitsubishi Chemical Co., Ltd., trade name; comparative adsorption by performing the same operation as that of the adsorbent 2 except that the strong acid cation exchange resin SK1B was used. Agent C was prepared.
The obtained adsorbent has an average particle diameter of 731 μm, a volume change rate of 40%, an average pore diameter of the adsorbent in fats and oils of 100 kg, an Ag ⁺ amount in the adsorbent of 1.3 mmol / g, and an SO ₃ ⁻ amount of It was 1.6 mmol / g.

Reference example 1
In order to confirm that the sulfur-containing compound can be selectively adsorbed by the adsorbent of the present invention and that the adsorbent after use can be reused by the regeneration treatment, the following experiment was conducted as a model.

(Confirmation of selective adsorption)
Each column cartridge was filled with 5 g of the adsorbents 1 and 2 and the comparative adsorbents A and B obtained in Examples 1 and 2 and Preparation Examples 1 and 2, and impregnated with flowing hexane. Each 500 μg mixture of trilaurin (manufactured by Wako Pure Chemical Industries, Ltd.) and didodecyl sulfide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 1 mL of hexane and injected into the column cartridge at room temperature. Thereafter, 30 mL of hexane is circulated through the column cartridge at a flow rate of 1 mL / min, and then 30 mL of ethanol is circulated at a flow rate of 1 mL / min to quantify the amounts of trilaurin and didodecyl sulfide in each effluent. The value divided by the amount (500 μg) was defined as the recovery rate (%). The results are shown in Table 1.

  In adsorbents 1 and 2 having silver ions and comparative adsorbent B, didodecyl sulfide was not detected in the hexane solvent after distribution, but only trilaurin was eluted, and didodecyl sulfide was selectively adsorbed. It was confirmed that In Comparative Adsorbent B, silver ions were confirmed in the ethanol solvent after distribution, and the desorption of silver ions by ethanol was confirmed.

(Confirmation of reusability by reprocessing)
After performing regeneration treatment by pouring 100 mL each of ethanol, chloroform, and hexane at a flow rate of 1 mL / min into the adsorbent 1 and adsorbent 2 in the column cartridge used in the above (confirmation of selective adsorption). Again, the same operation as described above (confirmation of selective adsorption) was performed. The results are shown in Table 2.

  From the comparison between Table 1 and Table 2, it can be seen that the adsorbent of the present invention can be reused by the regeneration treatment.

Example 3 (Adsorption of sulfur-containing compounds in fats and oils)
Adsorbent 1 was filled in 5 g in a column cartridge, and impregnated by flowing 20 mL of hexane. Thereafter, oil derived from palm containing a sulfur-containing compound having a sulfur concentration of 3.5 ppm (Philippines, acid value: 10.3 mg KOH / g, hydroxy value: 7.8 mg KOH / g, iodine value: 8.3 g I2 / 100 g, water content 0.05%) 2 g dissolved in 1 mL of hexane was injected into the cartridge column at a flow rate of 0.3 mL / min at room temperature. Thereafter, 20 mL of hexane was passed at a flow rate of 1 mL / min, and the oils and fats were collected. The sulfur concentration in the recovered hexane solvent was 0.4 ppm on the basis of the amount of oil lipid.

Sulfur-containing compounds are desorbed by washing the column by flowing 100 ml each of chloroform, ethyl acetate, acetonitrile, and ethanol in order at a flow rate of 1 mL / min. -Collected and regenerated the adsorbent.
The same operation as described above was performed except that the obtained regeneration-treated adsorbent was used. The sulfur concentration in the recovered hexane solvent was 0.4 ppm on the basis of the amount of oil lipid.

Example 4 (Adsorption of sulfur-containing compounds in fats and oils)
0.05 g of the adsorbent 1 was added to 5 g of the fat used in Example 1, and the mixture was shaken at room temperature for 2 hours. Thereafter, filtration was performed to separate the adsorbent and the fats and oils. The sulfur concentration in the obtained oil and fat was 2.4 ppm.

Example 5 (Adsorption of sulfur-containing compounds in fats and oils)
0.05 g of adsorbent 2 was added to 5 g of oil and fat, and the mixture was shaken at room temperature for 2 hours, and then filtered to separate the adsorbent and oil and fat. The sulfur concentration in the obtained oil and fat was 1.9 ppm.

Comparative Example 1 (Adsorption of sulfur-containing compounds in fats and oils)
0.05 g of the comparative adsorbent C was added to 5 g of the oil and fat, and the mixture was shaken for 2 hours, followed by filtration to separate the adsorbent and the oil and fat. The sulfur concentration in the obtained fat was 3.5 ppm.

Claims (10)

It consists of a carrier bonded with a group represented by the following general formula (1), adsorbs sulfur-containing compounds in fats and oils using an adsorbent whose volume change rate is 50% or less, and then separates the fats and fats and the adsorbents. A method for purifying oils and fats.
_{^{-R 1 -SO 3 - M + (}} 1)
(In the formula, R ¹ represents a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, and M represents a cation of at least one atom selected from Groups 10 and 11 of the periodic table. .) The method for purifying fats and oils according to claim 1, wherein R ¹ in the general formula (1) is a hydrocarbon group represented by the following general formula (2).
_{- (CH 2) n -C 6} H 4 - (2)
(In the formula, n is an integer of 0 to 9.) The method for purifying fats and oils according to claim 1 or 2, wherein M ⁺ in the general formula (1) is silver ion or palladium ion.   The method for purifying fats and oils according to any one of claims 1 to 3, wherein the carrier is one or more selected from inorganic compounds and crosslinked organic polymer compounds. A sulfur-containing compound adsorbent in fats and oils comprising a carrier to which a group represented by the following general formula (1) is bonded, and having a volume change rate of 50% or less.
_{^{-R 1 -SO 3 - M + (}} 1)
(In the formula, R ¹ represents a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, and M represents a cation of at least one atom selected from Groups 10 and 11 of the periodic table. .) The sulfur-containing compound adsorbent according to claim 5, wherein R ¹ in the general formula (1) is a hydrocarbon group represented by the following general formula (2).
_{- (CH 2) n -C 6} H 4 - (2)
(In the formula, n is an integer of 1 to 9.) The sulfur-containing compound adsorbent according to claim 5 or 6, wherein M ⁺ in the general formula (1) is a silver ion or a palladium ion.   The sulfur-containing compound adsorbent according to any one of claims 5 to 7, wherein the carrier is one or more selected from inorganic compounds and crosslinked organic polymer compounds.   The sulfur-containing compound adsorbent according to claim 5, which is used for removing sulfur-containing compounds in fats and oils.   An oil and fat and a carrier having the group represented by the general formula (1) according to claim 1 bonded thereto, and an adsorbent having a volume change rate of 50% or less are brought into contact with the adsorbent, and sulfur in the oil and fat is brought into contact with the adsorbent. A method for producing fats and oils with a reduced content of sulfur-containing compounds, comprising the step of refining fats and oils after adsorbing the containing compounds and separating the fats and oils and the adsorbent.