JP6478630B2 - Method for producing hardened oil - Google Patents

Description

  The present invention relates to a method for producing a hardened fat.

  Conventionally, hardened fats and oils that have been used as raw materials for margarine, shortening, frying fats and the like have been produced by hydrogenating animal and vegetable fats and oils in the presence of a catalyst. In recent years, it has been pointed out that trans acids contained in hardened fats and oils are nutritionally unfavorable, and many attempts have been made to reduce the amount of transacids in hardened fats and oils.

  In general, hardened fats and oils are produced in a reaction temperature range of about 120 ° C. to 220 ° C. and a hydrogen pressure of 0.01 MPa to 2.0 MPa. The amount of trans acid generated by hydrogenation is determined by the reaction temperature of hydrogenation. It is known that the pressure increases or decreases depending on the difference in the hydrogen pressure, the amount of catalyst, the amount of unsaturated fatty acid in the raw oil and fat used for hydrogenation, and the like. And as conditions for reducing the amount of transacid, lowering the reaction temperature of hydrogenation and raising the hydrogen pressure have been studied.

  However, in general, the method of producing a hardened fat using nickel as a catalyst has a problem that the reaction takes a long time because the activity of the catalyst is remarkably lowered when the reaction temperature is 140 ° C. or lower. Therefore, as a method for solving such problems, the amount of nickel catalyst used is 0.05 to 3.0 parts by mass with respect to 100 parts by mass of the raw oil and fat, and the hydrogenation reaction is performed at 80 to 130 ° C. A method has been proposed for obtaining a hardened oil and fat (Patent Document 1).

  By using a nickel catalyst having an activity that takes less than 40 minutes to reduce the iodine value by 10 at 120 ° C., a hydrogenation reaction is performed at 20 ° C. or more and less than 80 ° C., and an oil and fat containing an emulsifier is used. Thus, a method of performing a hydrogenation reaction at a low temperature below the melting point of the fat has also been proposed (Patent Document 2).

  Furthermore, the hydrogenation reaction system is such that the temperature of the hydrogenation reaction is in the range of 60 ° C. to 75 ° C., and the oil temperature increase rate per unit of iodine value that decreases in the hydrogenation reaction is 0.5 or less. There has been proposed a method of adjusting the amount of cooling heat and / or the amount of hydrogen supplied to the water (Patent Document 3).

JP 2006-320275 A JP 2010-1366 A JP 2011-162744 A

  However, the method described in Patent Document 1 in which nickel catalyst is used in a large amount such as several times to several tens of times the usual amount is expensive, and the reaction is performed at a low temperature for the purpose of further reducing the amount of transacid. Therefore, even if the amount of the catalyst is increased, the hydrogenation reaction takes a long time and is not always practical.

  In the method described in Patent Document 2, it is difficult to remove the emulsifier after curing because the fat contains an emulsifier. When used as a raw material oil because it contains an emulsifier, the use is limited and the versatility is poor. Is pointed out.

  The method described in Patent Document 3 requires that the hydrogenation reaction of fats and oils at a low temperature is performed under extremely strictly controlled conditions, and therefore is connected to a temperature sensor that senses the temperature in the reaction vessel and a hydrogen supply path. There is a need to control the operation of the circulation pump and the flow control valve by providing an electronic controller for providing a control signal based on temperature information and pressure information detected by these sensors. As described above, since the method described in Patent Document 3 requires a specific device structure, it is necessary to renovate an existing production line for hardened fats or oils or to establish a new production line. It has not always been easy to produce hardened oils and fats with reduced levels.

  This invention is made | formed in view of the above situations, and makes it a subject to provide the manufacturing method of the hardened oil and fat which can shorten hardening time at the time of hydrogenation reaction, and can improve productivity.

  In order to solve the above-described problems, the method for producing a hardened fat according to the present invention is characterized in that at least one selected from the group consisting of calcium hydroxide and an adsorbent is added to the raw material oil in the hardening step.

  In this method for producing hardened oils and fats, the adsorbent is preferably preliminarily treated with an alkaline solution.

  In this method for producing hardened oils and fats, it is preferable that the addition amount of at least one selected from the group consisting of the calcium hydroxide and the adsorbent is 0.005% by mass or more and 5% by mass or less with respect to the raw material oil.

  According to the present invention, it is possible to shorten the curing time during the hydrogenation reaction and improve productivity.

  The present invention is described in detail below.

  The method for producing a hardened fat according to the present invention is characterized in that in the hardening step, at least one selected from the group consisting of calcium hydroxide and an adsorbent is added to the raw material oil.

  The curing step in the present invention is a step of curing the raw material oil. As the raw material oil, it is possible to use oils and fats obtained by degreasing, deoxidizing and decoloring oils and fats extracted from plants and animal oils by pressing, heating and solvent, and oils and oils deodorized after purification.

  A hardening process adds at least 1 sort (s) chosen from the group which consists of a hardening catalyst, calcium hydroxide, and an adsorbent to raw material oil, and performs the hydrogenation reaction of fats and oils.

  For example, in the curing step, raw material oil to which at least one selected from the group consisting of a curing catalyst, calcium hydroxide and an adsorbent is added is put into a reaction kettle whose inside is evacuated, and heated and stirred. When the raw material oil reaches a predetermined temperature, heating is stopped, hydrogen of a required pressure (0.01 MPa to 2.0 MPa) is fed into the reaction kettle, a hydrogenation reaction is started, and hydrogen is added as desired. As the end point of the curing reaction, the end point of the reaction is determined using values such as iodine value, refractive index, melting point, and hydrogen consumption as a guide, hydrogen is blown, the inside of the reaction vessel is evacuated, and hydrogen is completely discharged from the reaction vessel. Exhaust. Then, it is cooled with circulating cooling water until the temperature of the fats and oils reaches around 90 ° C., and at least one selected from the group consisting of a catalyst in the fats and oils, added calcium hydroxide and an adsorbent using a filter press or the like. Remove.

  Oils and fats that have undergone such a curing step can undergo a decolorization step and a deodorization step.

  Examples of the raw material oil used for hydrogenation in the present invention include palm oil, palm kernel oil, coconut oil, soybean oil, rapeseed oil, corn oil, cottonseed oil, safflower oil, rice oil, olive oil, MCT (medium chain fatty acid) Containing oil), beef tallow, pork tallow and fish oil, fractionated oils thereof, transesterified oil, and the like. These may be used alone or in combination of two or more.

  The calcium hydroxide to be added to the raw material oil may be in the form of powder or a solution dissolved in a solvent such as water or alcohol, but is preferably in the form of powder from the viewpoint of workability during curing. By adding calcium hydroxide to the raw material oil, it is possible to shorten the hardening time of the raw material oil by about 20% to 40%.

  Examples of the adsorbent added to the raw material oil include acid clay, activated clay, bentonite, activated carbon, silica gel, silica / alumina, aluminum silicate, diatomaceous earth, and ion exchange resin. In particular, when acidic clay, activated clay, activated carbon, and silica gel are used, the causative substances that delay the curing reaction such as free fatty acids, phospholipids, sulfur compounds, unsaponifiable substances, soaps, proteins, oxidation products, water, oxygen, etc. It is presumed that the curing time can be shortened because any or a plurality of substances are adsorbed and the curing reaction is not inhibited.

  Active carbon includes powdered activated carbon, charcoal, coconut shell charcoal, coal (lignite, lignite, bituminous coal, anthracite, etc.), oil, etc. Examples thereof include granular activated carbon made from carbon, phenolic resin, etc., fibrous activated carbon made from rayon, acrylonitrile, coal pitch, petroleum pitch, phenolic resin, etc. as raw materials. As activation treatment, activation treatment with chemicals such as phosphoric acid, zinc chloride, sulfuric acid, calcium chloride, sodium hydroxide, potassium hydroxide, or activation treatment with gas such as water vapor, carbon dioxide, air, combustion gas, etc. Can be used. Moreover, as pH of activated carbon, the range whose pH is 3.0 or more and 12.0 or less is illustrated, for example. These activated carbons may be used alone or in combination of two or more. The shape of the activated carbon is not particularly limited, but powdered activated carbon is used because the dispersibility in the raw material oil is good and the contact area with the raw material oil becomes large and the curing time can be further shortened. It is preferable.

  As the white clay, an acidic white clay having a white viscosity mainly composed of kaolin or montmorillonite, or an activated white clay obtained by subjecting the acidic white clay to an activation treatment with sulfuric acid or hydrochloric acid can be used. Commercial products of acid clay include Mizuka Ace # 20, Mizuka Ace # 300, Mizuka Ace # 400, Mizulite (manufactured by Mizusawa Chemical Industry Co., Ltd.), and the like. NVZ, Galleon Earth NV, etc. (above made by Mizusawa Chemical Co., Ltd.) can be used.

  Examples of the ion exchange resin include phenol resin and polystyrene resin because of its heat resistance. These ion exchange resins may be used alone or in combination of two or more.

  These calcium hydroxide and adsorbent may be used alone or in combination of two or more.

  The adsorbent is preferably preliminarily treated with an alkaline solution. The alkaline solution treatment includes a step of removing the solvent by mixing the adsorbent with the alkaline solution and then filtering or centrifuging.

  Examples of the alkali used for the alkaline solution treatment include alkali metal, alkaline earth metal hydroxide, carbonate, alkoxide compound and the like. These may be used alone or in combination of two or more.

  As a solvent for dissolving the alkali, alcohol such as ethanol and methanol can be used in addition to water. These may be used alone or in combination of two or more.

  As a preferable density | concentration of an alkaline solution, the range of 0.01 mol / L-5 mol / L is illustrated, for example. Within this range, the fats and oils are hydrolyzed by alkali to produce soap, which is preferable without inhibiting the curing reaction.

  In the present invention, the addition amount of at least one selected from the group consisting of calcium hydroxide and an adsorbent is 0.005% by mass or more and 5% by mass or less, preferably 0.01% by mass or more and 4% by mass with respect to the raw material oil. %, More preferably in the range of 0.01% by mass to 3% by mass. If the addition amount is within the above range, the curing time of the raw material oil can be shortened by about 10 to 40%.

  The catalyst to be added to the raw material oil is not particularly limited as long as it is a curing catalyst for edible fats and oils approved by the Japanese Food Sanitation Law. Examples thereof include those in which nickel is supported on a porous carrier such as diatomaceous earth, or those that are further coated with oils and fats to form flakes, granules, and the like.

  As a commercially available nickel catalyst, SO-100A, SO-750R, SO-850 etc. of the flake nickel catalyst by Sakai Chemical Industry Co., Ltd. are illustrated, for example.

  The amount of the nickel catalyst used is preferably in the range of 0.05% by mass to 1.0% by mass with respect to the raw material oil.

  In the present invention, the reaction temperature at the time of hydrogenation using the above nickel catalyst is 220 ° C. or less, but it is necessary to carry out in a state where the raw oil and fat used for hydrogenation and the oil and fat after hydrogenation are melted. The hydrogenation is preferably performed at 60 ° C. or more and 220 ° C. or less in a state where the fats and oils are melted. The hydrogenation reaction is preferably carried out while stirring at a hydrogen pressure of 0.01 MPa to 2.0 MPa, a volume ratio of the oil phase to the hydrogen phase of 1: 1 to 1: 5, and within a range of 300 to 1500 rpm.

  Confirmation and judgment of the degree of progress of the hydrogenation reaction and completion of the hydrogenation reaction are made by measuring the iodine value (IV), refractive index, melting point, hydrogen consumption, etc. of fats and oils over time and using the measured values as a guide. Can be determined.

  It is exemplified that the iodine value is measured in accordance with 2.3.4.1-2013 (Wiis-cyclohexane method) of the standard fat analysis method (Japan Oil Chemical Society).

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The addition amount of the nickel catalyst is mass% with respect to the fats and oils. In addition, the addition amount of each component in Table 1-Table 4 shows the mass% with respect to fats and oils. The iodine value was measured in accordance with 2.3.4.1-2013 (Wiis-cyclohexane method) of the standard oil and fat analysis test method (Japan Oil Chemical Society).
<1> Test with alkali addition (Reference Example 1)
350 g of fish oil (iodine number 161) was added to a 1 liter autoclave, 0.3% by mass (1.05 g) of anti-oil (SO-750R manufactured by Sakai Chemical Industry Co., Ltd.) as a nickel catalyst, and a hydrogen pressure of 0.12 MPa was stirred. While stirring at several 750 rpm, a hydrogenation reaction was performed at 180 ° C., and the time required for the iodine value of the oil to fall to 70 was measured, and this time was taken as the curing time. In the test <1>, it was determined whether the curing times of the examples and comparative examples were shortened or extended based on the curing time of (Reference Example 1).
Example 1
In a 1 liter autoclave, 350 g of fish oil (iodine number 161), powdered calcium hydroxide (Ca (OH) ₂ ) (food additive grade manufactured by Kanto Chemical Co., Inc.), 0.01% by mass (0.035 g) Addition of 0.3% by mass (1.05 g) of nickel catalyst to oil, hydrogenation reaction at 180 ° C. while stirring at a hydrogen pressure of 0.12 MPa and a stirring speed of 750 rpm, and the iodine value of fats and oils decreased to 70 The time required to do this was measured, and this time was taken as the curing time.
(Example 2)
The curing time was measured in the same manner as in Example 1 except that the addition amount of Ca (OH) ₂ was changed to 0.025% by mass (0.0875 g) of oil.
(Example 3)
The curing time was measured in the same manner as in Example 1 except that the addition amount of Ca (OH) ₂ was changed to 0.05% by mass (0.175 g) of oil.
(Comparative Example 1)
Except for changing the alkali added to fish oil from Ca (OH) ₂ to 0.1% by mass (0.35 g) of powdered sodium carbonate (Na ₂ CO ₃ ) (manufactured by Kanto Chemical Co., Ltd.) The curing time was measured in the same manner as in Example 1.
(Comparative Example 2)
Except for changing the alkali added to fish oil from Ca (OH) ₂ to 0.1% by mass (0.35 g) of powdered calcium carbonate (CaCO ₃ ) (manufactured by Wako Pure Chemical Industries, Ltd.) The curing time was measured in the same manner as in Example 1.
(Comparative Example 3)
The alkali added to fish oil is changed from Ca (OH) ₂ to 0.1% by mass (0.35 g) of powdered potassium dihydrogen phosphate (KH ₂ PO ₄ ) (manufactured by Wako Pure Chemical Industries, Ltd.) Except for this, the curing time was measured in the same manner as in Example 1.
(Comparative Example 4)
Except for changing the alkali added to fish oil from Ca (OH) ₂ to 0.01% by mass (0.035 g) of powdered sodium methoxide (NaOCH ₃ ) (manufactured by Tokyo Chemical Industry Co., Ltd.) The curing time was measured in the same manner as in Example 1.
(Comparative Example 5)
Alkaline added to fish oil is Ca (OH) ₂ to 0.1 mass% (0.35 g) of powdered sodium hydroxide (granular sodium hydroxide (NaOH) (manufactured by Kanto Chemical Co., Ltd.)) in a mortar The curing time was measured in the same manner as in Example 1 except that it was changed to (obtained by grinding).
(Comparative Example 6)
Example 1 except that the alkali added to the fish oil was changed from Ca (OH) ₂ to powdered NaOCH ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.) of 0.1% by mass (0.35 g) of oil. Then, the curing time was measured.

[Evaluation of curing time reduction rate]
The curing time shortening rate (%) was calculated by the following formula.

Curing time shortening rate (%) = 100 − {(curing time of Example or Comparative Example) / (curing time of Reference Example 1)} × 100
Table 1 shows the time reduction rates of the examples and comparative examples.

In Examples 1-3, it became clear that hardening time shortened depending on the density | concentration of calcium hydroxide. On the other hand, the fish oil to which the alkali shown in Comparative Examples 1 and 2 was added and the fish oil to which the acid shown in Comparative Example 3 was added showed an extension of the curing time as compared to the reference example without addition. Moreover, although the fish oil which added the alkali shown to Comparative Examples 4-6 performed hardening reaction for 80 minutes like a reference example, fish oil was liquid and the hydrogenation reaction did not advance. Therefore, it became clear that the hardening time can be shortened by about 20% to 40% by adding calcium hydroxide to the raw material oil.
<2> Test by curing temperature (Reference Example 2)
The curing time was measured in the same manner as in Reference Example 1 except that the curing temperature was changed to 190 ° C.
(Reference Example 3)
The curing time was measured in the same manner as in Reference Example 1 except that the curing temperature was changed to 195 ° C. In the test of <2>, whether the curing time was shortened or extended was determined for Example 4 in Reference Example 2 and Example 5 on the basis of the curing time in Reference Example 3.
Example 4
The curing time was measured in the same manner as in Example 1 except that the curing temperature was changed to 190 ° C.
(Example 5)
The curing time was measured in the same manner as in Example 1 except that the curing temperature was changed to 195 ° C.
[Evaluation of curing time reduction rate]
The curing time shortening rate (%) was calculated by the following formula.

Curing time shortening rate (%) = 100 − {(curing time of example) / (curing time of reference example)} × 100
Table 2 shows the time reduction rate of each example.

From Examples 4 and 5, calcium hydroxide was confirmed to have a time shortening effect even in a high temperature range where the hydrogenation reaction rate is relatively fast (curing time is short). Further, the curing time of Reference Example 3 having no addition and a curing temperature of 195 ° C. was 54 minutes, whereas the curing time of Example 4 in which calcium hydroxide was added and the curing temperature was 190 ° C. was 45 minutes. That is, it was confirmed that the curing time was shortened by adding calcium hydroxide rather than increasing the curing temperature by 5 ° C. From this, it was suggested that the curing time shortening rate is higher when calcium hydroxide is used than when the curing temperature is increased.
<3> Test with adsorbent (Reference Example 4)
350 g of fish oil (iodine value 161) and 0.3% by mass of nickel catalyst are added to a 1 liter autoclave, hydrogenation reaction is performed at 180 ° C. while stirring at a hydrogen pressure of 0.5 MPa and a stirring speed of 750 rpm. The time required for the iodine value to decrease to 70 was measured, and this time was taken as the curing time. In the test <3>, whether the curing time of the example was shortened or extended was determined based on the curing time of Reference Example 4.
(Example 6)
Add 350 g of fish oil (iodine number 161), 3% by mass of activated carbon GLC-P (manufactured by Kuraray Chemical Co., Ltd.) (10.5 g) and 0.3% by mass of nickel catalyst to oil in a 1 liter autoclave. While stirring at a hydrogen pressure of 0.5 MPa and a stirring speed of 750 rpm, a hydrogenation reaction was carried out at 180 ° C., and the time required for the iodine value of the oil to fall to 70 was measured, and this time was taken as the curing time.
(Example 7)
The curing time was measured in the same manner as in Example 6 except that the adsorbent was changed from GLC-P to S-W50 (manufactured by Phutamura Chemical Co., Ltd.) which is activated carbon.
(Example 8)
The curing time was measured in the same manner as in Example 6 except that the adsorbent was changed from GLC-P to Wako Gel C-200 (hereinafter referred to as silica gel, manufactured by Wako Pure Chemical Industries), which is silica gel.
Example 9
The curing time was measured in the same manner as in Example 6 except that the adsorbent was changed from GLC-P to GALLEON EARTH V2 (hereinafter referred to as V2; manufactured by Mizusawa Chemical Co., Ltd.), which is an activated clay.
(Example 10)
The curing time was measured in the same manner as in Example 6 except that the adsorbent was changed from GLC-P to MIZUKA-ACE # 300 (hereinafter referred to as MA300, manufactured by Mizusawa Chemical Co., Ltd.), which is acidic clay.
[Evaluation of curing time reduction rate]
The curing time shortening rate (%) was calculated by the following formula.

Curing time shortening rate (%) = 100 − {(curing time of example) / (curing time of reference example)} × 100
Table 3 shows the curing time reduction rate of each example.

In Examples 6 to 10, it was confirmed that the curing time was reduced by about 10% to 40% when any adsorbent was added.
<4> Adsorbent, Adsorbent Treated with Alkaline Solution, and Test Using Combination of Calcium Hydroxide and Adsorbent <4> In the test of Reference Example 1, the curing time of the example was shortened or extended based on the curing time of Reference Example 1. Judged whether to do.
(Example 11)
Into a 1 liter autoclave, 350 g of fish oil (iodine number 161), activated carbon PW-D (pH 8.8, manufactured by Kuraray Chemical Co., Ltd.) 1 mass% of oil, nickel catalyst 0.3 mass% of oil, and hydrogen While stirring at a pressure of 0.12 MPa and a stirring speed of 750 rpm, a hydrogenation reaction was performed at 180 ° C., and the time required for the iodine value of the oil to fall to 70 was measured, and this time was taken as the curing time.
(Example 12)
The curing time was measured in the same manner as in Example 11 except that the amount of PW-D added was changed to 3% by mass with respect to oil.
(Example 13)
The same as in Example 11 except that the adsorbent was changed from PW-D to Plum Bee IE Mark Activated Carbon with 3% by mass of oil (hereinafter referred to as Plum Bee IE Mark, pH 9.7 manufactured by Ohira Chemical Industry Co., Ltd.). Then, the curing time was measured.
(Example 14)
Example 11 except that the adsorbent was changed from PW-D to NORIT HB-PLUS with 0.1% by mass of oil (hereinafter referred to as HB-PLUS, pH 10.1 manufactured by Cabot Norit Japan). Similarly, the curing time was measured.
(Example 15)
Add 5 volumes of 1 mol / L (1N) sodium hydroxide / ethanol solution to HB-PLUS in advance, stir for 3 hours at room temperature and normal pressure, filter, dry at 70 ° C. for 60 minutes, and remove the solvent for alkali. Solution processed. The curing time was measured in the same manner as in Example 11 except that the adsorbent was changed from PW-D to HB-PLUS (pH 11.9) treated with an alkaline solution of 0.1% by mass of oil.
(Example 16)
Example except that the adsorbent added to the raw material oil was changed from PW-D to HB-PLUS with 0.1% by mass of oil and 0.05% by mass of powdered Ca (OH) ₂ was added. The curing time was measured in the same manner as in No. 11.
[Evaluation of curing time reduction rate]
The curing time shortening rate (%) was calculated by the following formula.

Curing time shortening rate (%) = 100 − {(curing time of example) / (curing time of reference example)} × 100
Table 4 shows the curing time reduction rate of each example.

  In Examples 11 to 14, it was confirmed that the curing time was shortened by about 10% to 15% when any adsorbent was added. Further, when Examples 15 to 16 and Example 14 are compared, it is possible to cure more than the untreated adsorbent alone by treating the adsorbent with alkali in advance, or using adsorbent and calcium hydroxide together. It was confirmed that the shortening rate increased. That is, it was suggested that the curing time shortening rate is further improved by increasing the pH of the activated carbon or by allowing calcium hydroxide to coexist in the curing reaction system.

Claims (4)

In the curing step, at least one selected from the group consisting of a catalyst, calcium hydroxide and an adsorbent is added to the raw material oil,
The adsorbent is at least one selected from the group consisting of activated carbon, silica gel, diatomaceous earth, and ion exchange resin,
At least 1 sort (s) chosen from the group which consists of the said calcium hydroxide and adsorption agent does not carry | support the said catalyst, and adds separately with the said catalyst, The manufacturing method of the hardened fats and oils characterized by the above-mentioned . The method for producing a hardened fat according to claim 1, wherein the adsorbent is at least one selected from the group consisting of activated carbon and silica gel. In the curing step, at least one selected from the group consisting of a catalyst, calcium hydroxide and an adsorbent is added to the raw material oil,
The adsorbent has been previously treated with an alkaline solution ,
At least 1 sort (s) chosen from the group which consists of the said calcium hydroxide and adsorption agent does not carry | support the said catalyst, and adds separately with the said catalyst, The manufacturing method of the hardened fats and oils characterized by the above-mentioned . Wherein the at least one additive amount selected from the group consisting of calcium hydroxide and sorbent, one of claims 1 to equal to or less than 0.005 mass% to 5 mass% with respect to the feed oil 3 The manufacturing method of hardened oil and fat as described in any one of Claims .