JPH08170092A - Removal of catalyst from fat and oil - Google Patents

Abstract

PURPOSE: To remove a catalyst from fat and oil at an extremely high removing ratio and keep residual activity of the removed catalyst at a high level, and enable a continuous treating by subjecting a specific treatment to fat and oil after finishing hydrogenation in the presence of a catalyst. CONSTITUTION: Fat and oil are subjected to hydrogenation reaction in the presence of a catalyst (preferably reduced Ni catalyst) and heated water (preferably water of 30-95 deg.C) or steam (preferably steam of 110-115 deg.C) in an amount of 0.5-10wt.% is added to the fat and oil at a constant pressure, preferably a pressure difference of 0.5-4kgf/cm<2> from the fat and oil, to obtain a mixture of the fat and oil, the catalyst and water. The mixture is kept or stirred for a prescribed time, preferably for 10-600sec to substitute the fat and oil attached to the catalyst with water. Then, water and the catalyst are separated from the mixture preferably by a centrifugation causing a three-layer separation. In the centrifugation, preferably a centrifugal force of 2000-10000G is applied to the system.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fat or oil such as a hardened oil by removing the catalyst contained in the fat or oil from which the hydrogenation reaction has been completed in the presence of the catalyst.

[0002]

2. Description of the Related Art At present, solid fats and oils of stable quality which can be used for margarine and shawning are produced by using a catalyst having extremely fine particles and high activity to form hydrogen atoms in double bonds depending on fatty acids contained in triglyceride in fats and oils. It is produced by increasing the melting point of fats and oils and reducing unsaturated fatty acids by carrying out a hydrogenation reaction by addition. The conventional catalyst removal method will be described below with reference to FIG.
The oil / fat containing the catalyst of fine particles after completion of the hydrogenation reaction in the reaction tank 1 of FIG. 1 is filtered using a filter or the like indicated by 3 in the figure immediately after being cooled to around 100 ° C. Although not shown, the catalyst was removed by gravity separation such as centrifugation. The removal of the catalyst by filtration is carried out by adding a filter aid such as diatomaceous earth in the precoat tank 2 and further filtering the catalyst with a filter press using a filter cloth or a leaf filter using mesh steel treated with a sealing agent. It moved to the machine 3 and was performing it, forming a filtration layer. Further, in the method of gravity separation such as centrifugation, the oil and fat containing the catalyst and cooled is put in a centrifuge in an untreated state and separated by utilizing the difference in specific gravity. The oil and fat from which the catalyst has been removed in this way is transferred to a decolorization reaction tank 4 which carries out a decolorization step (post-bleaching), and after passing a decolorizing agent such as white clay, it is decolorized and passed through a clay filter 5 which removes the white clay. Then, the oils and fats were manufactured through various processes.

[0003]

Therefore, there are various problems as described below. That is, in the conventional method of removing the catalyst by filtration using the oil and fat after cooling, the filter cloth or mesh steel cannot be continuously used, so that the batch method is inevitable, and the filter layer is removed each time. The filter aid had to be added to the fats and oils that had been freshly finished and cooled. In this filtration, the removal rate was less than 99% even if the sealing agent was added, and never reached a value of 99% or more. Even when the removed catalyst is reused, the catalyst contains a filter aid and a sealing agent, and the activity of the catalyst decreases due to the oxidation reaction due to the contact of the catalyst with the air. The activity was 40 to 70, and there were some that could not be reused, resulting in processing costs and manpower. Also in the case of centrifugation, the removal rate is 94 if the equipment such as separator, pump and sludge handling is installed and the centrifugation is performed.
%, Which is inferior to that of filtration and could not be actually used. In any case, with the conventional method for removing the catalyst in the oil or fat by gravity separation such as filtration or centrifugation with a filter aid, the oil or fat that has undergone the hydrogenation reaction cannot obtain a removal rate of 99% or more. The residual activity of the prepared catalyst is 7
It was as low as less than 0, and high cost was required for reuse. In addition, continuous treatment is not possible with filtration, and continuous treatment is possible with centrifugation, but there are advantages and disadvantages such as low removal rate.If this removal rate is low, it is necessary to decolorize in order to remove the remaining catalyst from fats and oils. However, since the decoloring step is always required, the manufacturing cost has increased.

Therefore, when the catalyst is removed from the fats and oils that have undergone such hydrogenation reaction, the removal rate is 99% or more, and the residual activity of the removed catalyst is as high as 70 or more.
Further, it is an object of the present invention to provide a method for removing a catalyst in a fat or oil, which enables continuous treatment and simplifies or does not perform a decoloring step performed after removing the catalyst.

[0005]

DISCLOSURE OF THE INVENTION As a result of earnest studies, the present invention has revealed that a catalyst removal rate of 99% or more and a catalyst removed by adding warm water or steam to fats and oils cooled after completion of hydrogenation reaction. The residual activity was as high as 70 or more, and further continuous treatment was possible, leading to the production of oils and fats without simplifying or passing through the decolorizing step performed after removing the catalyst. That is, the oil temperature after completion of the hydrogenation reaction in the presence of a catalyst is 30
A step of adding 0.5 to 10% by weight of heated water or steam to the oil / fat at a temperature of up to 95 ° C. at a constant pressure to obtain a mixture of the oil / fat, the catalyst, and water; This is due to the method of removing the catalyst in the oil and fat, which comprises a step of placing or stirring and a step of separating water and the catalyst from the mixture.

Further, in the method of removing the catalyst from the oil and fat using a nickel-supported catalyst as the catalyst, and in the step of adding heated water or steam at a constant pressure to obtain a mixture of the oil and fat and the catalyst and water, the oil and fat can be mixed with 0. In the step of removing the catalyst from the oil or fat by adding warm water or steam with a pressure difference of 5 to 4.0 kgf / cm ^{2, in} the step of performing standing or stirring for a certain period of time, the standing or stirring time is 10 to 600 seconds. The above problem can also be solved by a method for removing a catalyst in oil and fat, and a method for removing a catalyst in oil and fat, in which the step of separating the catalyst is performed by centrifugation. Also, three-layer separation can be used for centrifugation.

The fats and oils or fatty acids which are the subject of the present invention are selected from fish oil, soybean oil, rapeseed oil, palm oil, palm kernel oil, coconut oil, corn oil, sunflower oil, lard, beef tallow and the like. At least one or more substances are used as raw materials, and diglycerides, triglycerides, fatty acids and the like contained therein can also be used. Further, as the fatty acid, a saturated or unsaturated fatty acid such as palmitic acid, stearic acid, arachidonic acid, oleic acid, vaccenic acid, nervonic acid, linoleic acid, linolenic acid, sardine acid can be used. Therefore, the catalyst used for the hydrogenation reaction in the present invention is one that promotes the reaction without itself changing in the chemical reaction,
It is one for producing a solid oil and fat by carrying out a hydrogenation reaction of the oil and fat, and preferably a nickel carrier catalyst in which nickel fine particles are supported on a porous carrier such as diatomaceous earth is used. Examples of the nickel carrier catalyst include a reduced nickel catalyst and a nickel formate catalyst, but it is preferable to use a low cost reduced nickel catalyst because there are many kinds which are commercially available. The catalyst may be in the form of flakes or particles for facilitating the hydrogenation reaction. Further, the hydrogenation reaction is completed to bring the oil temperature to 30 to 95 ° C., and preferably the oil temperature is 30 to 8
It is desirable to use fats and oils at 0 ° C. That is, if the oil temperature, which is the temperature of the oil or fat, is less than 30 ° C., the oil or fat is often solidified, and heated water or steam cannot be added, and if it is higher than 95 ° C. Because of this, the oil temperature tends to be higher than 100 ° C., and the added water vapor easily evaporates from the fat and oil, so the above range is desirable. Further, the hydrogenation reaction in the present invention, hydrogen is generally added to a liquefied fat or oil to reduce the double bond or triple bond of unsaturated fatty acid contained in triglyceride in the fat or oil to give a saturated fatty acid. It means a reaction and is also called a curing reaction.

In the step of adding warm water or steam to oils and fats at a constant pressure, the amount to be added is
0.5 to 10% by weight, preferably 1 to 5 relative to fats and oils
% By weight can be added. That is, when the amount is less than 0.5% by weight, the amount added is small, and the removal rate value when the catalyst is removed from the fats and oils does not reach 99% or more. Since the temperature rises to 100 ° C. or higher and heated water or steam cannot be retained in the oil and fat, and the removal rate of the catalyst decreases, the above range is preferable. When water vapor is added to fats and oils, the fats and oils cool to water to form a mixture of fats and oils, catalysts and water. Further, by adding warm water or steam at a constant pressure, the warm water or steam can always be uniformly dispersed in the oil and fat. In particular, in the step of adding heated water or steam to obtain a mixture of oil / fat, catalyst and water, heated water or steam can be added to the oil / fat with a constant pressure difference. 0.5 to 4.0 kgf / cm ² (4.99032)
A pressure difference of 5 × 10 ^{4 to} 39.2266 × 10 ⁴ Pa) is desirable. That is, higher the difference between the pressures is less than 0.5 kgf / cm ^2, pressurized hot water or steam not uniformly dispersed in the oil, also when the pressure difference is higher than 4.0 kgf / cm ^2, the cost of equipment Therefore, the above range is preferable. After the hydrogenation reaction is completed, the oil temperature is 30-
The preferable temperature of the heated water or steam added to the oil and fat at 95 ° C is 30 to 95 ° C for heated water and 110 for steam.
The thing of -155 degreeC can be used.

Further, the constant time in the step of stirring or allowing the mixture to stir or stand for a certain period of time means the time until the oil or fat adhering to the catalyst in the mixture is replaced with water. That is, the above substitution can be performed by allowing the mixture of the fat and oil, the catalyst and the water to stand or stirring. The stationary means a state of being left without stirring. Further, in the case of stirring, it is preferable to gently stir without stirring such as bubbling or forming a vortex, and it is desirable that the flow rate be 10 to 100 cm / sec. Therefore, as a method for stirring, stirring is carried out by inserting a stirring means such as a propeller into the oil and fat, stirring is carried out by inserting a rotor enclosing a magnet like a magnetic stirrer, and a rotating disk like a washing machine is used. It can be carried out by the agitation used. Then, the step of stirring or standing is
It is preferably 10 to 600 seconds. If it is less than 10 seconds, the catalyst and water will not bond well, and if it is longer than 600 seconds, the processing capacity will be deteriorated, so the above range is preferable.

In the step of separating water and catalyst from the mixture, unnecessary water and catalyst are removed from the fat and oil. In particular, it can be carried out by a separation method capable of obtaining a removal rate of 99% or more. For this purpose, it is possible to use centrifugal separation, which is one of gravity separation, which can be continuously treated and is easy to reuse and regenerate the catalyst by separating it into three types of fats and oils, water and a catalyst. For the centrifugation, batch-type centrifugation or three-layer separation capable of continuous treatment can be used, and it is preferable to use three-layer separation. When separating by such centrifugation, it is desirable to give a centrifugal force of 2000 to 10000G.

[0011]

The hydrogenation reaction is terminated in the presence of the catalyst of the present invention, and the oil or fat having an oil temperature of 30 to 95 ° C.
5 to 10% by weight of warm water or steam is added at a constant pressure to obtain a mixture of fat and oil, a catalyst and water, the mixture is allowed to stand for a certain period of time or stirred, and water and the mixture are mixed. According to the method for removing the catalyst from the oil and fat, which comprises the step of separating the catalyst and the step, the oil and fat attached to the surface of the catalyst in the oil and fat is replaced with warm water or water produced by adding steam. . Then, the catalyst to which the water adheres is agglomerated by the aggregating action of the water to have a larger specific gravity with respect to the fat and oil, and is more likely to settle. Also,
The water added to the fats and oils dissolves many water-soluble components contained in the fats and oils to reduce impurities, and subsequent decolorization can be reduced or omitted.

Further, in the method for removing the catalyst in the fat or oil, a method for removing the catalyst in the fat or oil using a nickel-supported catalyst as a catalyst, or adding heated water or steam at a constant pressure to obtain a mixture of the fat and oil, the catalyst and water. In the step, a method for removing the catalyst in the oil or fat by adding heated water or steam to the oil or fat with a pressure difference of 0.5 to 4.0 kgf / cm ² , or in the step of performing the stationary time or stirring for a certain period of time, The method for removing the catalyst in the oil and fat with a stirring time of 10 to 600 seconds, the step of separating the catalyst adheres to the surface of the catalyst in the oil and fat by the method for removing the catalyst in the oil and fat that is performed by centrifugation. The oils and fats that exist replace the heating water or water produced by adding steam. Then, the catalyst to which the water adheres is agglomerated by the aggregating action of water to have a larger specific gravity with respect to the oil and fat, and is in a state of easily settling. In addition, the water added to the oil / fat dissolves the water-soluble components contained in the oil / fat to reduce impurities, and the subsequent discoloration can be reduced or omitted. Further, if the centrifugal separation uses a three-layer separation, it is possible to more efficiently separate the fat and oil, the catalyst and the water.

[0013]

EXAMPLES Details of the present invention will be described based on examples and figures. (Example 1) A reduced nickel catalyst (nickel: 20% by weight, carrier content: 20% by weight, oil: containing 60% by weight) was added to terminate the hydrogenation reaction, and 500 ppm of nickel was added to cool to 70 ° C. While adjusting the concentration of the rapeseed oil to 2.0% by weight, 3.0 kgf of oil and fat
Water vapor was added with a pressure difference of / cm ^{2 and} the mixture was allowed to stand for 30 seconds. Then, using a general-purpose disc type centrifuge (three-layer separator), separation was performed while applying a centrifugal gravity of 2000 G to obtain rapeseed oil as Example 1.

Comparative Example 1 In the reaction tank 1 shown in FIG. 1, the rapeseed oil cooled to 90 ° C. after completion of the hydrogenation reaction using the same nickel carrier catalyst as in Example 1 was transferred to the precoat tank 2. Then, 0.33% by weight of a filter aid composed of diatomaceous earth was added to the rapeseed oil and stirred to disperse the filter aid in the rapeseed oil. The oil and fat containing the filter aid was removed with a catalyst filter 3 having a mesh of 220 (trade name: Hunder Filter, manufactured by Ishikawajima Harima Heavy Industries Ltd.) to remove the nickel carrier catalyst to obtain rapeseed oil as Comparative Example 1. .

Comparative Example 2 As Comparative Example 2, Example 1 was used.
Using rapeseed oil cooled to 90 ° C. after completion of the same hydrogenation reaction as described above, separation was performed by a general-purpose disk type centrifuge (three-layer separator) while giving a centrifugal gravity of 8000 G. As rapeseed oil.

Therefore, in Example 1, Comparative Example 1 and Comparative Example 2, the residual rate of nickel contained in the fat and oil and the residual activity of the nickel carrier catalyst taken out were measured.

(Measurement of removal rate of catalyst) The content of nickel carrier catalyst in fats and oils is 2.2.9 of "Standard oil and fat analysis test method" published by Japan Oil Chemistry Inspection Association in 1972.
It was carried out according to page 4-77. That is, nickel
-Extracted as sodium diethyldithiocarbamate complex salt, and using an atomic absorption spectrophotometer (trade name: Z-6100, manufactured by Hitachi Ltd.) at a measurement wavelength of 232 nm to obtain Example 1, Comparative Example 1, and Comparative Example 2. The amount of nickel remaining was measured, and the amount of nickel remaining was subtracted from the addition amount of 500 ppm to calculate the amount removed. Then, the removal rate divided by the above-mentioned addition rate was multiplied by 100 to obtain the removal rate of the catalyst.

(Measurement of Residual Activity of Catalyst) Residual activity was measured by measuring the iodine value of palm olein oil with respect to the fresh fresh catalyst and the sludge containing the catalyst recovered from the fat and oil after completion of the hydrogenation reaction. The time required to complete the hydrogenation reaction by hydrogenating until (IV) reached 56 was determined, and the time required for the fresh catalyst was divided by the time required for sludge to be multiplied by 100 to obtain the residual activity. The conditions are shown in Table 1.

[0019]

[Table 1]

Then, the removal rate of the catalyst and the residual activity of the catalyst were measured for three kinds of Example 1, Comparative Example 1 and Comparative Example 2, and the results are shown in Table 2.

[0021]

[Table 2]

From Table 2, the nickel removal rate in Example 1 was 99.9%, while in Comparative Example 1 it was 98.8%.
Comparative Example 2 was 94.0%. Further, the residual activity was 80 or more in Example 1, while Comparative Example 1 and Comparative Example 2 had a residual activity of less than 70, and it was found that the Example was superior.

[0023]

EFFECTS OF THE INVENTION According to the method for removing a catalyst in oils and fats of the present invention according to claim 1, 2, 3, 4, 5 or 6, the oils and fats adhering to the surface of the catalyst in the oils and fats are heated with water. Alternatively, it is replaced with water produced by adding steam. Then, the catalyst to which the water adheres is aggregated by the aggregating action of water, the specific gravity is larger than that of the fat and oil, and the sedimentation due to gravity occurs to facilitate removal of the catalyst in the fat and oil, resulting in a removal rate of 99% or more. And the residual activity of the removed catalyst is always higher than 80, and it can be reused. Further, since the added water dissolves the water-soluble component contained in the fat and oil to reduce impurities and reduce the decolorizing load, the decolorizing agent can be reduced or the decolorizing step can be omitted, so that the manufacturing cost can be reduced. be able to.

[Brief description of drawings]

FIG. 1 is an explanatory view of a method for removing a catalyst from oil and fat using a conventional filter.

[Explanation of symbols]

 1. Reaction tank 2. Precoat tank 3. Catalyst filter 4. Decolorization reaction tank 5. Clay filter

Claims (6)

[Claims] 1. A fat or oil having an oil temperature of 30 to 95 ° C. which is obtained by terminating the hydrogenation reaction in the presence of a catalyst, and having a fat content of 0.5 to
A step of adding 10% by weight of warm water or steam at a constant pressure to obtain a mixture of oil and fat, a catalyst and water; a step of allowing the mixture to stand or stirring for a certain time; and water and the catalyst from the mixture. A method for removing a catalyst from oil and fat, which comprises a step of separating. 2. The method for removing a catalyst from oil and fat according to claim 1, wherein the catalyst is a nickel carrier catalyst. 3. In the step of adding heated water or steam at a constant pressure to obtain a mixture of fats and oils, a catalyst and water, there is a pressure difference of 0.5 to 4.0 kgf / cm ² with respect to the fats and oils. The method for removing a catalyst from oil or fat according to claim 1 or 2, wherein steam is added. 4. The method for removing a catalyst in oil or fat according to claim 1, 2 or 3, wherein the standing or stirring time is 10 to 600 seconds in the step of standing or stirring for a certain period of time. 5. The method for removing a catalyst from oil or fat according to claim 1, wherein the step of separating the catalyst from water is performed by centrifugation. 6. The method for removing a catalyst from oil and fat according to claim 5, wherein the centrifugation is a three-layer separation.