JPH07116464B2 - Method for separating oily substances into various melting point components - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for separating an oily substance composed of various melting point components such as fats and oils, fatty acids, etc. into various melting point components in order to make effective use thereof. It is a thing.

[Conventional technology and problems]

In order to effectively utilize oily substances consisting of various melting point components,
Separation into components having various melting points has been conventionally performed, and various methods have been studied. The most basic method is the wintering method. This method is the cheapest in terms of cost, but the solid-liquid separation efficiency is extremely poor, such as when a large amount of liquid components are mixed into the solid components, and the solid component content increases the viscosity and further Since it solidifies, the solid-liquid separation operation becomes difficult and there is a drawback that its range of use is narrow, and it cannot be used as a separation method especially for the purpose of separating solid components.

A solvent fractionation method using a solvent is known as a method for improving this drawback. This method can reduce the viscosity by lowering the solid component ratio by using a solvent, so it can be used even if the solid component content is high, and by washing with a solvent, high quality with little mixing of liquid components It is an effective fractionation method as a method of obtaining a solid component, such as being able to obtain the solid component, but on the contrary, since a part of the solid component dissolves in the solvent and remains on the liquid component side, the quality of the liquid component Is low, the separation temperature is low because a solvent is used, a solvent recovery device is required, and it is necessary to use an explosion-proof device as a whole. It has the drawback of being very expensive.

In addition to these two separation methods, a wetting agent fractionation method using a wetting agent (surfactant) is known (Japanese Patent Publication No. 31-9986).
Issue). In this method, in a mixed state of a solid component and a liquid component, a wetting agent aqueous solution (in many cases, an inorganic electrolyte is coexistent for the purpose of preventing emulsification) is applied to transfer and suspend the solid component in the wetting agent aqueous solution. Separates the light phase consisting of a liquid component and two phases consisting of an aqueous phase in which a solid component is suspended and having different specific gravities. The two phases are separated using a centrifuge method and then suspended from the aqueous phase part. The starting oily substance is separated into a solid component and a liquid component by separating the solid component. This wetting agent fractionation method is cheaper in cost than the solvent fractionation method, and since mixing of the solid component into the liquid component unlike the solvent fractionation method does not easily occur, a high quality liquid component is obtained, etc. Although it is used for the separation of palm oil (separation of palm stearin and palm olein), it cannot sufficiently prevent the mixing of liquid components into solid components, so the solid-liquid separation efficiency is not sufficient and the solvent fractionation method is used. It is only in the middle of the wintering method and the solvent separation method in terms of cost, quality and separation efficiency, such as not obtaining a solid component of such high quality, and it is still a sufficient separation method. I can not say.

As described above, the currently known fractionation methods have their respective drawbacks and are properly used according to the purpose, but in order to highly effectively utilize the oily substance by dividing it into various melting point components, There is a demand for a fractionation method capable of obtaining high-quality liquid components and solid components in good yield and at low cost.

[Means for solving problems]

In order to develop a separation method in which a high-quality liquid component and solid component can be obtained from an oily substance composed of various melting point components with high yield and at low cost, the inventors have made mutual mixing of the solid component and the liquid component as much as possible. As a result of diligent studies on a method of separating a wetting agent to be suppressed, a solid component crystallized while precipitating part or all of the solid component as crystals in a water / oil type emulsion system in the presence of a wetting agent is a dispersed phase. Transfer and suspend in water droplets,
By aging (aggregating / growing) the solid component in water droplets as the dispersed phase, it was found that the solid component with less mixing of the liquid component can be concentrated in the aqueous phase, and the first invention was completed.

That is, the first invention of the present invention divides an oily substance composed of various melting point components into two phases, a light phase composed of a liquid component and a heavy phase composed of an aqueous phase in which a solid component is suspended by using a wetting agent. In the method of separating the starting oily substance into components having different melting points by separating the solid components from the suspension aqueous phase, a part or all of the solid components may be mixed with water / water in the presence of a wetting agent.
The solid component crystallized while precipitating as crystals in an oil-based emulsion system is transferred to and suspended in water droplets that are the dispersed phase, and the solid components are aged (aggregated and grown) in the water droplets that are the dispersed phase, then separated The present invention relates to a method for separating an oily substance into various melting point components.

According to the wetting agent fractionation method of the first invention of the present invention, the solid component is crystallized in the liquid component of the continuous phase which is the precipitating matrix, and then rapidly transferred to and suspended in the water droplets which are the dispersed phase, and the continuous phase. In the state of being isolated from the liquid component of (i.e., a double emulsion system of crystal / water / oil type as a system), aging (aggregation / growth) is carried out. Therefore, the crystal during aging (aggregation / growth) does not undergo secondary contact with the liquid component of the continuous phase, which causes a decrease in the purity of the solid component, and is maintained in high purity in the water droplets.
As described above, by performing crystallization and aging in a water / oil type emulsion system, a high-purity solid component is concentrated in water droplets, so that excellent separation efficiency can be obtained.

However, among the conventional wetting agent fractionation methods, Japanese Patent Publication Nos. 31-9986 and 59-21919 or JP-A-5-21919.
No. 0-94003, a method of crystallizing in a non-emulsifying system, that is, after the solid component to be separated is sufficiently crystallized and aged (aggregation / growth) in a liquid component as a precipitation matrix. In the method of transferring and suspending crystals in an aqueous phase by treating with a moistening agent aqueous solution, crystallization and aging (aggregation / growth) are performed in a liquid component, and therefore, crystals and The liquid component is contained in the intercrystalline matrix,
In that state, since it is transferred to the aqueous phase and suspended, mixing of the liquid component into the solid component occurs, the purity of the solid component decreases, and at the same time, the separation efficiency also decreases.

As another method, a method of cooling and crystallizing in an emulsion system in the presence of a wetting agent is also known (Japanese Patent Publication No. 39-7911, Japanese Patent Publication No. 46-35272, Japanese Patent Publication No. 51-15048). And JP-B-58-24480), all of these methods are oil / water emulsion systems, and the purpose of use is to increase the cooling efficiency, and the separation efficiency is hardly improved. The reason is not clear, but it can be considered as follows. That is oil /
In the water-based emulsion system, the solid component is crystallized in oil droplets as a dispersed phase, transferred and suspended in the aqueous phase as a continuous phase, and aged in the aqueous phase. The fact that the aging (aggregation / growth) of the crystal of the solid component is performed in the aqueous phase is the same in both the water / oil type emulsion system and the oil / water type emulsion system, but the emulsion system after crystal precipitation is When the first emulsion system is a water / oil type emulsion system, it becomes a double crystal / water / oil type emulsion system, and the crystals and liquid components are completely separated by water, whereas the first emulsion system is The oil / water emulsion system is (oil + crystal) / water emulsion system, so the crystals re-associate (secondary contact) with the oil droplets that are simultaneously dispersed during aging (aggregation / growth), resulting in a liquid component. It is considered that the liquid component is mixed with the solid component to lower the purity of the solid component and the separation efficiency is deteriorated as compared with the crystallization in the water / oil type emulsion system. Moreover, this tendency becomes more remarkable as the amount of the solid component increases.

As a method of suppressing the secondary contact with the liquid component during the ripening (coagulation / growth) of the crystal in the water phase in such an oil / water type emulsion system, the amount of the wetting agent is extremely increased and the crystal is aggregated. -A method of suppressing the growth is also conceivable, but in this case, a very large amount of the wetting agent is required, and the separation cost becomes high.
Also, depending on the type of wetting agent, the emulsion stability of the liquid component may be too good, and the separation from the aqueous phase may be poor.

As described above, the first aspect of the present invention is such that cooling crystallization and aging (coagulation / growth) in a water / oil type emulsification system in the presence of a wetting agent, which has never been used in the past, are performed. It has been found that it becomes possible to obtain a high-purity solid component that could not be obtained by the wetting agent method, and the separation efficiency is remarkably improved.

The solid component concentrated in the water droplets of the dispersed phase, when the ratio of the solid component is small, is divided into a light phase composed of a liquid component and a heavy phase composed of an aqueous phase in which the solid component is suspended by simply performing centrifugation. It can be easily separated. However, when the amount of the solid component is large, the amount of the liquid component which is the continuous phase may relatively decrease at the stage when the ripening (aggregation / growth) of the crystals is completed, and the viscosity may increase to a cream. This cream-like thickened emulsion does not easily separate into two phases, and therefore it is necessary to lower the viscosity of the system and combine the water droplets in order to separate the liquid component and the solid component. As a method of lowering the viscosity of the system, addition of a solvent or the like can be considered, but there is a problem in cost.

The present inventors simply separated the creamy thickened water / oil type emulsion into two phases and separated two phases, a light phase consisting of a liquid component and a heavy phase consisting of an aqueous phase in which a solid component was suspended. As a result of diligent study on the method of obtaining, the result of sufficient aging (aggregation / growth) is that re-association with oil droplets as a dispersed phase does not occur even under an oil / water type emulsification system, and liquid components to solid components It was found that entrainment did not occur, and therefore the purity of solid components and the separation efficiency were not degraded. As a result, water or an aqueous wetting agent solution is added to a water / oil type emulsion containing a sufficiently aged (aggregated / grown) crystal and thickened in a creamy form to invert the phase into an oil / water type emulsion system. As a result, the continuous phase becomes an aqueous phase, the viscosity of the system becomes low, and at the same time, coalescence of oil droplets that became a dispersed phase easily occurs, and a light phase consisting of a liquid component and a heavy phase consisting of an aqueous phase in which a solid component is suspended Can be easily separated into two phases, and the purity of the solid components does not decrease,
It was found that good separation efficiency was maintained, and the second invention of the present invention was completed.

In other words, the second invention of the present invention is the same as the first invention.
After the solid component crystallized while precipitating as crystals in an oil-based emulsion system is transferred / suspended in water droplets as a disperse phase, and the solid components are aged (aggregated / growth) in the water droplets as a disperse phase,
Inverting the system into an oil / water type emulsion system to separate a light phase composed of a liquid component and a heavy phase composed of an aqueous phase in which a solid component is suspended, and an oily substance having various melting points. It is about the method of separating into.

By using the separation method in the wetting agent fractionation according to the second aspect of the present invention, it is possible to obtain a high quality solid component and liquid component simultaneously and efficiently even when the solid component ratio is large.

As described above, by using the wetting agent fractionation method of the present invention, as compared with the conventional wetting agent fractionation method, a high-purity solid component can be obtained, at the same time, the yield of the liquid component is good, and the conventional solvent fractionation method can be used. Compared with the conventional fractionation method, the wetting agent fractionation method of the present invention can obtain a solid component of comparable quality and yield, and at the same time, a higher quality (low melting point) liquid component with substantially the same yield. It is a very good separation method.

The wetting agent fractionation method of the present invention comprises crystallization and aging in a water / oil type emulsion system in the presence of a wetting agent to concentrate high-purity solid components in water droplets as a dispersed phase, and if necessary, It is characterized by inversion by oil / water type emulsion system before separation.
For that purpose, a wetting agent that is easy to make a water / oil type emulsion system and has the action of transferring and suspending solid components in the water phase and that can easily undergo phase inversion is required. Surfactants with a more suitable balance of hydrophilicity and lipophilicity than those with high water solubility such as alkyl sulfonates, alkylbenzene sulfonates, alcohol sulfates and soaps, such as HLB (lipophilic Hydrophilic balance) 7
The front and rear surface active agents are preferable, but are not particularly limited. For example, polyglycerin fatty acid ester, glycerin fatty acid ester, sorbitol or sorbitan fatty acid ester, polyoxyethylene adducts thereof, polyoxyethylene alcohol ether and the like can be used.

〔Example〕

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. All parts and% in the examples are by weight.

Example 1 Polyoxyethylene lauryl ether (number of moles of ethylene oxide added: 4) per 100 parts of palm oil having an iodine value of 51.0
Add 8 parts and 80 parts water and stir at 50 ° C for 4 hours
It was cooled to 25 ° C., crystallized, and aged at 25 ° C. for 1 hour. The emulsion system at this time was a water / oil type emulsion system. Then, this emulsion was centrifuged to separate a light phase composed of a liquid component and an aqueous phase in which a solid component was suspended to obtain a liquid component. The obtained suspended aqueous phase was heated to 80 ° C. to melt the solid component and then centrifuged again to obtain a solid component.

The yields and iodine values of the obtained liquid and solid components are shown in Table 1.
It was shown to.

Comparative Example 1 Polyoxyethylene lauryl ether (4 moles of ethylene oxide added) based on 100 parts of palm oil used in Example 1
8 parts and 200 parts of water were added, cooled and crystallized from 50 ° C. to 25 ° C. over 4 hours with stirring, and aged at 25 ° C. for 1 hour.
The emulsion system at this time was an oil / water emulsion system. Next, this emulsion was centrifuged to separate a light phase composed of a liquid component and an aqueous phase in which a solid component was suspended to obtain a liquid component. The obtained suspended aqueous phase was heated to 80 ° C. to melt the solid component and then centrifuged again to obtain a solid component.

The yields and iodine values of the obtained liquid and solid components are shown in Table 1.
It was shown to.

Comparative Example 2 100 parts of palm oil used in Example 1 was cooled and crystallized from 50 ° C. to 25 ° C. over 4 hours with stirring, and aged at 25 ° C. for 1 hour. 3% by weight of magnesium sulfate and 0.5% by weight of sodium dodecylsulfate were added to the oily slurry containing the obtained crystals.
An emulsion of palm oil was prepared by adding 200 parts of an aqueous solution containing 25 ° C and mixing well. The emulsion system at this time was an oil / water emulsion system. Next, this emulsion was centrifuged to separate a light phase composed of a liquid component and an aqueous phase in which a solid component was suspended to obtain a liquid component. The obtained suspended aqueous phase was heated to 80 ° C. to melt the solid component and then centrifuged again to obtain a solid component.

The yields and iodine values of the obtained liquid and solid components are shown in Table 1.
It was shown to.

As shown in Table 1, Example 1 in which cooling crystallization and aging were performed in a water / oil type emulsion system was cooled in an oil / water type emulsion system, although the same wetting agent was used in the same amount. Compared with Comparative Example 1 in which crystallization and aging were performed and Comparative Example 2 in which cooling crystallization and aging were performed with oil alone and then a wetting agent treatment was performed, the yield of liquid components having almost the same iodine value was It can be seen that the solid component which is high and has high separation efficiency at the same time has a small iodine value and a small amount of liquid component mixed therein, and thus has excellent separation efficiency.

Example 2 To 100 parts of palm olein having an iodine value of 55.0, 5 parts of caprylic acid monoglyceride and 50 parts of water were added, and the mixture was cooled and crystallized from 50 ° C. to 12 ° C. over 10 hours with stirring.
Time aged. The emulsion system at this time was a water / oil type emulsion system. Next, 150 parts of water at 12 ° C was added to this emulsion with stirring, and the mixture was stirred at 12 ° C for 10 minutes. At this time, the emulsion system was phase-inverted into an oil / water emulsion system. The phase-inverted emulsion was centrifuged to divide it into a light phase composed of a liquid component and an aqueous phase in which a solid component was suspended to obtain a liquid component. The resulting suspended aqueous phase is 80
After heating to ℃ to melt the solid component, it was centrifuged again to obtain a solid component.

The yields and iodine values of the obtained liquid and solid components are shown in Table 2.
It was shown to.

Comparative Example 3 To 100 parts of palm olein used in Example 2, 5 parts of caprylic acid monoglyceride and 200 parts of water were added and stirred under stirring.
Crystallized by cooling from 12 ℃ to 12 ℃ over 10 hours, then 12 ℃
It was aged for 5 hours. At this time, the emulsion system was an oil / water emulsion system. Next, this emulsion was centrifuged to separate a light phase composed of a liquid component and an aqueous phase in which the solid component was suspended to obtain a liquid component. The obtained suspension aqueous phase was heated to 80 ° C. to melt the solid component and then centrifuged again to obtain a solid component.

The yields and iodine values of the obtained liquid and solid components are shown in Table 2.
It was shown to.

Comparative Example 4 100 parts of palm olein used in Example 2 was cooled and crystallized from 50 ° C. to 12 ° C. over 10 hours with stirring, and further aged for 5 hours. 3% by weight of magnesium sulfate and sodium decyl sulfate were added to the slurry oil containing the obtained crystals.
200 parts of a 12 ° C. aqueous solution containing 0.5% by weight was added and mixed well to prepare an emulsion. The emulsion system at this time was an oil / water emulsion system. Next, this emulsion was centrifuged to separate a light phase composed of a liquid component and an aqueous phase in which the solid component was suspended to obtain a liquid component. The obtained suspended aqueous phase was heated to 80 ° C. to melt the solid component and then centrifuged again to obtain a solid component.

The yields and iodine values of the obtained liquid and solid components are shown in Table 2.
It was shown to.

As shown in Table 2, cooling / crystallization and aging were performed in a water / oil type emulsion system, and after phase inversion to the oil / water type emulsion system, separation into a liquid phase and a water phase in which a solid component was suspended was carried out. In Example 2, the same wetting agent was used in the same amount, but Comparative Example 3 in which cooling crystallization and aging were performed from the beginning in an oil / water emulsion system, and after cooling crystallization and aging were performed in oil alone. The yield of the liquid component having substantially the same iodine value as that of Comparative Example 4 treated with the wetting agent is high, and the solid component obtained at the same time is a high-quality solid component having a small iodine value and less mixing of the liquid component. From this, it can be seen that it has excellent separation efficiency.

Example 3 Oil 100 of liquid component (iodine number 65.0) obtained in Example 2
6 parts of caprylic acid monoglyceride and 60 parts of water were added to each part, and the mixture was cooled and crystallized from 30 ° C. to 3 ° C. over 10 hours with stirring, and aged at 3 ° C. for 5 hours. At this time, the emulsifying system is water /
It was an oil type emulsion system. Next, 140 parts of water at 3 ° C. was added to this emulsion with stirring, and the mixture was stirred at 3 ° C. for 10 minutes. At this time, the emulsion system was phase-inverted into an oil / water emulsion system. The phase-inverted emulsion was centrifuged to divide it into a light phase composed of a liquid component and an aqueous phase in which a solid component was suspended to obtain a liquid component. The obtained suspended aqueous phase was heated to 80 ° C. to melt the solid component and then centrifuged again to obtain a solid component.

Table 3 shows yields of the obtained liquid component and solid component, iodine value, and low temperature resistance of the liquid component at 5 ° C (days until crystal precipitation).

Comparative Example 5 Oil 100 of liquid component (iodine number 64.4) obtained in Comparative Example 4
The mixture was cooled and crystallized from 30 ° C. to 3 ° C. over 10 hours with stirring, and further aged at 3 ° C. for 5 hours. An emulsion was prepared by adding 200 parts of an aqueous solution containing 3% by weight of magnesium sulfate and 0.5% by weight of sodium decylsulfate at 3 ° C. to the obtained oil in the form of a slurry containing crystals and mixing them well. The emulsion system at this time was an oil / water emulsion system. Next, this emulsion was centrifuged to separate into a light phase consisting of a liquid component and an aqueous phase in which a solid component was suspended to obtain a liquid component. The obtained suspended aqueous phase was heated to 80 ° C. to melt the solid component and then centrifuged again to obtain a solid component.

Table 3 shows yields of the obtained liquid component and solid component, iodine value, and low temperature resistance of the liquid component at 5 ° C.

Comparative Example 6 Oil 100 of liquid component (iodine value 65.0) obtained in Example 2
To 200 parts of acetone, add 200 parts of acetone to dissolve uniformly at 30 ° C, then cool from 30 ° C to -5 ° C over 15 hours, and then cool to -5 ° C.
After aging for 2 hours, the solid component was crystallized. The precipitated crystals were separated by filtration, washed with 50 parts of acetone at −5 ° C., and the crystal parts were collected and the solvent was removed to obtain a solid component. The filtrate from which the crystal part was filtered off and the washed filtrate were mixed and then desolvated to obtain a liquid component.

Table 3 shows yields of the obtained liquid component and solid component, iodine value, and low temperature resistance of the liquid component at 5 ° C.

As shown in Table 3, cooling / crystallization and aging were performed in a water / oil type emulsification system, and after phase inversion to the oil / water type emulsification system, the liquid component and the solid component suspended aqueous phase were separated. In Example 3, the yield of the liquid component having substantially the same iodine value was significantly higher than that in Comparative Example 5 in which the oil was cooled and crystallized and matured and then the wetting agent was treated. The solid component is a high-quality solid component having a small iodine value and little mixing of the liquid component, and its separation efficiency is almost the same as that of the solvent fractionation method (Comparative Example 6) which is said to have the highest efficiency in the past. Separation efficiency (yield and iodine value).

Furthermore, the low temperature resistance of the liquid component at 5 ° C. is far superior to that of Comparative Example 6 showing the same separation efficiency, and the wetting agent fractionation method of the present invention is a conventional fractionation method (conventional wetting agent fractionation method and conventional wetting agent fractionation method). It can be seen that the method is an excellent fractionation method in which not only separation efficiency but also high quality solid and liquid components are obtained compared to the solvent fractionation method).

〔The invention's effect〕

According to the first method of the invention by the present inventors, the solid component of the oily substance is crystallized in the liquid component of the continuous phase which is the precipitating matrix, and then immediately transferred to and suspended in the water droplets which are the dispersed phase, and continuously. It is aged (aggregated and grown) in a state separated from the liquid component of the phase (that is, the system is a crystal / water / oil type double emulsion system). Therefore, the crystal during aging (aggregation / growth) does not cause secondary contact with the liquid component of the continuous phase, which causes a decrease in the purity of the solid component, and is maintained in high purity in the water droplets. As described above, by performing crystallization and aging in a water / oil type emulsion system, a high-purity solid component is concentrated in water droplets, so that excellent separation efficiency can be obtained.

The solid component concentrated in the water droplets of the dispersed phase is separated into a light phase composed of a liquid component and a heavy phase composed of an aqueous phase in which the solid component is suspended by simply centrifuging when the ratio of the solid component is small. However, when the amount of the solid component is large, the amount of the liquid component that is the continuous phase may relatively decrease at the stage when the ripening (aggregation / growth) of the crystals is completed, and the viscosity may increase to a cream. This cream-like thickened emulsion does not easily separate into two phases, but
Using the method of the invention, the creamy thickened water /
The oil-based emulsion can be easily separated into two phases, and the solid component and the liquid component of high quality can be efficiently obtained without lowering the purity of the solid component.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-58-198423 (JP, A) JP-A-57-196 (JP, A) JP-A-57-195 (JP, A) JP-A-49- 11902 (JP, A) JP-A-63-193991 (JP, A) JP-B-51-15048 (JP, B1)

Claims (2)

[Claims] 1. An oily substance composed of various melting point components is separated into two phases of a light phase composed of a liquid component and a heavy phase composed of an aqueous phase in which a solid component is suspended by using a wetting agent, and then the solid component is separated. In the method of separating the starting oily substance into components having different melting points by separating from the suspended aqueous phase, a part or all of the solid components are precipitated as crystals in a water / oil type emulsion system in the presence of a wetting agent. While crystallizing solid components are transferred / suspended in water droplets that are the dispersed phase, and the solid components are aged (aggregated / grown) in the water droplets that are the dispersed phase, and then separated, various oily substances. Method of separating into melting point components. 2. An oily substance composed of various melting point components is divided into two phases, a light phase composed of a liquid component and a heavy phase composed of an aqueous phase in which a solid component is suspended by using a wetting agent, and then the solid component is separated. In the method of separating the starting oily substance into components having different melting points by separating from the suspended aqueous phase, a part or all of the solid components are precipitated as crystals in a water / oil type emulsion system in the presence of a wetting agent. Meanwhile, the crystallized solid component is transferred to and suspended in water droplets that are the disperse phase, and the solid components are aged (aggregated and grown) in the water droplets that are the disperse phase, and then the system is converted to an oil / water emulsion system. Characterized by separating a light phase composed of a liquid component and a heavy phase composed of an aqueous phase in which a solid component is suspended.
A method of separating an oily substance into components having various melting points.