KR101889822B1 - Purification method of cashew nut shell liquid and other raw animal fats or vegetal oil - Google Patents

Abstract

The present invention relates to a purification method of cashew nut shell oil and other raw animal fat or vegetal oil. More specifically, the present invention relates to a purification method of raw animal fat or vegetal oil which effectively removes components of alkali metal or alkaline earth metal and which, thereby having the possibility of being applied to bio heavy oil, and exhibiting high yield and improved productivity.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for purifying cashew nut husk oil and other co-

The present invention relates to a process for the purification of cashew nut shell oil and other coarse material oils. More particularly, the present invention relates to a method for purifying cashew shell husk oil and other coarse-grained material oils, which can effectively remove components of alkali metals or alkaline earth metals to be applied to bio-heavy oils, and to improve high yield and productivity.

Biofuels include biomass-related products such as plants, microorganisms, and animals that are energy sources that can produce bioenergy. They are products that have undergone chemical processes including pyrolysis, fermentation or esterification, hydrolysis, Maintenance refers to fuel made by itself.

Cashew Nut Shell Liquid (CNSL) is a vegetable oil extracted from the nuts and shells of a plant called Cashew that lives in the tropics. And the value of utilization as fuel oil is high.

However, the above-mentioned cashew shell husk oil has a limitation in that it does not satisfy the components of alkali metal or the like due to the bio-heavy oil quality standard. In addition, unlike other plant and animal oils composed of fatty acids, when a flushing system using sulfuric acid is applied, the treatment process including the alkali metal or alkaline earth metal component for satisfying the bio-oil quality standard can not be performed due to the characteristic that solid impurities are generated , Corrosion of facilities is accelerated due to the use of sulfuric acid, and corrosion of equipment is also caused.

In the case of the coarse type physical property containing alkali metal or alkaline earth metal in the composition including the above cashew nutshell oil, there is a need for a technique for a purification method capable of satisfying the biofuel oil quality standard.

The present invention relates to a method for purifying cashew shell husk oil and other animal or vegetable oils and fats, which does not generate solid impurities, and which is excellent in process efficiency, has no burden on facility corrosion, and can be applied to a biofuel channel having a high yield and improved productivity Research and development is necessary.

Korean Patent No. 10-1635974 (June 26, 2016)

The present invention relates to a refining method of a coarse type material retention which can increase the utilization value of a biofuel channel which can replace a heavy oil for power generation by lowering the content of an alkali metal or an alkaline earth metal component contained in cashew nut shell oil and other animal or vegetable oil And a refined cashew shell husk oil and other vegetable oil preservatives produced by the above production method.

It is another object of the present invention to provide a method for purifying cashew shell husk oil and other coarse-grained material oils which can improve productivity without producing solid impurities in the process and prevent corrosion of process equipment.

In order to accomplish the above object, one aspect of the present invention is a method for producing an organic-inorganic hybrid material, comprising the steps of increasing the temperature while stirring a coarse type physical property containing an alkali metal or an alkaline earth metal, mixing the organic acid aqueous solution with the coarse- Layer separation and dehydration filtration to recover the reactants, wherein the content of each of the alkali metal and alkaline earth metal is maintained at 50 ppm or less.

In the method of purifying crude physical properties according to an embodiment of the present invention, the aqueous solution of the organic acid is selected from the group consisting of oxalic acid, citric acid, acetic acid, malonic acid, tartaric acid, lactic acid, boric acid, glutaric acid, butyric acid and maleic acid And may include one or more organic acids.

In the method of purifying crude physical properties according to an embodiment of the present invention, the organic acid aqueous solution may contain 0.1 to 20 parts by weight of organic acid per 100 parts by weight of the coarse type physical property.

In the method for purifying crude physical fatigue according to an embodiment of the present invention, the temperature may be raised to a range of 40 to 100 ° C.

In the method for purifying the coarse material retention according to an embodiment of the present invention, the mixing may be carried out at a temperature in the range of 40 to 100 DEG C for 10 to 120 minutes.

In the method for purifying the coarse physical property retention according to an embodiment of the present invention, the coarse physical property retention may include a cashew nut shell oil.

In the method of purifying crude physical fatigue according to an embodiment of the present invention, the recovery may be performed under a reduced pressure condition in which the pressure is 10 to 700 mmHg.

Further, the present invention provides the same vegetable oil purified by the above-mentioned method.

The present invention also provides a biofuel oil containing the refined vegetable oil as described above.

The method of refining crude physical fatigue according to the present invention is advantageous in that it can provide a biofuel having a low unit cost including the same vegetable oil refined by a simple process using the same vegetable oil as raw material such as cashew nut shell oil, .

In addition, since solid impurities are not generated in the process, it is possible to increase the process efficiency, to obtain the refined vegetable oil with high yield, and to prevent corrosion of the equipment.

Further, the present invention has the effect of replacing heavy oil for power generation by producing bio-heavy oil having a high heating value at low cost.

Hereinafter, the method for purifying cashew nutshell oil of the present invention and other coarse physical property oils will be described in detail. The invention can be better understood by the following examples. The following examples are for illustrative purposes only and are not intended to limit the scope of protection defined by the appended claims. The technical terms and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs, unless otherwise defined.

In the present invention, " roughened physical property maintenance " means animal or vegetable oil or fat preservation of the raw material before treatment, and includes cashew shell oil unless otherwise specified.

The inventor of the present invention has found that, in the case of the coarse physical property retention which can be used as fuel oil because of its low price and high calorific value, the content of alkali metal or alkaline earth metal such as potassium, calcium and sodium is high, The inventors of the present invention have conducted studies on a purification method capable of efficiently lowering the content of the alkali metal or alkaline earth metal component in the above-mentioned coarse type physical property retention by the above simple process. As a result, it has been found that an organic acid aqueous solution is used, The present inventors have found a method for refining coarse physical property retention which has an improved process efficiency and is capable of preventing erosion of equipment without generating impure solid substances generated by using a conventional strong acid.

Specifically, the purification method of the coarse type physical property retention according to the present invention

A step of raising the temperature while stirring the coarse type physical property containing an alkali metal or an alkaline earth metal,

Mixing an organic acid aqueous solution with the above-mentioned coarse type physical property keeping and

Separating and dewatering the mixed solution to recover the reactant

.

It is required to control the content of the alkali metal or alkaline earth metal contained in the biofuel, which is the biofuel, to be used in the biofuel. Particularly, it is preferable that the calcium content is not more than 50 ppm, the calcium content is not more than 30 ppm, and the sodium content is not more than 50 ppm on the quality standard of biofuel.

The above-mentioned coarse physical property retention can be achieved by maintaining the physical properties of the fishes collected from plants such as cashew nuts, palm, rapeseed, soybean, sunflower and the like, particularly maintaining the physical properties of the fishes obtained from the cashew nuts husk channel or from animals such as tallow, lard, The resulting crude animal fat may be preserved. Also, it may be a mixture of the above-mentioned breakfast physical property maintenance and crude animal maintenance, but is not limited thereto. In addition, in the present invention, the coarse physical property retention includes a cashew nut shell oil.

In the method for purifying the coarse-type physical property retention according to the present invention, first, the coarse type physical property containing the alkali metal or the alkaline earth metal is put into the reactor and the step of raising the temperature while stirring is performed.

At this time, the temperature rise is not limited to a great extent within the scope of achieving the object of the present invention, but it is preferable to heat up the temperature to preferably 40 to 100 占 폚, more preferably 60 to 90 占 폚.

The rate of temperature rise at the time of heating is not particularly limited within a range in which the stirring process of the coarse physical property maintenance is well performed, but is preferably carried out at a rate of 0.1 to 10 ° C / min, more preferably 0.5 to 5 ° C / good.

The temperature raising step is preferably performed at the same time as stirring in terms of refining efficiency in connection with the subsequent step, and it is more preferable to satisfy the temperature raising rate and the temperature raising temperature range as described above.

Thereafter, an aqueous solution of an organic acid is charged into the reactor and mixed with the above-mentioned coarse type physical property maintenance.

The organic acid aqueous solution may be selected from oxalic acid, citric acid, acetic acid, malonic acid, tartaric acid, lactic acid, boric acid, glutaric acid, and at least one organic acid selected from the group consisting of glutaric acid, n-butyric acid, and maleic acid.

The organic acid aqueous solution may be a mixed solution of any one or more of the above-mentioned selected organic acids in purified water. At this time, it is preferable to use at least one organic acid selected from oxalic acid, citric acid, boric acid, lactic acid and butyric acid, among the organic acids, from the viewpoint of purification efficiency.

The organic acid can efficiently lower the content of each component of the alkali metal and alkaline earth metal as well as the purification of the sustained physical property retention. In addition, when a strong acid such as sulfuric acid is used, solid impurities are not generated in the process, It is possible to improve the productivity because no additional process is required, and it is better because there is no burden on the equipment corrosion.

Furthermore, the organic acid aqueous solution may contain 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight of organic acid per 100 parts by weight of the coarse type physical property. When the above-mentioned range is satisfied, the reduction efficiency of the content of the alkali metal or alkaline earth metal is excellent, which is more preferable. When the content of the organic acid exceeds the above range, the effect of reducing the content of the alkali metal or alkaline earth metal may be insignificant or the yield may be lowered.

The organic acid aqueous solution reacts with the coarse physical property retention through contact with the coarse physical property retention in the reactor. At this time, the mixing is not limited to a great extent to achieve the object of the present invention, but it is preferable that the mixing is carried out in a temperature range of 40 to 100 ° C, preferably 60 to 90 ° C. In terms of process efficiency, the mixing is preferably carried out with stirring for 10 minutes to 120 minutes, more preferably 20 minutes to 90 minutes.

The stirring may be performed using a stirring impeller installed in the reactor, but is not limited thereto. At this time, stirring may induce sufficient contact between the organic acid aqueous solution and the coarse type physical property retaining, and includes those which are generally performed by known mechanical or electromagnetic means. For example, a homogenization homogenizer or the like may be used. The stirring speed is not particularly limited, but is preferably 50 to 2,000 rpm, preferably 100 to 1,000 rpm. It is more preferable that the stirring step is carried out for 30 minutes to 6 hours, preferably 1 hour to 4 hours, more preferably 1 hour to 2 hours. This can be controlled by the diameter of the stirring impeller and the capacity of the reactor.

The stirring step may further include a step of applying a pulse electric field before or after the stirring. The pulse electric field can be repeatedly performed by flowing a current in a short time in the mixed solution and not flowing the current for a long time, but is not limited thereto. This can increase purification efficiency, and it is also possible to carry out ultrasonic treatment (sonicating) in parallel.

Further, the mixing can be carried out under a pressure condition of 1 to 10 atm, preferably 2 to 5 atm. When the above range is satisfied, the purification efficiency can be further improved, which is more preferable.

Next, the step of separating and dehydrating the mixed solution and recovering the reactant is carried out.

When the mixing process is completed, stirring is stopped and the reaction is allowed to stand or be transferred to a separate separating tank. The reactants are then layer separated. At this time, a water layer is formed in the lower layer portion, and a reaction product is present in the upper layer portion. Thus, the water layer in the lower layer is drained, and the remaining upper layer is dehydrated and filtered. The filtration step can be carried out under pressure or reduced pressure, and it is preferable to carry out the filtration under reduced pressure, more preferably 10 to 700 mmHg in terms of process efficiency.

It may also be washed using an appropriate solvent if necessary. The solvent may be a polar solvent such as a lower alcohol, but is not limited thereto. The filtration step is preferably carried out at 100 占 폚 or lower, preferably 60 to 90 占 폚.

The filtered filtrate is dehydrated under reduced pressure to obtain the final refined vegetable oil. The thus obtained purified isobutane vegetable oil can stably maintain the contents of the alkali metal and alkaline earth metal components at 50 ppm or less for a long period of time. Specifically, the present invention provides a purified vegetable oil fat having a potassium content of not more than 50 ppm, a calcium content of not more than 30 ppm, and a sodium content of not more than 50 ppm in the vegetable oil preservation.

The present invention also provides a biofuel feedstock comprising the purified vegetable oil and the feedstock thereof.

Hereinafter, the present invention will be described in more detail with reference to a method for purifying coarse-grained property retention according to the present invention, but the present invention is not limited thereto.

Biological Heavy Oil Quality Standard for Power Generation

(Content of potassium (K), calcium (Ca), sodium (Na), silicon (Si) + aluminum (Al) + iron (Fe)

- measured in accordance with ASTM D2709, in ppm.

(Example 1)

1,000 g of CNSL (Cashew Nut Shell Liquid) was added to the reactor, and the temperature was raised to 80 캜 while stirring. Thereafter, the mixed solution obtained by mixing 150 g of purified water and 40 g of oxalic acid was introduced into the reactor, stirred at 70 ° C for 1 hour, and the reaction was stopped. Then, the contents were transferred to a separator, layered at 70 ° C, . The upper CNSL layer was dehydrated under reduced pressure conditions and the final reaction was obtained using a filter.

(Example 2)

After 1,000 g of CNSL was added to the reactor, the temperature was raised to 80 DEG C with stirring. Thereafter, a mixed solution prepared by mixing 150 g of purified water and 20 g of oxalic acid was charged into a reactor, and stirred at 70 ° C for 1 hour. After the reaction was stopped, the contents were transferred to a separator and layered at 70 ° C to drain the lower layer . The upper CNSL layer was dehydrated under reduced pressure conditions and the final reaction was obtained using a filter.

(Example 3)

After 1,000 g of CNSL was added to the reactor, the temperature was raised to 80 DEG C with stirring. Thereafter, the mixed solution obtained by mixing 150 g of purified water and 80 g of citric acid was introduced into the reactor, stirred at 70 ° C for 1 hour, and the reaction was stopped. The contents were transferred to a separator, layered at 70 ° C, . The upper CNSL layer was dehydrated under reduced pressure conditions and the final reaction was obtained using a filter.

(Example 4)

After 1,000 g of CNSL was added to the reactor, the temperature was raised to 80 DEG C with stirring. Thereafter, a mixed solution prepared by mixing 150 g of purified water and 5 g of oxalic acid was charged into the reactor, and the mixture was stirred at 70 ° C for 1 hour. After the reaction was stopped, the contents were transferred to a separator and layered at 70 ° C to drain the lower layer . The upper CNSL layer was dehydrated under reduced pressure conditions and the final reaction was obtained using a filter.

(Example 5)

After 1,000 g of CNSL was added to the reactor, the temperature was raised to 80 DEG C with stirring. Thereafter, the mixed solution obtained by mixing 150 g of purified water and 250 g of oxalic acid was introduced into the reactor, stirred at 70 ° C for 1 hour, and the reaction was stopped. Then, the contents were transferred to a separator, layered at 70 ° C, . The upper CNSL layer was dehydrated under reduced pressure conditions and the final reaction was obtained using a filter.

(Comparative Example 1)

After 1,000 g of CNSL was added to the reactor, the temperature was raised to 80 DEG C with stirring. Thereafter, a mixed solution prepared by mixing 150 g of purified water with 40 g of para-toluenesulfonic acid (PTSA) was added to the reactor and stirred at 70 ° C for 1 hour. After the reaction was stopped, the contents were transferred to a separator and layered at 70 ° C The lower layer of the next layer was drained. The upper CNSL layer was dehydrated under reduced pressure conditions and the final reaction was obtained using a filter.

(Comparative Example 2)

After 1,000 g of CNSL was added to the reactor, the temperature was raised to 80 DEG C with stirring. Thereafter, the mixed solution obtained by mixing 150 g of purified water and 50 g of sulfuric acid was charged into the reactor, and stirred at 70 ° C for 1 hour. After the reaction was stopped, the contents were transferred to a separator and layered at 70 ° C to drain the lower layer . The upper CNSL layer was dehydrated under reduced pressure conditions and the final reaction was obtained using a filter.

[Table 1]

As can be seen from the above Table 1, Examples 1 to 3 according to the present invention show that the content of potassium, calcium and sodium is drastically reduced and the yield is also high, . In Examples 4 and 5, the content of organic acid was somewhat low or high, indicating that the potassium content was high or the yield was poor, but the reduction of other components was good. On the other hand, in Comparative Example 1, the content of potassium and calcium was high using PTSA and the yield was not satisfactory because the content of potassium hector oil was not satisfied. In Comparative Example 2, the yield was decreased by using sulfuric acid.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (9)

A step of raising the temperature while stirring the coarse type physical property containing an alkali metal or an alkaline earth metal,
Mixing an aqueous solution of an organic acid containing at least one organic acid selected from the group consisting of oxalic acid, citric acid, acetic acid, malonic acid, tartaric acid, lactic acid, glutaric acid, butyric acid and maleic acid into the above-
Separating and dewatering the mixed solution to recover the reactant
Wherein the content of each of the elements corresponding to the alkali metal or alkaline earth metal is 50 ppm or less.
delete The method according to claim 1,
Wherein the organic acid aqueous solution contains 0.1 to 20 parts by weight of an organic acid per 100 parts by weight of the coarse type physical property.
The method according to claim 1,
Wherein the temperature is raised to a range of 40 to 100 占 폚.
The method according to claim 1,
Wherein the mixing is carried out at a temperature in the range of 40 to 100 DEG C for 10 to 120 minutes.
The method according to claim 1,
Wherein said coarse physical property retention comprises a cashew nut shell oil.
The method according to claim 1,
Wherein the recovery is carried out under a reduced pressure of 10 to 700 mmHg.
6. The vegetable oil preserved by the method of any one of claims 1 and 3 to 7.
10. A biofuel oil comprising the refined vegetable oil of claim 8.