KR100654962B1 - Process for separating sterols from deodorizer sludge - Google Patents

Abstract

A process for separating sterols from deodorizing sludge of soybean oil is provided to obtain sterols with high purity and high yield by using deodorizer sludge of soybean oil from which tocopherol is removed. The process for separating sterols from deodorizing sludge includes the steps of: saponifying by adding sodium hydroxide solution in deodorizing sludge of soybean oil; neutralizing by injecting sulphuric acid in the saponified reaction product, removing water layer to separate oil layer, washing the separated oil layer with purified water two or three times and removing water-insoluble organic solvent through vacuum distillation and then filtrating; and re-crystallizing by adding methanol on the filtrated material obtained in the neutralizing step, extracting, filtrating and drying sterol.

Description

Process for separating sterols from deodorizer sludge

1 schematically shows an agitator with a baffle plate used for preparing sterols;

The present invention relates to a method for preparing sterols for separating and purifying sterols from soybean oil deodorized distillate remaining after removing tocopherol, and in particular, preparing a sterol using soybean oil deodorized distillate obtained by separating and purifying sterols in high yield and high purity. It is about a method.

In general, vegetable sterols have a strong ability to stabilize the emulsification state is used as an emulsifier in the manufacture of cosmetics and inks, stigma sterol and beta-sitosterol is important as a pharmaceutical raw material. These sterols can be obtained by various methods, but can also be obtained by separating from the deodorizing distillate obtained in the production of soybean oil.

Soybean oil deodorant distillate refers to the by-products that are collected in the trap when fat and oil components in soybean oil are blown with steam under vacuum, and soybean oil deodorant distillate contains tocopherol esters, sterol esters, glycerides, free fatty acids, hydrocarbons, and the like. Various methods for separating tocopherol and sterol from the soybean oil deodorized distillate have been proposed.

In US Pat. No. 3,153,054, a method for separating tocopherol and sterol by liquid solution extraction has been presented because tocopherol is very fragile under alkaline pH conditions. That is, extract solvents are prepared by mixing a polar solvent and a non-polar solvent in an appropriate ratio. Then, the extraction process is performed twice and the extract is dissolved in a third solvent and cooled. The sterol is separated into a solid and the tocopherol is separated into a liquid. do.

In Korean Laid-Open Patent No. 1992-4554, a mixed solution of normal hexane and methanol is added from soybean oil deodorized distillate, followed by cooling to separate sterols, and methyl esterification of the remaining sample, followed by concentrating tocopherols using a molecular distillation unit. Here's how.

In addition, in US Patent No. 3,335,154, in order to separate sterols and tocopherols from soybean oil deodorized distillate, a saponification reaction and an esterification reaction are carried out, and acetone is added to separate sterols, and then the tocopherols are separated and concentrated by molecular distillation. It is showing how to pay.

In British Patent No. 774,855, caustic soda is added to a soybean oil deodorized distillate, followed by acid treatment, followed by removal of an aqueous phase to separate an oily mixture, and the resulting oily mixture is lower monohydric alcohols such as methanol, fatty alcohols and hydrochloric acid. A method of esterifying the free fatty acid component by reacting by mixing with a catalyst such as, and then separating the sterol by a method such as recrystallization is proposed.

However, the techniques of separating and purifying sterols from soybean oil deodorized distillate using the aforementioned method have a problem in that the recovery and purity are very low. In particular, the techniques disclosed in US Pat. No. 3,335,154 and UK Pat. No. 774,855 have a problem that the sterol is converted to the sterol ester by a reaction with a fatty acid ester and is lost, resulting in a poor yield.

Accordingly, an object of the present invention is to provide a method for preparing sterol using soybean oil deodorized distillate which can obtain sterol in high purity and high yield using soybean oil deodorized distillate remaining after separating tocopherol.

The present invention to achieve the above object

Saponification step of removing tocopherol and adding sodium hydroxide solution to the remaining soybean oil deodorized distillate; Neutralizing by adding sulfuric acid solution to the saponified reactant, neutralizing and removing the aqueous layer to separate the oil layer, washing the separated oil layer with purified water three to four times, and then distilling off and removing the non-aqueous organic solvent under reduced pressure; In the method for producing a sterol using a soybean oil deodorized distillate, comprising; recrystallization step of adding methanol to precipitate the sterol as a crystal and then filtered and dried to the filtrate obtained in the neutralization step,

The saponification was added to 80 to 120 parts by weight of a non-aqueous organic solvent with respect to 100 parts by weight of the remaining soybean oil deodorant distillate after removing the tocopherol and heated to 85 to 95 ℃ while stirring, here 25% (w / w) sodium hydroxide solution 150 Provided is a method for preparing sterol using soybean oil deodorized distillate, which is added slowly to 300 parts by weight and then reacted for 2 to 4 hours.

Hereinafter, the present invention will be described in more detail.

Soybean oil deodorized distillate used in the present invention for preparing sterols was generally commercially available and used as the sludge remaining after removing the tocopherol, so commercially available soybean oil deodorized distillate in the sludge state from which tocopherol was removed. The sterol is contained in about 25 to 30%.

In order to prepare sterols from the remaining soybean oil deodorized distillate after removing tocopherol, a saponification step is first performed by adding sodium hydroxide solution to the raw material, and the saponification operation is an ester sterol in the soybean oil deodorized distillate raw material. This is the conversion of esters to alcohol sterols.

In general, saponification using soybean oil deodorized distillate is conducted through water or through a water-soluble organic solvent. However, the remaining sterol ester residue after removing tocopherol from soybean oil deodorized distillate contains a large amount of oil as a sludge phase and is highly viscous, so that the saponification reaction can be carried out completely by water or through a water-soluble organic solvent. It is difficult, and therefore has a disadvantage in that the yield is very low and the purity is also very low.

In order to solve this problem, in the present invention, the saponification reaction was performed through a non-aqueous organic solvent capable of completely dissolving the sterol ester. That is, the saponification according to the present invention is to add a sodium hydroxide solution in a state in which a sterol ester is completely dissolved in a non-aqueous organic solvent by adding a non-aqueous organic solvent to the soybean oil deodorized distillate remaining in the sludge after removing the tocopherol. Is done. More specifically, the saponification is added to 80 to 120 parts by weight of a non-aqueous organic solvent with respect to 100 parts by weight of the remaining soybean oil deodorized distillate after removing tocopherol and heated to 85 to 95 ℃ while stirring, 25% (w / w) hydroxide It consists of slowly adding 150-300 parts by weight of sodium solution and then reacting for 2-4 hours.

At this time, the non-aqueous organic solvent may be selected from an organic solvent which is excellent in dissolving the sterol ester but can be easily separated from water, preferably selected from toluene or benzene. The water-insoluble organic solvent may be added in an amount sufficient to completely dissolve the sterol ester contained in the soybean oil deodorized distillate, preferably 80 parts by weight or more based on 100 parts by weight of the soybean oil deodorized distillate, more preferably 80 to 120 parts by weight of soybean oil deodorized distillate is preferably added. At this time, when the amount of the non-aqueous organic solvent is less than 80 parts by weight, there is a problem that a saponification reaction is induced. When the amount is more than 120 parts by weight, there is a problem that the reaction efficiency is lowered and the yield or purity may be lowered.

As described above, when sodium hydroxide is slowly added and saponified in a state in which sterol is completely dissolved in the non-aqueous organic solvent, the reaction proceeds smoothly as the reaction occurs in the water-in-oil type, and the yield is increased. In order to make the reaction more smoothly, it is preferable to add mucus to the sodium hydroxide solution over 20 to 40 minutes. At this time, when the mucus addition time of the sodium hydroxide solution is less than 20 minutes, the reaction does not occur sufficiently, the saponification reaction of the reactants may also occur due to the shortening of the input time, and there is a problem that the yield drops, and the mucus addition time of the sodium hydroxide solution is 40 minutes. If it exceeds, there is a problem that the productivity is lowered, the sodium hydroxide solution is preferably added to the mucus within the above range.

Here, the sodium hydroxide solution does not need to limit its concentration, and the amount of the sodium hydroxide solution may be used in an excessive amount so that a sufficient reaction is achieved. In the present invention, 150 to 300 parts by weight of 25% (w / w) sodium hydroxide solution was added.

In the process of allowing the reaction to occur in the water-in-oil state by adding the sodium hydroxide solution to the mucus, it is preferable that the stirring speed is 200 to 300 rpm in order to suppress the reaction well. This stirring speed increases the contact area to increase the reaction efficiency, thereby increasing the yield. At this time, when the stirring speed is less than 200rpm there is a problem that the reaction yield and purity is lowered, and when the stirring speed exceeds 300rpm no further improved yield increase effect can be obtained, the stirring speed is preferably within the above range.

In addition, as shown in FIG. 1 in the process of adding the caustic soda aqueous solution as described above, as shown in FIG. 1, it is preferable to use a baffle plate 110 installed therein. Here, the baffle plate 110 is generally installed in a stirred reactor in order to increase the reaction efficiency, so that the reaction efficiency is increased by utilizing the present invention. As such, when the stirrer 100 having the obstruction plate 110 is used, the reaction solution forms turbulent flow by the obstruction plate 110, thereby easily transferring the material, thereby increasing the reaction efficiency.

When the saponification is completed as described above, neutralize by adding sulfuric acid solution to the saponified reactant, remove the aqueous layer to separate the oil layer, wash the separated oil layer with purified water three to four times, and then remove the water-insoluble organic solvent by distillation under reduced pressure. The filter is then neutralized.

At this time, the concentration of sulfuric acid used for neutralization need not be limited, but in order for the neutralization reaction to occur more efficiently in the present invention, the reaction product produced in the saponification is 50% while stirring at 300-400 rpm at 70-90 ℃ (w / w) 100 to 200 parts by weight of sulfuric acid solution was added mucus for 20 to 40 minutes and then reacted for 10 to 30 minutes. In other words, by the addition of sulfuric acid and agitation, the efficient neutralization reaction occurs to increase the production yield of sterols.

After the neutralization step, methanol is added to the filtrate obtained in the neutralization step to precipitate sterols as crystals, followed by a recrystallization step of filtration and drying. Recrystallization of sterols using lower alcohols such as methanol is generally carried out when the sterols are purified in soybean oil deodorized distillate. In the present invention, 300 to 400 parts by weight of methanol is added to 100 parts by weight of the filtrate obtained in the neutralization step to remove the residual fat component obtained in the neutralization step, and the temperature is increased to 65 to 80 ° C. After cooling and stirring for 24 hours, the resulting solid product was filtered and dried.

Through the above steps, sterols can be prepared in high yield and high purity from soybean oil deodorized distillate from which tocopherol containing sterol ester is removed. In particular, the yield of the sterol prepared according to the invention is 70% or more, the purity is 90% or more.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are presented to aid the understanding of the present invention and the present invention is not limited thereto.

<Example 1>

Into a stirrer equipped with a baffle plate, 200 g of tocopherol-free deodorized distillate with 27% sterol content and 200 g of toluene were added and heated to 90 ° C. while stirring at 300 rpm. Then, 200 g of a 25% (w / w) NaOH solution for 30 minutes After the addition of the mucus over the reaction for 2.5 hours,

While stirring the reaction product at 80 ° C. at 300 rpm, 150 g of 50% (w / w) sulfuric acid solution was added to the solution over 20 minutes, followed by stirring for 15 minutes, and after standing and removing the aqueous layer to obtain an oil layer. Washed with water over and distilled under reduced pressure at 110 ℃ to remove toluene and filtered,

300 g of methanol was added to the filtrate, and the mixture was added to a reactor, heated to 65 ° C, and reacted for 30 minutes, cooled to room temperature, stirred for 24 hours, and the solid product produced by stirring was filtered and then 200 g of methanol. After washing, the solid product was distilled under reduced pressure to completely remove methanol to prepare a sterol. The yield and purity of the prepared sterols are shown in Table 1 below.

<Example 2>

A sterol was prepared in the same manner as in Example 1, except that 160 g of toluene was added. The yield and purity of the prepared sterols are shown in Table 1 below.

<Example 3>

A sterol was prepared in the same manner as in Example 1, except that 240 g of toluene was added. The yield and purity of the prepared sterols are shown in Table 1 below.

Comparative Example 1

A sterol was prepared in the same manner as in Example 1, except that 100 g of toluene was added. The yield and purity of the prepared sterols are shown in Table 1 below.

Comparative Example 2

A sterol was prepared in the same manner as in Example 1 except that 300 g of toluene was added. The yield and purity of the prepared sterols are shown in Table 1 below.

Comparative Example 3

Sterol was prepared in the same manner as in Example 1, except that 200 g of a water-soluble organic solvent methanol was added to 200 g of soybean oil deodorized distillate instead of toluene. The yield and purity of the prepared sterols are shown in Table 1 below.

division Toluene addition amount (g) 25% (w / w) NaOH Sterol yield (%) Sterol Purity (%) Remarks  Addition amount (g) Stirring Speed (rpm) Addition time (min) Example 1 200 200 300 30 70 98 Example 2 160 200 300 30 80 90 Example 3 240 200 300 30 75 95 Comparative Example 1 100 200 300 30 - - Solid Formation During Reaction Comparative Example 2 300 200 300 30 78 92 Comparative Example 3 Methanol 200g 200 300 30 48 78

As shown in Table 1, in Examples 1 to 3 where the saponification reaction was carried out using a non-aqueous organic solvent, toluene within the preferred range of the present invention, the yield of sterol compared to Comparative Example 3 using methanol as a water-soluble organic solvent. And the purity is very excellent. In the case of Comparative Example 1, the reaction was impossible to proceed due to the formation of solid soap during the reaction, and in Comparative Example 2, the purity and yield of sterols were excellent, but excessive toluene was added and the corresponding enhanced effect was obtained. There is a disadvantage in that it cannot be obtained, leading to an increase in manufacturing cost.

<Example 4>

A sterol was prepared in the same manner as in Example 1 except that 150 g of the NaOH solution was added. The yield and purity of the prepared sterols are shown in Table 2 below.

Example 5

A sterol was prepared in the same manner as in Example 1, except that 300 g of the NaOH solution was added. The yield and purity of the prepared sterols are shown in Table 2 below.

<Comparative Example 4>

A sterol was prepared in the same manner as in Example 1 except that 100 g of the NaOH solution was added. The yield and purity of the prepared sterols are shown in Table 2 below.

Comparative Example 5

A sterol was prepared in the same manner as in Example 1, except that 400 g of the NaOH solution was added. The yield and purity of the prepared sterols are shown in Table 2 below.

division Toluene addition amount (g) 25% (w / w) NaOH Sterol yield (%) Sterol Purity (%) Remarks  Addition amount (g) Stirring Speed (rpm) Addition time (min) Example 4 200 150 300 30 85 90 Example 5 200 300 300 30 80 93 Comparative Example 4 200 100 300 30 90 65 Comparative Example 5 200 400 300 30 - - Solid Formation During Reaction

In the case of Examples 4 and 5 in which the amount of the sodium hydroxide solution was added within the preferred range of the present invention, it can be confirmed that the yield and purity of sterols are superior to those of Comparative Example 4, which is out of range. In Comparative Example 5, the stirring was difficult due to the generation of solid soap during the reaction, making it impossible to proceed with the reaction.

<Example 6>

A sterol was prepared in the same manner as in Example 1 except that the stirring speed was 200 rpm when the NaOH solution was added. The yield and purity of the prepared sterols are shown in Table 3 below.

Comparative Example 6

A sterol was prepared in the same manner as in Example 1 except that the stirring speed of the NaOH solution was 150 rpm. The yield and purity of the prepared sterols are shown in Table 3 below.

Comparative Example 7

A sterol was prepared in the same manner as in Example 1, except that the stirring speed of the NaOH solution was 350 rpm. The yield and purity of the prepared sterols are shown in Table 3 below.

division Toluene addition amount (g) 25% (w / w) NaOH Sterol yield (%) Sterol Purity (%) Remarks  Addition amount (g) Stirring Speed (rpm) Addition time (min) Example 6 200 200 200 30 75 95 Comparative Example 6 200 200 150 30 85 85 Comparative Example 7 200 200 350 30 70 98

As shown in Table 3, in the case of Example 6 in which the stirring speed is within the scope of the present invention, it can be seen that the purity is higher than that of Comparative Example 6, which has a low stirring speed. In the case of Comparative Example 7, the yield and purity were high, which shows that the enhanced effect is no longer obtained when compared with Example 1 having a stirring speed of 300 rpm.

<Example 7>

A sterol was prepared in the same manner as in Example 1 except that the NaOH solution was added over 20 minutes. The yield and purity of the prepared sterols are shown in Table 4 below.

<Example 8>

A sterol was prepared in the same manner as in Example 1 except that the NaOH solution was added over 40 minutes. The yield and purity of the prepared sterols are shown in Table 4 below.

<Comparative Example 8>

A sterol was prepared in the same manner as in Example 1 except that the NaOH solution was added over 10 minutes. The yield and purity of the prepared sterols are shown in Table 4 below.

Comparative Example 9

A sterol was prepared in the same manner as in Example 1 except that the NaOH solution was added over 50 minutes. The yield and purity of the prepared sterols are shown in Table 4 below.

division Toluene addition amount (g) 25% (w / w) NaOH Sterol yield (%) Sterol Purity (%) Remarks  Addition amount (g) Stirring Speed (rpm) Addition time (min) Example 7 200 200 300 20 70 97 Example 8 200 200 300 40 75 98 Comparative Example 8 200 200 300 10 - - Solid Formation During Reaction Comparative Example 9 200 200 300 50 75 98

As shown in Table 4, it can be seen that in Example 7 and Example 8, in which the addition time of sodium hydroxide was carried out within the preferred range of the present invention, sterol can be obtained in excellent yield and purity. Particularly, in the case of Comparative Example 8 having a short addition time, the saponification reaction proceeded, and in the case of Comparative Example 9 having a long addition time, it can be seen that no further improved efficiency can be obtained.

As described above, the present invention uses soybean oil deodorized distillate remaining after removing tocopherol as a raw material, and saponification in the state in which the sterol ester residue is completely dissolved in the non-aqueous organic solvent by saponifying in the state where the non-aqueous organic solvent is added thereto. The reaction yield can be increased. Especially, sterol which maximizes the reaction yield and purity by reacting by adding mucus over 20-40 minutes while stirring sodium hydroxide solution at 200-300rpm with the blockage plate installed in the reactor during saponification. There is a useful effect of providing a method for preparing sterol using soybean oil deodorized distillate that can be prepared.

Claims (6)

Saponification step of removing tocopherol and adding sodium hydroxide solution to the remaining soybean oil deodorized distillate; Neutralizing by adding sulfuric acid solution to the saponified reactant, neutralizing and removing the aqueous layer to separate the oil layer, washing the separated oil layer with purified water two to three times, and then distilling off and removing the non-aqueous organic solvent under reduced pressure; In the method for producing a sterol using a soybean oil deodorized distillate, comprising; recrystallization step of adding methanol to precipitate the sterol as a crystal and then filtered and dried to the filtrate obtained in the neutralization step, The saponification was added to 80 to 120 parts by weight of a water-insoluble organic solvent with respect to 100 parts by weight of soybean oil deodorized distillate after removing tocopherol and heated to 85 to 95 ℃ while stirring, here 25 (w / w)% sodium hydroxide solution 150 Method of producing a sterol using soybean oil deodorized distillate characterized in that it is added slowly to 300 parts by weight and then reacted for 2 to 4 hours. The method according to claim 1, Method for producing a sterol using a soybean oil deodorized distillate, characterized in that selected from toluene or benzene as the water-insoluble organic solvent. The method according to claim 1 or 2, The sodium hydroxide solution is a method of producing a sterol using a soybean oil deodorized distillate characterized in that the mucus is added over 20 to 40 minutes. The method according to claim 3, When the sodium hydroxide solution is added, the stirring is carried out in a stirrer equipped with a baffle plate, characterized in that the sterol using a soybean oil deodorized distillate characterized in that 200 ~ 300rpm. The method according to claim 4, In the neutralization step, while neutralizing the reaction product produced in saponification at 200-300 rpm at 70-90 ° C., 100-200 parts by weight of 50% (w / w) sulfuric acid solution was added to the mucus for 20-40 minutes, followed by 10-30 minutes. Method for producing a sterol using soybean oil deodorized distillate characterized in that the reaction. The method according to claim 5, In the recrystallization step, 300 to 400 parts by weight of methanol is added to 100 parts by weight of the filtrate obtained in the neutralization step, and the reaction mixture is heated at 65 to 80 ° C for 30 minutes, cooled to room temperature, stirred for 24 hours, and then the resulting solid product is filtered. Method of producing a sterol using soybean oil deodorized distillate characterized in that it is dried after.

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