阅读说明：本技术 一种油茶油精炼方法 (Oil tea oil refining method ) 是由 陈同铸 魏星 陈伟 徐春林 方成俊 李晓龙 谢燕飞 于 2021-10-25 设计创作，主要内容包括：本发明涉及一种油茶油精炼方法,属于油脂加工技术领域,包括如下步骤：将经过初级处理的油茶籽油与吸附材料混合,混合温度为105℃、搅拌时间30min、真空压力控制在-0.06MPa,然后经过过滤,得到精炼油茶油；本发明在一种油茶油精炼方法中加入了吸附材料,该吸附材料属于硅酸镁材料,与现有的材料的区别在于,制备该吸附材料的原料为改性纳米二氧化硅,提高了在油茶油精炼过程中的稳定性,提高油茶油中有效成分的稳定性,有效降低油茶籽油的酸价,提高了油茶籽油的抗氧化性,保证了油的品质。(The invention relates to a method for refining oil tea oil, which belongs to the technical field of oil processing and comprises the following steps: mixing the oil tea seed oil subjected to primary treatment with an adsorption material at 105 ℃, stirring for 30min, and controlling the vacuum pressure at-0.06 MPa, and then filtering to obtain refined oil tea oil; the adsorption material is added in the camellia oil refining method, belongs to a magnesium silicate material, and is different from the existing material in that the raw material for preparing the adsorption material is modified nano silicon dioxide, so that the stability in the camellia oil refining process is improved, the stability of effective components in the camellia oil is improved, the acid value of the camellia oil is effectively reduced, the oxidation resistance of the camellia oil is improved, and the oil quality is ensured.)

1. A method for refining oil tea oil is characterized by comprising the following steps: mixing the oil tea seed oil subjected to primary treatment with an adsorption material at 105 ℃, stirring for 30min, and controlling the vacuum pressure at-0.06 MPa, and then filtering to obtain refined oil tea oil;

the adsorbing material is prepared by the following steps:

mixing the modified nano silicon dioxide with deionized water, and performing ultrasonic dispersion for 1min to obtain a first dispersion liquid; mixing magnesium chloride hexahydrate, ammonium chloride and deionized water, stirring for 10min, and then adding ammonia water to obtain a second dispersion liquid; and mixing and stirring the first dispersion liquid and the second dispersion liquid for 5min at the temperature of 20 ℃, then reacting for 12h at the temperature of 190 ℃, filtering, washing and drying to constant weight after the reaction is finished, thus obtaining the adsorbing material.

2. The camellia oil refining method according to claim 1, wherein the dosage-mass ratio of the camellia oil subjected to primary treatment to the adsorbing material is 1000: 3.1-3.5.

3. The method for refining the oil tea camellia oil according to claim 1, wherein the amount ratio of the modified nano silica to the deionized water in the first dispersion is 1 g: 12 mL; the dosage ratio of the magnesium chloride hexahydrate, the ammonium chloride, the deionized water and the ammonia water in the second dispersion liquid is 12.5 g: 5 g: 60mL of: 3mL, wherein the mass fraction of ammonia water is 40%; the volume ratio of the first dispersion to the second dispersion is 1: 1.

4. the oil tea camellia oil refining method according to claim 1, wherein the modified nano silica is prepared by the following steps:

s11, ultrasonically dispersing nano silicon dioxide and absolute ethyl alcohol in 40kHz frequency for 20min to obtain a suspension, mixing the absolute ethyl alcohol and deionized water, adjusting the pH value to 5 by using glacial acetic acid, then adding 3-aminopropyltrimethoxysilane, stirring for 10min, adding the suspension, and stirring and reacting for 24h at 25 ℃ to obtain a solid a;

step S12, mixing triacetyl gallic acid and chloroform, adding thionyl chloride while stirring at 40 ℃, keeping the temperature unchanged, and continuously stirring for reaction for 5 hours to obtain a modifier;

and step S13, adding the solid a and potassium carbonate into deionized water, adding a toluene solution of a modifier at the temperature of 0 ℃, heating to 25 ℃ after the addition, and reacting for 24 hours to obtain the modified nano silicon dioxide.

5. The method for refining the oil tea camellia oil according to claim 4, wherein the amount ratio of the nano silicon dioxide to the absolute ethyl alcohol in the suspension in the step S11 is 3.5 g: 175 mL; the dosage ratio of the absolute ethyl alcohol, the deionized water, the 3-aminopropyl trimethoxy silane and the suspension is 160 mL: 20mL of: 7 g: 160 mL; in the step S12, the dosage ratio of the triacetyl gallic acid to the chloroform to the thionyl chloride is 5 g: 50mL of: 12 mL; in the step S13, the dosage ratio of the solid a, the potassium carbonate, the deionized water and the modifier is 5 g: 2 g: 40mL of: 2g of the total weight of the mixture; the toluene solution of the modifier is the modifier and toluene according to the dosage ratio of 1 g: 10mL of the above-mentioned components were mixed.

6. The method for refining the oil tea camellia oil according to claim 1, wherein the primary treatment process is as follows:

mixing the filtered and impurity-removed crude oil of the camellia seeds with phosphoric acid with the mass fraction of 85%, reacting for 80-100min, heating to 50-60 ℃, adding a sodium hydroxide solution with the Baume degree of 15, uniformly mixing, and stirring for 20min to obtain mixed oil; centrifugally separating the mixed oil, and separating soapstock in the mixed oil to obtain soapstock-removed oil; adding the desquamated oil into citric acid with the mass fraction of 50% and hot water with the temperature of 90 ℃, mixing, and then centrifugally dewatering.

Technical Field

The invention belongs to the technical field of oil processing, and particularly relates to a method for refining oil tea oil.

Background

The refining process of the oil tea oil has great influence on the quality of the oil tea oil, and the traditional refining process needs degumming, deacidification, decoloration, deodorization, dewaxing and the like. Degumming to remove colloid and impurities in oil; deacidifying is to neutralize free fatty acid in the grease with alkali; the decolorization is to remove pigments and trace metals in the grease, residual gum such as trace soap particles, phospholipid and the like and some substances with odor; deodorizing by steam distillation at high temperature and high vacuum, including foreign odor from the added auxiliary materials such as decolorizer; dewaxing is the removal of trace amounts of wax from oils and fats. Because the traditional refining process needs 5 working procedures, the process is complex and tedious, the refining consumption is high, auxiliary materials such as phosphoric acid, caustic soda flakes, activated clay and activated carbon are added, a large amount of loss of active ingredients such as vitamin e, tea polyphenol, squalene and sterol in the camellia seed oil is easily caused in long-time and high-strength (high-alkalinity substances such as caustic soda flakes participate in the reaction) treatment, the quality of the finished oil is seriously influenced, the risk of external hazards in the tea oil is increased due to the addition of various auxiliary materials, and the quality of the finished oil is reduced.

Disclosure of Invention

In order to solve the technical problems mentioned in the background technology, the invention provides a method for refining oil tea oil.

The purpose of the invention can be realized by the following technical scheme:

a method for refining oil tea, which comprises the following steps:

mixing the oil tea seed oil subjected to primary treatment with an adsorption material, stirring at 105 deg.C for 30min under vacuum pressure of-0.06 MPa, and filtering to obtain refined oil tea oil;

further, the dosage-mass ratio of the oil-tea camellia seed oil subjected to primary treatment to the adsorbing material is 1000: 3.1-3.5.

The adsorbing material is prepared by the following steps:

mixing the modified nano silicon dioxide with deionized water, and performing ultrasonic dispersion for 1min under the condition that the ultrasonic frequency is 45kHz to obtain a first dispersion liquid;

mixing magnesium chloride hexahydrate, ammonium chloride and deionized water, stirring for 10min, and then adding ammonia water to obtain a second dispersion liquid;

and mixing and stirring the first dispersion liquid and the second dispersion liquid for 5min at the temperature of 20 ℃, then reacting for 12h at the temperature of 190 ℃, filtering after the reaction is finished, washing a filter cake with distilled water, and finally drying to constant weight at the temperature of 80 ℃ to obtain the adsorbing material.

Further, the dosage ratio of the modified nano silicon dioxide to the deionized water in the first dispersion liquid is 1 g: 12 mL; the dosage ratio of the magnesium chloride hexahydrate, the ammonium chloride, the deionized water and the ammonia water in the second dispersion liquid is 12.5 g: 5 g: 60mL of: 3mL, wherein the mass fraction of ammonia water is 40%; the volume ratio of the first dispersion to the second dispersion is 1: 1;

the modified nano-silica is prepared by the following steps:

step S11, modification by coupling agent: ultrasonically dispersing nano silicon dioxide and absolute ethyl alcohol in 40kHz frequency for 20min to obtain a suspension, mixing the absolute ethyl alcohol with deionized water, adjusting the pH value to 5 by using glacial acetic acid, then adding 3-aminopropyltrimethoxysilane, stirring for 10min, adding the suspension, stirring and reacting for 24h at the temperature of 25 ℃, then centrifuging the reaction solution, cleaning and centrifuging by using the absolute ethyl alcohol, the absolute tetrahydrofuran and acetone after centrifuging, dispersing the solid by using the deionized water, and freeze-drying to obtain a solid a; modifying the nano silicon dioxide by using a coupling agent to introduce amino;

step S12, mixing triacetyl gallic acid and chloroform, adding thionyl chloride while stirring at 40 ℃, keeping the temperature constant, continuously stirring for reaction for 5 hours, and after the reaction is finished, carrying out reduced pressure concentration to remove the solvent to obtain a modifier; performing chlorination modification on triacetyl gallic acid serving as an antioxidant component to obtain a modifier;

and step S13, adding the solid a and potassium carbonate into deionized water, adding a toluene solution of a modifier at the temperature of 0 ℃, heating to 25 ℃ after the addition is finished, reacting for 24 hours, performing vacuum filtration after the reaction is finished, washing with distilled water, and drying to constant weight under the vacuum condition of 50 ℃ after the washing is finished to obtain the modified nano-silica. The obtained solid a is prepared by reacting with a modifier, so that the nano silicon dioxide is modified, the stability of the modifier under the high-temperature condition is improved, and the nano silicon dioxide can be used as a raw material for preparing an adsorption material.

Further, in step S11, the ratio of the nano-silica to the absolute ethyl alcohol in the suspension is 3.5 g: 175 mL; the dosage ratio of the absolute ethyl alcohol, the deionized water, the 3-aminopropyl trimethoxy silane and the suspension is 160 mL: 20mL of: 7 g: 160 mL;

in the step S12, the dosage ratio of the triacetyl gallic acid to the chloroform to the thionyl chloride is 5 g: 50mL of: 12 mL;

in the step S13, the dosage ratio of the solid a, the potassium carbonate, the deionized water and the modifier is 5 g: 2 g: 40mL of: 2g of the total weight of the mixture; the toluene solution of the modifier is the modifier and toluene according to the dosage ratio of 1 g: 10mL of the above-mentioned components were mixed.

Further, the primary treatment process is as follows:

mixing the filtered and impurity-removed camellia seed crude oil with 85% of phosphoric acid by mass, wherein the addition amount of the phosphoric acid is 0.12-0.15% of the total weight of the camellia seed crude oil, reacting for 80-100min, heating to 50-60 ℃, adding a sodium hydroxide solution with Baume degree of 15, fully and uniformly mixing, and slowly stirring for about 20min to obtain mixed oil; the addition amount of the sodium hydroxide solution is as follows: 1 multiplied by 0.713 multiplied by Q/1000, wherein Q is the flow T/h of the crude oil of the camellia seeds; centrifugally separating the mixed oil, and separating soapstock in the mixed oil to obtain soapstock-removed oil; adding the desquamated oil into citric acid with the mass fraction of 50% and hot water with the temperature of 90 ℃, fully mixing, and then putting into a washing centrifuge for dehydration. The addition amount of citric acid is 0.01% of the total weight of the camellia seed crude oil, and the addition amount of hot water is 8% of the total weight of the camellia seed crude oil.

The invention has the beneficial effects that:

the adsorption material is added in the camellia oil refining method, belongs to a magnesium silicate material, and is different from the existing material in that the raw material for preparing the adsorption material is modified nano silicon dioxide, so that the stability in the camellia oil refining process is improved, the stability of effective components in the camellia oil is improved, the acid value of the camellia oil is effectively reduced, the oxidation resistance of the camellia oil is improved, and the oil quality is ensured.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Preparing modified nano silicon dioxide:

step S11, modification by coupling agent: ultrasonically dispersing nano silicon dioxide and absolute ethyl alcohol in 40kHz frequency for 20min to obtain a suspension, mixing the absolute ethyl alcohol with deionized water, adjusting the pH value to 5 by using glacial acetic acid, then adding 3-aminopropyltrimethoxysilane, stirring for 10min, adding the suspension, stirring and reacting for 24h at the temperature of 25 ℃, then centrifuging the reaction solution, cleaning and centrifuging by using the absolute ethyl alcohol, the absolute tetrahydrofuran and acetone after centrifuging, dispersing the solid by using the deionized water, and freeze-drying to obtain a solid a; wherein the dosage ratio of the nano silicon dioxide to the absolute ethyl alcohol in the suspension is 3.5 g: 175 mL; the dosage ratio of the absolute ethyl alcohol, the deionized water, the 3-aminopropyl trimethoxy silane and the suspension is 160 mL: 20mL of: 7 g: 160 mL;

step S12, mixing triacetyl gallic acid and chloroform, adding thionyl chloride while stirring at 40 ℃, keeping the temperature constant, continuously stirring for reaction for 5 hours, and after the reaction is finished, carrying out reduced pressure concentration to remove the solvent to obtain a modifier; wherein the dosage ratio of the triacetyl gallic acid to the chloroform to the thionyl chloride is 5 g: 50mL of: 12 mL;

and step S13, adding the solid a and potassium carbonate into deionized water, adding a toluene solution of a modifier at the temperature of 0 ℃, heating to 25 ℃ after the addition is finished, reacting for 24 hours, performing vacuum filtration after the reaction is finished, washing with distilled water, and drying to constant weight under the vacuum condition of 50 ℃ after the washing is finished to obtain the modified nano-silica. Wherein the dosage ratio of the solid a, the potassium carbonate, the deionized water and the modifier is 5 g: 2 g: 40mL of: 2g of the total weight of the mixture; the toluene solution of the modifier is the modifier and toluene according to the dosage ratio of 1 g: 10mL of the above-mentioned components were mixed.

Example 2

Preparing an adsorbing material:

mixing the modified nano silicon dioxide with deionized water, and performing ultrasonic dispersion for 1min under the condition that the ultrasonic frequency is 45kHz to obtain a first dispersion liquid; wherein the dosage ratio of the modified nano silicon dioxide to the deionized water is 1 g: 12 mL;

mixing magnesium chloride hexahydrate, ammonium chloride and deionized water, stirring for 10min, and then adding ammonia water to obtain a second dispersion liquid; wherein the dosage ratio of the magnesium chloride hexahydrate, the ammonium chloride, the deionized water and the ammonia water is 12.5 g: 5 g: 60mL of: 3mL, wherein the mass fraction of ammonia water is 40%;

and mixing and stirring the first dispersion liquid and the second dispersion liquid for 5min at the temperature of 20 ℃, then reacting for 12h at the temperature of 190 ℃, filtering after the reaction is finished, washing a filter cake with distilled water, and finally drying to constant weight at the temperature of 80 ℃ to obtain the adsorbing material. Wherein the volume ratio of the dosage of the first dispersion liquid to the dosage of the second dispersion liquid is 1: 1;

example 3

A method for refining oil tea, which comprises the following steps:

mixing the oil tea seed oil subjected to primary treatment with an adsorption material, stirring at 105 deg.C for 30min under vacuum pressure of-0.06 MPa, and filtering to obtain refined oil tea oil;

wherein the dosage mass ratio of the oil-tea camellia seed oil subjected to primary treatment to the adsorption material is 1000: 3.1. the adsorbent material was prepared as in example 2.

Primary treatment of camellia seed crude oil:

mixing the filtered and impurity-removed camellia seed crude oil with 85% phosphoric acid by mass, wherein the addition amount of the phosphoric acid is 0.12% of the total weight of the camellia seed crude oil, reacting for 80min, heating to 50 ℃, adding a sodium hydroxide solution with Baume degree of 15, fully and uniformly mixing, and slowly stirring for about 20min to obtain mixed oil; the addition amount of the sodium hydroxide solution is as follows: 1 multiplied by 0.713 multiplied by Q/1000, wherein Q is the flow T/h of the crude oil of the camellia seeds; centrifugally separating the mixed oil, and separating soapstock in the mixed oil to obtain soapstock-removed oil; adding the desquamated oil into citric acid with the mass fraction of 50% and hot water with the temperature of 90 ℃, fully mixing, and then putting into a washing centrifuge for dehydration. The addition amount of citric acid is 0.01% of the total weight of the camellia seed crude oil, and the addition amount of hot water is 8% of the total weight of the camellia seed crude oil.

Example 4

A method for refining oil tea, which comprises the following steps:

mixing the oil tea seed oil subjected to primary treatment with an adsorption material, stirring at 105 deg.C for 30min under vacuum pressure of-0.06 MPa, and filtering to obtain refined oil tea oil;

wherein the dosage mass ratio of the oil-tea camellia seed oil subjected to primary treatment to the adsorption material is 1000: 3.3. the adsorbent material was prepared as in example 2.

Primary treatment of camellia seed crude oil:

mixing the filtered and impurity-removed camellia seed crude oil with 85% phosphoric acid by mass, wherein the addition amount of the phosphoric acid is 0.13% of the total weight of the camellia seed crude oil, reacting for 90min, heating to 55 ℃, adding a sodium hydroxide solution with Baume degree of 15, fully and uniformly mixing, and slowly stirring for about 20min to obtain mixed oil; the addition amount of the sodium hydroxide solution is as follows: 1 multiplied by 0.713 multiplied by Q/1000, wherein Q is the flow T/h of the crude oil of the camellia seeds; centrifugally separating the mixed oil, and separating soapstock in the mixed oil to obtain soapstock-removed oil; adding the desquamated oil into citric acid with the mass fraction of 50% and hot water with the temperature of 90 ℃, fully mixing, and then putting into a washing centrifuge for dehydration. The addition amount of citric acid is 0.01% of the total weight of the camellia seed crude oil, and the addition amount of hot water is 8% of the total weight of the camellia seed crude oil.

Example 5

A method for refining oil tea, which comprises the following steps:

mixing the oil tea seed oil subjected to primary treatment with an adsorption material, stirring at 105 deg.C for 30min under vacuum pressure of-0.06 MPa, and filtering to obtain refined oil tea oil;

wherein the dosage mass ratio of the oil-tea camellia seed oil subjected to primary treatment to the adsorption material is 1000: 3.5. the adsorbent material was prepared as in example 2.

Primary treatment of camellia seed crude oil:

mixing the filtered and impurity-removed camellia seed crude oil with 85% phosphoric acid by mass, wherein the addition amount of the phosphoric acid is 0.15% of the total weight of the camellia seed crude oil, reacting for 100min, heating to 60 ℃, adding a sodium hydroxide solution with Baume degree of 15, fully and uniformly mixing, and slowly stirring for about 20min to obtain mixed oil; the addition amount of the sodium hydroxide solution is as follows: 1 multiplied by 0.713 multiplied by Q/1000, wherein Q is the flow T/h of the crude oil of the camellia seeds; centrifugally separating the mixed oil, and separating soapstock in the mixed oil to obtain soapstock-removed oil; adding the desquamated oil into citric acid with the mass fraction of 50% and hot water with the temperature of 90 ℃, fully mixing, and then putting into a washing centrifuge for dehydration. The addition amount of citric acid is 0.01% of the total weight of the camellia seed crude oil, and the addition amount of hot water is 8% of the total weight of the camellia seed crude oil.

Comparative example 1

The adsorbent material of example 4 was replaced with magnesium silicate and the rest of the process was kept unchanged.

The test results of the camellia oil obtained in examples 3 to 5 and comparative example 1 are shown in table 1 below:

TABLE 1

	Acid value (KOHmg/g)	Peroxide number (mmol/kg)
			Example 3	0.34	1.14
Example 4	0.34	1.13
			Example 5	0.35	1.14
Comparative example 1	1.22	2.51

From the above table 1, it can be seen that the refining method of the present invention can effectively reduce the acid value of the camellia seed oil and improve the oxidation resistance of the camellia seed oil.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.