Refining process of camellia oil

Abstract

The invention provides a refining process of camellia oil, and belongs to the technical field of vegetable oil processing, the refining process comprises the following steps: drying and shelling camellia seeds to obtain camellia seed kernels, crushing and sieving the camellia seed kernels, adding an antioxidant additive, and squeezing at low temperature to obtain crude camellia oil; dewaxing the crude camellia oil, and filtering to obtain crude camellia oil; then adding the crude camellia oil into the pretreated macroporous adsorption resin column for sample loading, eluting with an ethanol aqueous solution, centrifugally demulsifying, extracting, and carrying out reduced pressure distillation to obtain purified crude camellia oil; adding modified camellia seed shell activated carbon into the purified crude camellia oil, and performing adsorption decoloration, centrifugation and filtration to obtain decolorized crude camellia oil; and adding the decolored crude camellia oil into a deodorization machine, and carrying out vacuum deodorization to obtain the camellia oil. The obtained camellia oil is high in activity, stable in storage performance and more suitable for cosmetics.

Description

Technical Field

[0001] The invention belongs to the technical field of vegetable oil processing, and in particular relates to a camellia oil refining process. Background Art

[0002] Camellia oil, also known as camellia seed oil or wild camellia oil, is a vegetable oil extracted from the seeds of Camellia oleifera Abel, a plant of the Theaceae family. This oil is known for its unique nutritional value and health benefits. It is rich in monounsaturated fatty acids, especially oleic acid, which helps lower bad cholesterol and increase good cholesterol, and is particularly beneficial to cardiovascular health. Camellia oil is also rich in vitamin E, squalene, and a variety of antioxidants, which help protect the skin from free radical damage and delay skin aging. In addition, camellia oil has a high smoke point, is suitable for high-temperature cooking, and is not prone to producing harmful substances, making it an ideal choice for healthy cooking. Due to its mild taste and many health benefits, camellia oil is widely used in Asia, especially in southern China, and is known as the "Oriental Olive Oil."

[0003] At present, the preparation processes of camellia oil in the prior art mainly include the following: (1) Mechanical pressing method, as a traditional extraction process, includes several stages such as traditional pressing, hydraulic oil pressing and screw oil pressing. Low temperature pressing process usually refers to processing under an environment below 60°C, which retains the natural flavor and color of the oil and completely preserves the physiologically active substances in the oil, such as vitamin E and sterols, but the oil yield is relatively low and the cost is high. (2) Solvent extraction method, this method uses organic solvents to fully soak the oil and then extract it at high temperature. The oil yield is high, but there will be chemical solvent residues, and it may be contaminated by chemical solvents during the extraction process. (3) Aqueous enzyme method, this is a method that uses mechanical and enzyme means to degrade the cellulose skeleton of the plant cell wall to release the oil. The conditions are mild, the color is light, and it is easy to refine; the protein denaturation of the defatted cake is low and the availability is good; but the oil emulsification phenomenon may occur during the processing, the oil yield is not high, the price of the enzyme is high, and it is limited in practical application. (4) Supercritical CO2 extraction method is to contact the supercritical fluid with the substance to be separated under supercritical state, control the pressure and temperature of the system, so that it can selectively extract a certain component. The oil obtained by this method is lighter in color and has no residual solvent, but the equipment requirements are high, the price is expensive, and the operability of large-scale production is poor. (5) Fresh pressing method is to use fresh high-quality camellia seeds as raw materials, add a certain concentration of ethanol to extract the oil phase after pulping, and finally purify to obtain freshly squeezed camellia oil. Although this method increases the content of effective ingredients, it discards some water-soluble nutritional factors during the preparation process, resulting in the subsequent addition of emulsifiers. The emulsion has low nutritional content and poor stability, and the cost is significantly higher than other types of camellia oil.

[0004] Camellia oil has high added value when used as raw material for high-end cosmetic production. However, the current production process of camellia oil for cosmetics is mainly refined by referring to the edible oil refining process, ignoring the characteristics of camellia oil for cosmetics, and the refined camellia oil obtained often cannot meet the requirements of cosmetics in terms of color, smell, activity, etc. In order to overcome the above problems, the present invention aims to provide a refining process of camellia oil, which improves the traditional edible oil refining process, retains the active ingredients contained in camellia oil to the maximum extent, thereby obtaining camellia oil more suitable for cosmetic use, which has the characteristics of high activity, good stability, low peroxide value and low acid value. Summary of the invention

[0005] The purpose of the present invention is to provide a refining process for camellia oil, which comprises the following steps: adding an antioxidant auxiliary agent for low-temperature pressing, and then using a pretreated macroporous adsorption resin and modified camellia seed shell activated carbon to purify and decolorize the crude camellia oil, so that the obtained camellia oil maintains a low peroxide value and a low acid value, has stable storage performance, is clear and transparent, and has no odor, and is more suitable for cosmetics.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a camellia oil refining process, comprising the following steps:

[0008] Step (1): drying camellia seeds to a moisture content of 4-6%, then peeling the camellia seed shells with a shelling machine to obtain camellia seed kernels; crushing and sieving the camellia seed kernels, then adding an antioxidant additive, and then low-temperature pressing with a press to obtain camellia crude oil;

[0009] Step (ii): cooling and dewaxing the camellia crude oil for 16-20 hours, filtering with a plate and frame, removing the filter residue, and obtaining the camellia crude oil; soaking the macroporous adsorption resin in an ethanol aqueous solution for 32-38 hours, washing with water, and obtaining the pretreated macroporous adsorption resin; loading the pretreated macroporous adsorption resin into a column, and then adding the camellia crude oil to the pretreated macroporous adsorption resin column at a flow rate of 3-5 BV / h for loading, and then eluting with an ethanol aqueous solution at a flow rate of 3-5 BV / h until no oil flows out, centrifuging and demulsifying, extracting, and distilling under reduced pressure to obtain purified camellia crude oil;

[0010] Step (iii): adding the modified camellia seed shell activated carbon to the purified camellia crude oil, adsorbing and decolorizing for 1-2 hours, centrifuging, filtering, and obtaining decolorized camellia crude oil; adding the decolorized camellia crude oil to a deodorizer, vacuum deodorizing for 1-3 hours, cooling and depressurizing to normal temperature and pressure after deodorization, and obtaining the camellia oil.

[0011] Preferably, the present invention provides a camellia oil refining process, comprising the following steps:

[0012] Step (1): Select plump, mildew-free, normal-colored, and impurity-free camellia seeds (also called oil tea seeds), dry them at 45-60° C. to a moisture content of 4-6%, and then use a shelling machine to peel the camellia seed shells to obtain camellia seed kernels; grind the camellia seed kernels through an 80-120 mesh sieve, then add an antioxidant additive, and then use a press to perform low-temperature pressing to obtain camellia crude oil;

[0013] Step (ii): cooling and dewaxing the crude camellia oil for 16-20 hours, filtering with a plate and frame, removing the filter residue, and obtaining crude camellia oil; soaking the macroporous adsorption resin in a 92-96wt% ethanol aqueous solution for 32-38 hours, and then washing with water 4-6 times to obtain a pre-treated macroporous adsorption resin; loading the pre-treated macroporous adsorption resin into a column, and then adding the crude camellia oil to the pre-treated macroporous adsorption resin column at a flow rate of 3-5BV / h for loading, and then eluting with a 55-65wt% ethanol aqueous solution at a flow rate of 3-5BV / h until no oil flows out, centrifuging and demulsifying, extracting with ethyl acetate, and recovering the solvent by reduced pressure distillation to obtain purified crude camellia oil;

[0014] Step (iii): adding the modified camellia seed shell activated carbon to the purified camellia crude oil, adsorbing and decolorizing for 1-2 hours, centrifuging, filtering, and obtaining decolorized camellia crude oil; adding the decolorized camellia crude oil to a deodorizer, vacuum deodorizing for 1-3 hours, and then gradually cooling and depressurizing to normal temperature and pressure to obtain the camellia oil.

[0015] Camellia oil is rich in unsaturated fatty acids, especially oleic acid, which is the main active ingredient and has a much higher content than general vegetable oils. However, its unsaturated fatty acids are easily oxidized during the refining or subsequent storage process (especially high temperature, light and air contact, etc.). Oxidation will cause the activity of camellia oil to decrease, the color to change, and the smell to produce, thus deteriorating the quality.

[0016] The invention adds an antioxidant auxiliary agent for low-temperature pressing, then adopts cooling dewaxing treatment, pre-treats macroporous adsorption resin and modified camellia seed shell activated carbon to purify and decolorize the camellia crude oil, and performs vacuum deodorization treatment, so that the obtained camellia oil maintains a low peroxide value and a low acid value, and at the same time has stable storage performance, is clear and transparent, and has no odor, and is more suitable for cosmetics.

[0017] The invention can remove wax and solid impurities in the camellia crude oil through cooling dewaxing treatment, and then adopts pretreatment M130 macroporous adsorption resin and modified camellia seed shell activated carbon for joint treatment to purify the camellia crude oil twice, and can effectively adsorb pigments, free saturated fatty acids and the like in the camellia crude oil under mild conditions, so as to achieve rapid removal of impurities such as pigments under room temperature, reduce the acid value of the camellia oil, and ketone / aldehyde acid substances generated by peroxidation, and increase the content of unsaturated fatty acids.

[0018] The present invention can avoid the processes of hydration degumming, alkali refining and deacidification in traditional chemical refining by combining cooling dewaxing treatment, pretreatment of macroporous adsorption resin and modified camellia seed shell activated carbon adsorption treatment, thereby reducing the discharge of refining wastewater; the low treatment temperature of vacuum deodorization overcomes the shortcomings of traditional deodorization treatment with too high temperature and easy oxidation of oil and fat, and can effectively remove odorous substances in the oil.

[0019] The modified camellia seed shell activated carbon used in the present invention uses the camellia seed shell recovered in the refining step (I) as a raw material, turning waste into treasure, crushing the camellia seed shell, soaking it in a mixed acid composed of nitric acid and phosphoric acid, and then calcining it at high temperature to obtain initial activated carbon; then after 60Co-γ ray irradiation treatment, lauryl betaine and propyl gallate are added for modification, and finally the modified camellia seed shell activated carbon is obtained. The use of modified camellia seed shell activated carbon can further improve the adsorption performance, while reducing the degree of oxidation, reducing the rancid substances generated during the oxidation process, and significantly improving the quality of camellia oil. Among them, the mixed acid can effectively remove impurities in camellia seed shells, which is helpful for the purity and adsorption performance of activated carbon. It can also form more micropores and mesoporous structures on the surface of the material through acid corrosion, and promote the formation of more developed pore structures in subsequent high-temperature carbonization, thereby increasing the specific surface area and adsorption capacity of activated carbon; 60Co-γ ray irradiation treatment helps to improve the permeability of activated carbon and activate its surface activation force; the activated carbon after activation increases its binding ability with lauryl betaine and propyl gallate, which is conducive to better binding to the surface of activated carbon. The weak alkalinity of the amino group provided by lauryl betaine is conducive to the adsorption of free fatty acids to reduce the acid value. Propyl gallate is dispersed in camellia crude oil by binding to the surface of the activated carbon carrier, which can give it excellent antioxidant properties, thereby inhibiting the oxidation of active ingredients in camellia oil during the refining process and decomposing them into ketone / aldehyde substances with peculiar smell.

[0020] Preferably, the modified camellia seed shell activated carbon is prepared by the following method:

[0021] The camellia seed shell is crushed and sieved to obtain a raw material powder; 15-25 parts by weight of the raw material powder is added to 70-90 parts by weight of a mixed acid, soaked for 2-4 hours, filtered, washed and dried, and then calcined at high temperature for 2-4 hours to obtain initial activated carbon;

[0022] 5-7 parts by weight of initial activated carbon and 50-70 parts by weight of ethanol aqueous solution are uniformly mixed, irradiated with 60Co-γ rays for 20-40 minutes, then 0.1-0.2 parts by weight of lauryl betaine and 0.3-0.4 parts by weight of propyl gallate are added, heated and stirred for 5-7 hours, filtered, washed and dried to obtain modified camellia seed shell activated carbon.

[0023] Furthermore, the modified camellia seed shell activated carbon is prepared by the following method:

[0024] The camellia seed shell is crushed through an 80-120 mesh sieve to obtain a raw material powder; 15-25 parts by weight of the raw material powder is added to 70-90 parts by weight of a mixed acid, and the mixture is soaked at 23-27° C. and 100-250 rpm for 2-4 hours, filtered, washed, and dried, and then calcined at 450-550° C. and a nitrogen atmosphere for 2-4 hours to obtain an initial activated carbon; the mixed acid is composed of 10-20wt% nitric acid, 15-25wt% phosphoric acid, and the balance water;

[0025] 5-7 parts by weight of initial activated carbon and 50-70 parts by weight of 25-35wt% ethanol aqueous solution are uniformly mixed, and irradiated for 20-40 minutes under the conditions of irradiation dose rate of 1-2.5 kGy / h and 60Co-γ rays. Then, 0.1-0.2 parts by weight of lauryl betaine and 0.3-0.4 parts by weight of propyl gallate are added, and stirred for 5-7 hours at 45-60°C and 200-350rpm. The mixture is filtered, washed and dried to obtain modified camellia seed shell activated carbon.

[0026] Preferably, the antioxidant auxiliary agent in step (i) is a mixture of vitamin E and crocus sativus flower extract in a weight ratio of 1-3:1.

[0027] Among them, the CAS number of crocus sativus flower extract is 84604-17-1.

[0028] The present invention performs low-temperature pressing in an environment containing the above-mentioned specific antioxidant auxiliary agent, which can effectively avoid the oxidation damage of the active ingredients in the camellia oil caused by air contact and heating during the refining process, and overcomes the problem of low active ingredients in the camellia oil in the prior art. The present invention simultaneously uses vitamin E and saffron flower extract as antioxidant auxiliary agents, and the two play a role at different oxidation stages. Vitamin E can react with lipid oxygen free radicals or lipid peroxyl free radicals to interrupt the oil oxidation chain reaction, while the saffron flower extract can enhance the ability to remove primary free radicals, produce a synergistic effect with vitamin E, and improve the overall antioxidant capacity. The two are synergistic and complementary, which helps to form more effective antioxidant protection during low-temperature pressing, reduce the oxidation loss of active ingredients, and thus improve the quality and stability of camellia oil.

[0029] Preferably, the amount of the antioxidant added in step (i) is 0.06-0.1 wt % of the weight of the camellia seed kernel.

[0030] Preferably, the conditions for low temperature pressing in step (i) are: the feed temperature is controlled within 35°C, and the oil outlet temperature is controlled within 55°C.

[0031] Preferably, the conditions for the cooling dewaxing treatment in step (ii) are: temperature 1-3°C, rotation speed 10-20 rpm.

[0032] Preferably, the weight ratio of the macroporous adsorption resin to the ethanol aqueous solution in step (ii) is 1:3-5.

[0033] Preferably, the macroporous adsorption resin in step (ii) is DM130 macroporous adsorption resin.

[0034] Preferably, the loading amount of the pretreated macroporous adsorption resin in step (ii) is 1 / 3-2 / 3 of the column length.

[0035] Preferably, the weight ratio of the modified camellia seed shell activated carbon to the purified camellia crude oil in step (iii) is 1:35-45.

[0036] Preferably, the conditions for adsorption decolorization in step (iii) are: temperature 23-27° C., stirring speed 100-250 rpm.

[0037] Preferably, the vacuum deodorization conditions in step (iii) are: pressure 0.5-1.5 mbar, temperature 150-180°C.

[0038] The invention also provides a camellia oil prepared by the method.

[0039] The present invention also provides application of the camellia oil in preparing cosmetics.

[0040] Preferably, the application includes but is not limited to: using the camellia oil to prepare camellia oil facial cream, camellia oil body lotion, and camellia oil moisturizing lotion.

[0041] Compared with the prior art, the advantages and beneficial effects of the present invention are:

[0042] 1. The present invention provides a camellia oil refining process, which improves the process by adding a specific antioxidant auxiliary agent for low-temperature pressing, and then using a pre-treated macroporous adsorption resin and modified camellia seed shell activated carbon to purify and decolorize the camellia crude oil twice, thereby retaining the active ingredients contained in the camellia oil to the greatest extent, so that the obtained camellia oil maintains a low peroxide value and a low acid value, has stable storage performance, is clear and transparent, and is more suitable for preparing cosmetics.

[0043] 2. The present invention uses pre-treated macroporous adsorption resin and modified camellia seed shell activated carbon to purify camellia crude oil twice, directly removing impurities such as wax fat, free saturated fatty acids, colored substances, etc. in the oil, avoiding the addition of chemical substances such as sodium chloride, sodium hydroxide, acid, etc. in the oil during the water washing and alkali refining process in the prior art, and will not cause the loss of active ingredients in the oil.

[0044] 3. The modified camellia seed shell activated carbon used in the present invention uses the camellia seed shell recovered in the refining step (i) as raw material, turning waste into treasure. Compared with directly using activated carbon, it can further improve the adsorption performance, while reducing the degree of oxidation, reducing the rancid substances produced during the oxidation process, and significantly improving the quality of camellia oil. DETAILED DESCRIPTION

[0045] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0046] Example 1

[0047] This embodiment provides a camellia oil refining process, comprising the following steps:

[0048] Step (i): selecting plump, mildew-free, normal-colored, and impurity-free camellia seeds, drying them at 45° C. to a moisture content of 6%, and then peeling the camellia seed shells with a shelling machine to obtain camellia seed kernels; crushing the camellia seed kernels through an 80-mesh sieve, adding an antioxidant, and then performing low-temperature pressing with a press (the feed temperature of the low-temperature pressing is controlled at 30° C., and the oil outlet temperature is controlled at 50° C.) to obtain camellia crude oil; the antioxidant is a mixture of vitamin E and saffron flower extract in a weight ratio of 1:1; the amount of the antioxidant added is 0.06wt% of the weight of the camellia seed kernels;

[0049] Step (ii): cooling and dewaxing the camellia crude oil at 1°C and 10rpm for 16h, filtering on a plate and frame, removing the filter residue, and obtaining camellia crude oil; soaking the macroporous adsorption resin in a 92wt% ethanol aqueous solution for 38h, wherein the weight ratio of the macroporous adsorption resin to the ethanol aqueous solution is 1:3, and then washing with water 4 times to obtain a pre-treated macroporous adsorption resin; loading the pre-treated macroporous adsorption resin into a column, wherein the loading amount is 1 / 3 of the column length, and then adding the camellia crude oil to the pre-treated macroporous adsorption resin column at a flow rate of 3BV / h for loading, and then eluting with a 55wt% ethanol aqueous solution at a flow rate of 3BV / h until no oil flows out, centrifuging and demulsifying, extracting with ethyl acetate, and recovering the solvent by reduced pressure distillation to obtain purified camellia crude oil; wherein the macroporous adsorption resin adopts DM130 macroporous adsorption resin, which is purchased from Purui Pure Resin (Shanghai) Co., Ltd.;

[0050] Step (iii): adding the modified camellia seed shell activated carbon to the purified camellia crude oil, wherein the weight ratio of the modified camellia seed shell activated carbon to the purified camellia crude oil is 1:35, adsorbing and decolorizing for 2 hours at 23° C. and 100 rpm, centrifuging, and filtering to obtain decolorized camellia crude oil; adding the decolorized camellia crude oil to a deodorizer, vacuum deodorizing for 1 hour at 0.5 mbar and 180° C., and then gradually cooling and depressurizing to normal temperature and pressure to obtain the camellia oil.

[0051] The modified camellia seed shell activated carbon is prepared by the following method:

[0052] The camellia seed shells were crushed and passed through an 80-mesh sieve to obtain a raw material powder; 15 parts by weight of the raw material powder were added to 70 parts by weight of a mixed acid, and the mixture was soaked at 23°C and 100 rpm for 4 hours, filtered, washed, and dried, and then calcined at 450°C and in a nitrogen atmosphere for 4 hours to obtain initial activated carbon; the mixed acid was composed of 10wt% nitric acid, 25wt% phosphoric acid, and the balance water;

[0053] 5 parts by weight of initial activated carbon and 50 parts by weight of 25wt% ethanol aqueous solution were evenly mixed, irradiated for 40 minutes under the conditions of irradiation dose rate of 1 kGy / h and 60Co-γ rays, then 0.1 parts by weight of lauryl betaine and 0.3 parts by weight of propyl gallate were added, stirred for 7 hours at 45°C and 200rpm, filtered, washed and dried to obtain modified camellia seed shell activated carbon.

[0054] Example 2

[0055] This embodiment provides a camellia oil refining process, comprising the following steps:

[0056] Step (i): selecting plump, mildew-free, normal-colored, and impurity-free camellia seeds, drying them at 50° C. to a moisture content of 5%, and then peeling the camellia seed shells with a shelling machine to obtain camellia seed kernels; crushing the camellia seed kernels through a 100-mesh sieve, adding an antioxidant, and then performing low-temperature pressing with a press (the feed temperature of the low-temperature pressing is controlled at 30° C., and the oil outlet temperature is controlled at 50° C.) to obtain camellia crude oil; the antioxidant is a mixture of vitamin E and saffron flower extract in a weight ratio of 2:1; the amount of the antioxidant added is 0.08wt% of the weight of the camellia seed kernels;

[0057] Step (ii): cooling and dewaxing the camellia crude oil at 2°C and 15rpm for 18h, filtering on a plate and frame, removing the filter residue, and obtaining camellia crude oil; soaking the macroporous adsorption resin in a 95wt% ethanol aqueous solution for 36h, wherein the weight ratio of the macroporous adsorption resin to the ethanol aqueous solution is 1:4, and then washing with water 5 times to obtain a pre-treated macroporous adsorption resin; loading the pre-treated macroporous adsorption resin into a column, wherein the loading amount is 1 / 2 of the column length, and then adding the camellia crude oil to the pre-treated macroporous adsorption resin column at a flow rate of 4BV / h for loading, and then eluting with a 60wt% ethanol aqueous solution at a flow rate of 4BV / h until no oil flows out, centrifuging and demulsifying, extracting with ethyl acetate, and recovering the solvent by reduced pressure distillation to obtain purified camellia crude oil; wherein the macroporous adsorption resin adopts DM130 macroporous adsorption resin, which is purchased from Purui Pure Resin (Shanghai) Co., Ltd.;

[0058] Step (iii): adding the modified camellia seed shell activated carbon to the purified camellia crude oil, wherein the weight ratio of the modified camellia seed shell activated carbon to the purified camellia crude oil is 1:40, adsorbing and decolorizing for 1.5 hours at 25°C and 200rpm, centrifuging, and filtering to obtain decolorized camellia crude oil; adding the decolorized camellia crude oil to a deodorizer, vacuum deodorizing for 2 hours at 1 mbar and 160°C, and then gradually cooling and depressurizing to normal temperature and pressure to obtain the camellia oil.

[0059] The modified camellia seed shell activated carbon is prepared by the following method:

[0060] The camellia seed shells were crushed and passed through a 100-mesh sieve to obtain a raw material powder; 20 parts by weight of the raw material powder were added to 80 parts by weight of a mixed acid, and the mixture was soaked at 25°C and 200 rpm for 3 hours, filtered, washed, and dried, and then calcined at 500°C and a nitrogen atmosphere for 3 hours to obtain an initial activated carbon; the mixed acid was composed of 15wt% nitric acid, 20wt% phosphoric acid, and the balance water;

[0061] 6 parts by weight of initial activated carbon and 60 parts by weight of 30wt% ethanol aqueous solution were evenly mixed, irradiated for 30 minutes under an irradiation dose rate of 2kGy / h and 60Co-γ rays, then 0.15 parts by weight of lauryl betaine and 0.35 parts by weight of propyl gallate were added, stirred at 50°C and 300rpm for 6 hours, filtered, washed and dried to obtain modified camellia seed shell activated carbon.

[0062] Example 3

[0063] This embodiment provides a camellia oil refining process, comprising the following steps:

[0064] Step (i): selecting plump, mildew-free, normal-colored, and impurity-free camellia seeds, drying them at 60° C. to a moisture content of 4%, and then peeling the camellia seed shells with a shelling machine to obtain camellia seed kernels; crushing the camellia seed kernels through a 120-mesh sieve, adding an antioxidant, and then performing low-temperature pressing with a press (the feed temperature of the low-temperature pressing is controlled at 30° C., and the oil outlet temperature is controlled at 50° C.) to obtain camellia crude oil; the antioxidant is a mixture of vitamin E and saffron flower extract in a weight ratio of 3:1; the amount of the antioxidant added is 0.1wt% of the weight of the camellia seed kernels;

[0065] Step (ii): cooling and dewaxing the camellia crude oil at 3°C ​​and 20rpm for 20h, filtering on a plate and frame, removing the filter residue, and obtaining camellia crude oil; soaking the macroporous adsorption resin in a 96wt% ethanol aqueous solution for 32h, wherein the weight ratio of the macroporous adsorption resin to the ethanol aqueous solution is 1:5, and then washing with water 6 times to obtain a pretreated macroporous adsorption resin; loading the pretreated macroporous adsorption resin into a column, wherein the loading amount is 2 / 3 of the column length, and then adding the camellia crude oil to the pretreated macroporous adsorption resin column at a flow rate of 5BV / h for loading, and then eluting with a 65wt% ethanol aqueous solution at a flow rate of 5BV / h until no oil flows out, centrifuging and demulsifying, extracting with ethyl acetate, and recovering the solvent by reduced pressure distillation to obtain purified camellia crude oil; wherein the macroporous adsorption resin adopts DM130 macroporous adsorption resin, which is purchased from Purui Pure Resin (Shanghai) Co., Ltd.;

[0066] Step (iii): adding the modified camellia seed shell activated carbon to the purified camellia crude oil, wherein the weight ratio of the modified camellia seed shell activated carbon to the purified camellia crude oil is 1:45, adsorbing and decolorizing for 1 hour at 27° C. and 250 rpm, centrifuging, and filtering to obtain decolorized camellia crude oil; adding the decolorized camellia crude oil to a deodorizer, vacuum deodorizing for 3 hours at 1.5 mbar and 150° C., and then gradually cooling and depressurizing to normal temperature and pressure to obtain the camellia oil.

[0067] The modified camellia seed shell activated carbon is prepared by the following method:

[0068] The camellia seed shell is crushed through a 120-mesh sieve to obtain a raw material powder; 25 parts by weight of the raw material powder is added to 70-90 parts by weight of a mixed acid, and the mixture is soaked at 27°C and 250rpm for 2 hours, filtered, washed, and dried, and then calcined at 550°C and a nitrogen atmosphere for 2 hours to obtain an initial activated carbon; the mixed acid is composed of 20wt% nitric acid, 15wt% phosphoric acid, and the balance water;

[0069] 7 parts by weight of initial activated carbon and 70 parts by weight of 35wt% ethanol aqueous solution were evenly mixed, irradiated for 20 minutes under the conditions of irradiation dose rate of 2.5 kGy / h and 60Co-γ rays, then 0.2 parts by weight of lauryl betaine and 0.4 parts by weight of propyl gallate were added, stirred for 5 hours at 60°C and 350rpm, filtered, washed and dried to obtain modified camellia seed shell activated carbon.

[0070] Comparative Example 1

[0071] The difference between this comparative example and Example 2 is that the step (i) in the refining process of the camellia oil is different, specifically as follows: plump, mildew-free, normal-colored, and impurity-free camellia seeds are selected, dried at 50° C. to a moisture content of 5%, and then the camellia seed shells are peeled off with a shelling machine to obtain camellia seed kernels; the camellia seed kernels are crushed and passed through a 100-mesh sieve, and then an antioxidant is added, and then low-temperature pressing is performed with a press (the feed temperature of the low-temperature pressing is controlled at 30° C., and the oil outlet temperature is controlled at 50° C. to obtain camellia crude oil); the antioxidant is vitamin E; and the amount of the antioxidant added is 0.08wt% of the weight of the camellia kernel.

[0072] Comparative Example 2

[0073] The difference between this comparative example and Example 2 is that the step (i) in the refining process of the camellia oil is different, which is as follows: plump, mildew-free, normal-colored, and impurity-free camellia seeds are selected, dried at 50°C to a moisture content of 5%, and then the camellia seed shells are peeled off with a shelling machine to obtain camellia seed kernels; the camellia seed kernels are crushed and passed through a 100-mesh sieve, and then an antioxidant is added, and then low-temperature pressing is performed with a press (the feed temperature of the low-temperature pressing is controlled at 30°C, and the oil outlet temperature is controlled at 50°C) to obtain camellia crude oil; the antioxidant is a saffron flower extract; and the amount of the antioxidant added is 0.08wt% of the weight of the camellia seed kernels.

[0074] Comparative Example 3

[0075] The difference between this comparative example and Example 2 is that the step (ii) in the refining process of the camellia oil is different, specifically as follows: the crude camellia oil is cooled and dewaxed at 3°C ​​and 20rpm for 20h, plate and frame filtered, and the filter residue is removed to obtain purified crude camellia oil.

[0076] Comparative Example 4

[0077] The difference between this comparative example and Example 2 is that the step (three) in the refining process of the camellia oil is different, which is as follows: the purified camellia crude oil is added to a deodorizer, and vacuum deodorized for 3 hours at 1.5 mbar and 150° C., and then gradually cooled and depressurized to normal temperature and pressure to obtain the camellia oil.

[0078] Comparative Example 5

[0079] The difference between this comparative example and Example 2 is that the step (three) in the refining process of the camellia oil is different, which is as follows: adding camellia seed shell activated carbon to the above-mentioned purified camellia crude oil, the weight ratio of the camellia seed shell activated carbon to the purified camellia crude oil is 1:45, adsorption decolorization is carried out at 27°C and 250rpm for 1h, centrifugation is carried out, and filtration is carried out to obtain decolorized camellia crude oil; the decolorized camellia crude oil is added to a deodorizer, vacuum deodorization is carried out at 1.5mbar and 150°C for 3h, and after the deodorization is completed, the deodorization is gradually cooled and depressurized to normal temperature and pressure to obtain the camellia oil.

[0080] The camellia seed shell activated carbon is prepared by the following method:

[0081] Camellia seed shells are crushed and passed through a 120-mesh sieve to obtain raw powder; 25 parts by weight of the raw powder are added to 70-90 parts by weight of a mixed acid, soaked for 2 hours at 27°C and 250rpm, filtered, washed and dried, and then calcined at 550°C and a nitrogen atmosphere for 2 hours to obtain camellia seed shell activated carbon; the mixed acid is composed of 20wt% nitric acid, 15wt% phosphoric acid and the remainder water.

[0082] Comparative Example 6

[0083] The difference between this comparative example and Example 2 is that the modified camellia seed shell activated carbon used in step (iii) of the camellia oil refining process is different, specifically as follows: the modified camellia seed shell activated carbon is prepared by the following method:

[0084] The camellia seed shell is crushed through a 120-mesh sieve to obtain a raw material powder; 25 parts by weight of the raw material powder is added to 70-90 parts by weight of a mixed acid, and the mixture is soaked at 27°C and 250rpm for 2 hours, filtered, washed, and dried, and then calcined at 550°C and a nitrogen atmosphere for 2 hours to obtain an initial activated carbon; the mixed acid is composed of 20wt% nitric acid, 15wt% phosphoric acid, and the balance water;

[0085] 7 parts by weight of initial activated carbon and 70 parts by weight of 35 wt% ethanol aqueous solution were uniformly mixed, and then 0.4 parts by weight of propyl gallate was added, stirred at 60° C. and 350 rpm for 5 hours, filtered, washed and dried to obtain modified camellia seed shell activated carbon.

[0086] Performance Testing

[0087] 1. The camellia oil obtained in the above Examples 1-3 and Comparative Examples 1-6 was stored at room temperature in a cool environment for 2 weeks, and then the odor, transparency, insoluble impurities and color of the camellia oil were measured. Among them, the insoluble impurities were measured with reference to the national standard GB / T15688-2008, and the color (Lovibond colorimetric trough 25.4 mm) was measured with reference to the national standard GB / T 22460-2008. The test results are shown in Table 1.

[0088] Table 1. Stability test results

[0089] odor transparency Insoluble impurities / % Color Example 1 Odorless Clarity and transparency ≤0.02 Yellow 0.5 Red 0 Example 2 Odorless Clarity and transparency ≤0.02 Yellow 0.5 Red 0 Example 3 Odorless Clarity and transparency ≤0.02 Yellow 0.5 Red 0 Comparative Example 1 Odorless Clarity and transparency ≤0.02 Yellow 0.5 Red 0 Comparative Example 2 Odorless Clarity and transparency ≤0.02 Yellow 0.5 Red 0 Comparative Example 3 Grease smell Clarity and transparency ≤0.05 Yellow 1.0 Red 0 Comparative Example 4 Grease smell Clarity and transparency ≤0.05 Yellow 1.5 Red 0 Comparative Example 5 Grease smell Clarity and transparency ≤0.03 Yellow 1.0 Red 0 Comparative Example 6 Grease smell Clarity and transparency ≤0.03 Yellow 1.0 Red 0

[0090] 2. The peroxide value of the camellia oil obtained in the above examples 1-3 and comparative examples 1-6 was measured with reference to the national standard GB 5009.227-2016; the acid value of the camellia oil obtained in the above examples 1-3 and comparative examples 1-6 was measured with reference to the national standard GB 5009.229-2016; 5 groups were paralleled in each case, and the average value was taken. The test results are shown in Table 2.

[0091] Table 2. Peroxide value and acid value test results

[0092] Peroxide value / (g / 100g) Acid value (KOH) / (mg / g) Example 1 0.07 0.33 Example 2 0.08 0.35 Example 3 0.10 0.39 Comparative Example 1 0.13 0.42 Comparative Example 2 0.15 0.45 Comparative Example 3 0.37 0.80 Comparative Example 4 0.30 0.85 Comparative Example 5 0.21 0.73 Comparative Example 6 0.16 0.62

[0093] It can be seen from the above performance test results that the camellia oil prepared in Examples 1-3 has stable storage performance, is odorless, clear and transparent, has a low peroxide value and a low acid value, and in particular, the comprehensive performance of the camellia oil in Example 2 is the most outstanding. This is because the present invention adds an antioxidant additive for low-temperature pressing, and then combines a non-thermal processing method such as cooling dewaxing treatment, pretreatment with a macroporous adsorption resin and modified camellia seed shell activated carbon adsorption treatment, and a vacuum deodorization treatment, so as to quickly remove impurities such as pigments under mild conditions, reduce the acid value of the camellia oil, and the ketone / aldehyde acid substances produced by peroxidation, so that the obtained camellia oil maintains a low peroxide value and a low acid value, and at the same time has stable storage performance, is clear and transparent, and has no odor.

[0094] In comparison, Comparative Examples 1-6 are significantly inferior to Examples 1-3 in the corresponding performance tests because they do not adopt the necessary technical solutions. In Comparative Examples 3-6, the pre-treated macroporous adsorption resin and the specific modified camellia seed shell activated carbon are not used simultaneously for two purifications. In Comparative Example 1-2, vitamin E and saffron flower extract are not used simultaneously as antioxidant adjuvants in low-temperature pressing. From the results, it can be seen that the stability and quality of camellia oil are reduced. The above experimental results further prove the importance of the technical solutions defined in the present invention for its technical effects. The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention, and these improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A camellia oil refining process, characterized in that: The following steps are involved: Step (1): drying camellia seeds to a moisture content of 4-6%, then peeling the camellia seed shells with a shelling machine to obtain camellia seed kernels; crushing and sieving the camellia seed kernels, then adding an antioxidant additive, and then low-temperature pressing with a press to obtain camellia crude oil; the antioxidant additive is a mixture of vitamin E and saffron flower extract; Step (ii): cooling and dewaxing the crude camellia oil for 16-20 hours, filtering on a plate and frame to obtain crude camellia oil; soaking the macroporous adsorption resin in an ethanol aqueous solution for 32-38 hours, washing with water to obtain a pretreated macroporous adsorption resin; loading the pretreated macroporous adsorption resin into a column, then adding the crude camellia oil into the pretreated macroporous adsorption resin column for loading, eluting with an ethanol aqueous solution until no oil flows out, centrifuging and demulsifying, extracting, and distilling under reduced pressure to obtain purified crude camellia oil; Step (iii): adding the modified camellia seed shell activated carbon to the purified camellia crude oil, adsorbing and decolorizing for 1-2 hours, centrifuging, filtering, and obtaining decolorized camellia crude oil; adding the decolorized camellia crude oil to a deodorizer, vacuum deodorizing for 1-3 hours, cooling and depressurizing to normal temperature and pressure after deodorization, and obtaining the camellia oil.

2. The camellia oil refining process according to claim 1, characterized in that: The following steps are involved: Step (1): drying camellia seeds to a moisture content of 4-6%, then peeling the camellia seed shells with a shelling machine to obtain camellia seed kernels; crushing and sieving the camellia seed kernels, then adding an antioxidant additive, and then low-temperature pressing with a press to obtain camellia crude oil; the antioxidant additive is a mixture of vitamin E and saffron flower extract; Step (ii): cooling and dewaxing the crude camellia oil for 16-20 hours, filtering with a plate and frame, removing the filter residue, and obtaining crude camellia oil; soaking the macroporous adsorption resin in a 92-96wt% ethanol aqueous solution for 32-38 hours, and then washing with water 4-6 times to obtain a pre-treated macroporous adsorption resin; loading the pre-treated macroporous adsorption resin into a column, and then adding the crude camellia oil to the pre-treated macroporous adsorption resin column at a flow rate of 3-5BV / h for loading, and then eluting with a 55-65wt% ethanol aqueous solution at a flow rate of 3-5BV / h until no oil flows out, centrifuging and demulsifying, extracting with ethyl acetate, and recovering the solvent by reduced pressure distillation to obtain purified crude camellia oil; Step (iii): adding the modified camellia seed shell activated carbon to the purified camellia crude oil, adsorbing and decolorizing for 1-2 hours, centrifuging, filtering, and obtaining decolorized camellia crude oil; adding the decolorized camellia crude oil to a deodorizer, vacuum deodorizing for 1-3 hours, cooling and depressurizing to normal temperature and pressure after deodorization, and obtaining the camellia oil.

3. The camellia oil refining process according to claim 1 or 2, characterized in that: The modified camellia seed shell activated carbon is prepared by the following method: The camellia seed shell is crushed and sieved to obtain a raw material powder; 15-25 parts by weight of the raw material powder is added to 70-90 parts by weight of a mixed acid, soaked for 2-4 hours, filtered, washed and dried, and then calcined at high temperature for 2-4 hours to obtain initial activated carbon; 5-7 parts by weight of initial activated carbon and 50-70 parts by weight of ethanol aqueous solution are uniformly mixed, irradiated with 60Co-γ rays for 20-40 minutes, then 0.1-0.2 parts by weight of lauryl betaine and 0.3-0.4 parts by weight of propyl gallate are added, heated and stirred for 5-7 hours, filtered, washed and dried to obtain modified camellia seed shell activated carbon.

4. The camellia oil refining process according to claim 3, characterized in that: The mixed acid consists of 10-20wt% nitric acid, 15-25wt% phosphoric acid and the balance water.

5. The camellia oil refining process according to claim 1 or 2, characterized in that: The antioxidant auxiliary agent in step (a) is a mixture of vitamin E and saffron flower extract in a weight ratio of 1-3:

1.

6. The camellia oil refining process according to claim 1 or 2, characterized in that: The amount of the antioxidant added in step (i) is 0.06-0.1wt% of the weight of the camellia seed kernel.

7. The camellia oil refining process according to claim 1 or 2, characterized in that: The conditions for low temperature pressing in step (i) are: the feed temperature is controlled within 35°C, and the oil outlet temperature is controlled within 55°C.

8. The camellia oil refining process according to claim 1 or 2, characterized in that: In step (ii), the macroporous adsorption resin is DM130 macroporous adsorption resin.

9. A camellia oil, characterized in that: Prepared according to the method according to any one of claims 1 to 8.

10. Use of the camellia oil according to claim 9 in preparing cosmetics.