A refining process for camellia oil

Abstract

This invention provides a refining process for camellia oil, belonging to the field of vegetable oil processing technology. The refining process includes the following steps: drying and shelling camellia seeds to obtain camellia seed kernels, crushing and sieving them, adding antioxidants, and low-temperature pressing to obtain crude camellia oil; dewaxing the crude camellia oil, filtering it to obtain crude camellia oil; then loading the crude camellia oil onto a pretreated macroporous adsorption resin column, eluting it with an ethanol-water solution, centrifuging to break the emulsion, extracting, and distilling under reduced pressure to obtain purified crude camellia oil; adding modified camellia seed shell activated carbon to the purified crude camellia oil for adsorption and decolorization, centrifuging, and filtering to obtain decolorized crude camellia oil; adding the decolorized crude camellia oil to a deodorizer for vacuum deodorization to obtain the camellia oil. The camellia oil obtained by this invention has high activity and stable storage performance, making it more suitable for cosmetics.

Description

Technical Field

[0001] This invention belongs to the field of vegetable oil processing technology, and in particular relates to a refining process for camellia oil. Background Technology

[0002] Camellia oil, also known as tea seed oil or wild camellia oil, is a plant oil extracted from the seeds of the camellia (Camellia oleifera Abel), a species belonging to the Theaceae family. This oil is renowned for its unique nutritional value and health benefits. It is rich in monounsaturated fatty acids, particularly oleic acid, which helps lower bad cholesterol and raise good cholesterol, making it especially beneficial for cardiovascular health. Camellia oil is also rich in vitamin E, squalene, and various antioxidants, which help protect the skin from free radical damage and delay skin aging. Furthermore, camellia oil has a high smoke point, making it suitable for high-temperature cooking and less likely to produce harmful substances, making it an ideal choice for healthy cooking. Due to its mild taste and numerous health benefits, camellia oil is widely used in Asia, especially in southern China, and is hailed as the "olive oil of the East."

[0003] Currently, the existing technologies for preparing camellia oil mainly include the following: (1) Mechanical pressing method, as a traditional extraction process, includes several stages such as traditional pressing, hydraulic pressing and screw pressing. Low temperature pressing usually refers to processing in an environment below 60℃, which preserves the natural flavor and color of the oil and completely preserves the physiologically active substances in the oil, such as vitamin E and sterols. However, the oil yield is relatively low and the cost is high. (2) Solvent extraction method, which uses organic solvents to fully soak the oil and then extracts 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) Water enzymatic method, which uses mechanical and enzymatic means to degrade the cellulose skeleton of plant cell walls 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 usability is good. However, oil emulsification may occur during the processing, the oil yield is not high, the price of enzymes is high, and it is limited in practical applications. (4) Supercritical CO2 extraction involves contacting the substance to be separated with a supercritical fluid under supercritical conditions, controlling the pressure and temperature of the system to selectively extract a certain component. This method produces oil with a lighter color and no residual solvent, but it requires high-end equipment, is expensive, and has poor operability for large-scale production. (5) Fresh pressing method uses fresh, high-quality camellia seeds as raw material. After pulping, a certain concentration of ethanol is added to extract the oil phase, and finally, the oil is purified to obtain freshly pressed camellia oil. Although this method increases the content of active ingredients, some water-soluble nutrients are discarded during the preparation process, resulting in emulsions with lower nutritional content and poor stability after the addition of emulsifiers. The cost is significantly higher than other types of camellia oil.

[0004] Camellia oil has high added value as a raw material in high-end cosmetics. However, current production processes for cosmetic camellia oil mainly follow edible oil refining processes, neglecting the unique characteristics of cosmetic camellia oil. The resulting refined camellia oil often fails to meet cosmetic requirements in terms of color, odor, and activity. To overcome these problems, this invention aims to provide a camellia oil refining process that improves upon traditional edible oil refining procedures, maximizing the retention of active ingredients in camellia oil. This results in a camellia oil more suitable for cosmetic applications, characterized by high activity, good stability, low peroxide value, and low acid value. Summary of the Invention

[0005] The purpose of this invention is to provide a refining process for camellia oil. By adding antioxidants and performing low-temperature pressing, the crude camellia oil is purified and decolorized using pretreated macroporous adsorption resin and modified camellia seed shell activated carbon. This process results in camellia oil with low peroxide value and low acid value, stable storage performance, clarity and transparency, and no off-odor, making it more suitable for cosmetics.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

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

[0008] Step (1): Dry the camellia seeds to a moisture content of 4-6%, then peel off the camellia seed shells using a shelling machine to obtain camellia seed kernels; crush and sieve the camellia seed kernels, then add antioxidants, and then press them at low temperature using a press to obtain crude camellia oil;

[0009] Step (II): Cool and dewax the crude camellia oil for 16-20 hours, filter it using a plate and frame filter to remove the filter residue, and obtain crude camellia oil; soak the macroporous adsorption resin in an ethanol-water solution for 32-38 hours, wash it with water, and obtain pretreated macroporous adsorption resin; pack the pretreated macroporous adsorption resin into a column, and then add the crude camellia oil to the pretreated macroporous adsorption resin column at a flow rate of 3-5 BV / h for sample loading, and then elute with an ethanol-water solution at a flow rate of 3-5 BV / h until no oil flows out, centrifuge to break the emulsion, extract, and distill under reduced pressure to obtain purified crude camellia oil;

[0010] Step (3): Add the modified camellia seed shell activated carbon to the above purified camellia crude oil, adsorb and decolorize for 1-2 hours, centrifuge, filter, and obtain decolorized camellia crude oil; add the decolorized camellia crude oil to a deodorizer, vacuum deodorize for 1-3 hours, and after completion, cool and depressurize to room temperature and pressure to obtain the camellia oil.

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

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

[0013] Step (II): Cool and dewax the crude camellia oil for 16-20 hours, filter it using a plate and frame filter to remove the filter residue, and obtain crude camellia oil; soak the macroporous adsorption resin in 92-96wt% ethanol aqueous solution for 32-38 hours, and then wash it with water 4-6 times to obtain pretreated macroporous adsorption resin; pack the pretreated macroporous adsorption resin into a column, and then add the crude camellia oil to the pretreated macroporous adsorption resin column at a flow rate of 3-5 BV / h for sample loading, and then elute with 55-65wt% ethanol aqueous solution at a flow rate of 3-5 BV / h until no oil flows out, centrifuge to break the emulsion, extract with ethyl acetate, and recover the solvent by vacuum distillation to obtain purified crude camellia oil;

[0014] Step (3): Add the modified camellia seed shell activated carbon to the above purified camellia crude oil, adsorb and decolorize for 1-2 hours, centrifuge, filter, and obtain decolorized camellia crude oil; add the decolorized camellia crude oil to a deodorizer, vacuum deodorize for 1-3 hours, and after completion, gradually cool and reduce the pressure to room temperature and pressure to obtain the camellia oil.

[0015] Camellia oil is rich in unsaturated fatty acids, especially oleic acid, which is much higher than in ordinary vegetable oils and is the main active ingredient. However, during refining or subsequent storage, its unsaturated fatty acids are easily oxidized (especially by high temperature, light and air contact, etc.). Oxidation will reduce the activity of camellia oil, change its color, produce off-odors, and thus deteriorate its quality.

[0016] This invention involves adding antioxidants and performing low-temperature pressing, followed by cooling and dewaxing. The crude camellia oil is then purified and decolorized using pretreated macroporous adsorption resin and modified camellia seed shell activated carbon, and vacuum deodorization is performed. This process ensures that the resulting camellia oil maintains low peroxide and low acid values, while also exhibiting stable storage performance, clarity, transparency, and odorlessness, making it more suitable for cosmetics.

[0017] This invention removes wax and solid impurities from crude camellia oil through cooling dewaxing. Then, it uses pre-treated M130 macroporous adsorption resin and modified camellia seed shell activated carbon for combined treatment, purifying the crude camellia oil twice. Under mild conditions, it can effectively adsorb pigments, free saturated fatty acids, etc. in the crude camellia oil, thereby achieving rapid removal of pigments and other impurities at room temperature, reducing the acid value of camellia oil, as well as ketone / aldehyde acid substances produced by peroxidation, and increasing the content of unsaturated fatty acids.

[0018] This invention combines cooling dewaxing, pretreatment with macroporous adsorption resin, and adsorption treatment with modified camellia seed shell activated carbon—a non-thermal processing method—to avoid the hydration degumming and alkali deacidification processes in traditional chemical refining, thus reducing the discharge of refining wastewater. The low temperature of vacuum deodorization overcomes the shortcomings of traditional deodorization processes, such as excessively high temperatures and easy oxidation of oils, and can effectively remove odorous substances from oils.

[0019] This invention utilizes modified camellia seed shell activated carbon, which is made from camellia seed shells recovered in refining step (I). This process transforms waste into treasure. The camellia seed shells are crushed and soaked in a mixed acid consisting of nitric acid and phosphoric acid, followed by high-temperature calcination to obtain initial activated carbon. Subsequently, after 60Co-γ-ray irradiation, lauryl betaine and propyl gallate are added for modification, ultimately yielding modified camellia seed shell activated carbon. Using modified camellia seed shell activated carbon can further improve adsorption performance while reducing the degree of oxidation, decreasing rancid substances produced during oxidation, and significantly improving the quality of camellia oil. The mixed acid effectively removes impurities from camellia seed shells, contributing to the purity and adsorption performance of activated carbon. It also forms more micropores and mesopores on the material surface through acid corrosion, promoting the formation of a more developed pore structure during subsequent high-temperature carbonization, thereby increasing the specific surface area and adsorption capacity of the activated carbon. 60Co-γ-ray irradiation treatment helps improve the permeability of activated carbon and activates its surface activation power. The activated carbon has increased binding capacity with lauryl betaine and propyl gallate, facilitating better bonding to the activated carbon surface. The weakly basic amino acid provided by lauryl betaine is beneficial for the adsorption of free fatty acids, thus reducing the acid value. Propyl gallate, by binding to the surface of the activated carbon carrier and dispersing in the crude camellia oil, imparts excellent antioxidant properties, thereby inhibiting the oxidation and decomposition of active ingredients in the camellia oil into odorous ketone / aldehyde acid substances during refining.

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

[0021] Camellia seed shells are crushed and sieved to obtain raw material powder; 15-25 parts by weight of raw material powder are added to 70-90 parts by weight of 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] Mix 5-7 parts by weight of initial activated carbon and 50-70 parts by weight of ethanol aqueous solution evenly, irradiate with 60Co-γ rays for 20-40 min, then add 0.1-0.2 parts by weight of lauryl betaine and 0.3-0.4 parts by weight of propyl gallate, heat and stir for 5-7 h, filter, wash and dry to obtain modified camellia seed shell activated carbon.

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

[0024] Camellia seed shells are crushed and passed through an 80-120 mesh sieve to obtain raw material powder. 15-25 parts by weight of the raw material powder are added to 70-90 parts by weight of a mixed acid and soaked at 23-27℃ and 100-250 rpm for 2-4 hours. After filtration, washing, and drying, the mixture is calcined at 450-550℃ under a nitrogen atmosphere for 2-4 hours to obtain initial activated carbon. The mixed acid consists of 10-20 wt% nitric acid, 15-25 wt% phosphoric acid, and the balance being water.

[0025] Mix 5-7 parts by weight of initial activated carbon and 50-70 parts by weight of 25-35 wt% ethanol aqueous solution evenly, and irradiate for 20-40 min under irradiation dose rate of 1-2.5 kGy / h and 60Co-γ ray conditions. Then add 0.1-0.2 parts by weight of lauryl betaine and 0.3-0.4 parts by weight of propyl gallate, and stir at 45-60℃ and 200-350 rpm for 5-7 h. After filtration, washing and drying, modified camellia seed shell activated carbon is obtained.

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

[0027] The CAS number for the saffron (CROCUS SATIVUS) flower extract is 84604-17-1.

[0028] This invention utilizes low-temperature pressing in an environment containing the aforementioned specific antioxidant auxiliaries. This effectively avoids the oxidative damage to the active ingredients in camellia oil caused by air contact and heating during refining, overcoming the problem of low active ingredient content in camellia oil in existing technologies. This invention also employs vitamin E and saffron flower extract as antioxidant auxiliaries. Both play their roles at different stages of oxidation. Vitamin E can react with lipid peroxide free radicals or lipid oxygen free radicals, interrupting the chain reaction of oil oxidation. Saffron flower extract, by enhancing the ability to scavenge primary free radicals, synergistically enhances the overall antioxidant capacity with vitamin E. This synergistic and complementary approach helps to form more effective antioxidant protection during low-temperature pressing, reducing the oxidative loss of active ingredients and thus improving the quality and stability of camellia oil.

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

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

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

[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 used in step (ii) is DM130 macroporous adsorption resin.

[0034] Preferably, the amount of pretreated macroporous adsorption resin packed into the column in step (ii) is 1 / 3 to 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 and decolorization in step (iii) are: temperature 23-27℃ and stirring speed 100-250rpm.

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

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

[0039] This invention also provides the application of the above-mentioned camellia oil in the preparation of cosmetics.

[0040] Preferably, the applications include, but are not limited to: using the above-mentioned camellia oil to prepare camellia oil face 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 as follows:

[0042] 1. This invention provides a refining process for camellia oil. By adding specific antioxidants and performing low-temperature pressing, followed by two purification and decolorization steps using pretreated macroporous adsorption resin and modified camellia seed shell activated carbon, the active ingredients of camellia oil are preserved to the maximum extent. This results in camellia oil with low peroxide value and low acid value, stable storage performance, and clear and transparent properties, making it more suitable for the preparation of cosmetics.

[0043] 2. This invention uses pretreated macroporous adsorption resin and modified camellia seed shell activated carbon to purify camellia crude oil twice, directly removing impurities such as wax, free saturated fatty acids, and colored substances from the oil. This avoids the addition of chemicals such as sodium chloride, sodium hydroxide, and acids to the oil during the water washing and alkali refining processes in the prior art, and does not cause the loss of active ingredients in the oil.

[0044] 3. The modified camellia seed shell activated carbon used in this invention uses camellia seed shells recovered in refining step (I) as raw materials, 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 Implementation

[0045] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0046] Example 1

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

[0048] Step (1): Select plump, mold-free, normally colored, and impurity-free camellia seeds, dry them at 45℃ to a moisture content of 6%, then peel off the shells using a shelling machine to obtain camellia seed kernels; crush the camellia seed kernels through an 80-mesh sieve, then add an antioxidant, and then perform low-temperature pressing using a press (the feed temperature for low-temperature pressing is controlled at 30℃, and the oil output temperature is controlled at 50℃) to obtain crude camellia oil; the antioxidant is a mixture of vitamin E and saffron flower extract in a weight ratio of 1:1; the amount of antioxidant added is 0.06 wt% of the weight of the camellia seed kernels;

[0049] Step (II): Camellia crude oil was cooled and dewaxed at 1℃ and 10rpm for 16h, filtered through a plate and frame filter to remove the filter residue, and camellia crude oil was obtained. Macroporous adsorption resin was soaked in 92wt% ethanol aqueous solution for 38h, with the weight ratio of macroporous adsorption resin to ethanol aqueous solution being 1:3. Then, it was washed with water 4 times to obtain pretreated macroporous adsorption resin. The pretreated macroporous adsorption resin was packed into a column with a packing volume of 1 / 3 of the column length. Camellia crude oil was added to the pretreated macroporous adsorption resin column at a flow rate of 3BV / h for sample loading. Then, it was eluted with 55wt% ethanol aqueous solution at a flow rate of 3BV / h until no oil flowed out. Centrifugation was performed to break the emulsion, and extraction was performed with ethyl acetate. The solvent was recovered by vacuum distillation to obtain purified camellia crude oil. The macroporous adsorption resin used was DM130 macroporous adsorption resin, which was purchased from Piaoyi Pure Resin (Shanghai) Co., Ltd.

[0050] Step (3): Modified camellia seed shell activated carbon is added to the above purified camellia crude oil, wherein the weight ratio of modified camellia seed shell activated carbon to purified camellia crude oil is 1:35. Adsorption and decolorization are carried out at 23℃ and 100rpm for 2 hours, followed by centrifugation and filtration to obtain decolorized camellia crude oil. The decolorized camellia crude oil is added to a deodorizer and vacuum deodorized at 0.5mbar and 180℃ for 1 hour. After completion, the pressure is gradually reduced to room temperature and pressure to obtain the camellia oil.

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

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

[0053] Five parts by weight of initial activated carbon and 50 parts by weight of 25 wt% ethanol aqueous solution were mixed evenly and irradiated for 40 min under irradiation dose rate of 1 kGy / h and 60Co-γ ray conditions. Then, 0.1 parts by weight of lauryl betaine and 0.3 parts by weight of propyl gallate were added and stirred at 45℃ and 200 rpm for 7 h. After filtration, washing and drying, modified camellia seed shell activated carbon was obtained.

[0054] Example 2

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

[0056] Step (1): Select plump, mold-free, normally colored, and impurity-free camellia seeds, dry them at 50℃ to a moisture content of 5%, then peel off the shells using a shelling machine to obtain camellia seed kernels; crush the camellia seed kernels through a 100-mesh sieve, then add an antioxidant, and then perform low-temperature pressing using a press (the feed temperature for low-temperature pressing is controlled at 30℃, and the oil output temperature is controlled at 50℃) to obtain crude camellia oil; the antioxidant is a mixture of vitamin E and saffron flower extract in a weight ratio of 2:1; the amount of antioxidant added is 0.08 wt% of the weight of the camellia seed kernels;

[0057] Step (II): Camellia crude oil was cooled and dewaxed at 2℃ and 15rpm for 18h, filtered through a plate and frame filter to remove the filter residue, and camellia crude oil was obtained. Macroporous adsorption resin was soaked in 95wt% ethanol aqueous solution for 36h, with the weight ratio of macroporous adsorption resin to ethanol aqueous solution being 1:4. Then, it was washed with water 5 times to obtain pretreated macroporous adsorption resin. The pretreated macroporous adsorption resin was packed into a column with a packing volume of 1 / 2 of the column length. Camellia crude oil was added to the pretreated macroporous adsorption resin column at a flow rate of 4BV / h for sample loading. Elution was then performed with 60wt% ethanol aqueous solution at a flow rate of 4BV / h until no oil flowed out. Centrifugation was performed to break the emulsion, and extraction was performed with ethyl acetate. The solvent was recovered by vacuum distillation to obtain purified camellia crude oil. The macroporous adsorption resin used was DM130 macroporous adsorption resin, which was purchased from Piaoyi Pure Resin (Shanghai) Co., Ltd.

[0058] Step (3): Modified camellia seed shell activated carbon is added to the above purified camellia crude oil, wherein the weight ratio of modified camellia seed shell activated carbon to purified camellia crude oil is 1:40. The mixture is adsorbed and decolorized at 25℃ and 200rpm for 1.5h, centrifuged, and filtered to obtain decolorized camellia crude oil. The decolorized camellia crude oil is added to a deodorizer and deodorized under vacuum at 1mbar and 160℃ for 2h. After the deodorization is completed, the mixture is gradually cooled and depressurized to room temperature and pressure to obtain the camellia oil.

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

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

[0061] Six parts by weight of initial activated carbon and 60 parts by weight of 30 wt% ethanol aqueous solution were mixed evenly and irradiated for 30 min under irradiation dose rate of 2 kGy / h and 60Co-γ ray conditions. Then, 0.15 parts by weight of lauryl betaine and 0.35 parts by weight of propyl gallate were added and stirred at 50℃ and 300 rpm for 6 h. After filtration, washing and drying, modified camellia seed shell activated carbon was obtained.

[0062] Example 3

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

[0064] Step (1): Select plump, mold-free, normally colored, and impurity-free camellia seeds, dry them at 60℃ to a moisture content of 4%, then peel off the shells using a shelling machine to obtain camellia seed kernels; crush the camellia seed kernels through a 120-mesh sieve, then add an antioxidant, and then perform low-temperature pressing using a press (the feed temperature for low-temperature pressing is controlled at 30℃, and the oil output temperature is controlled at 50℃) to obtain crude camellia oil; the antioxidant is a mixture of vitamin E and saffron flower extract in a weight ratio of 3:1; the amount of antioxidant added is 0.1wt% of the weight of the camellia seed kernels;

[0065] Step (II): Camellia crude oil was cooled and dewaxed at 3℃ and 20rpm for 20h, filtered through a plate and frame filter to remove the filter residue, and camellia crude oil was obtained. Macroporous adsorption resin was soaked in 96wt% ethanol aqueous solution for 32h, with the weight ratio of macroporous adsorption resin to ethanol aqueous solution being 1:5. Then, it was washed with water 6 times to obtain pretreated macroporous adsorption resin. The pretreated macroporous adsorption resin was packed into a column with a packing volume of 2 / 3 of the column length. Camellia crude oil was added to the pretreated macroporous adsorption resin column at a flow rate of 5BV / h for sample loading. Elution was then performed with 65wt% ethanol aqueous solution at a flow rate of 5BV / h until no oil flowed out. Centrifugation was performed to break the emulsion, and extraction was performed with ethyl acetate. The solvent was recovered by vacuum distillation to obtain purified camellia crude oil. The macroporous adsorption resin used was DM130 macroporous adsorption resin, purchased from Piaoyi Pure Resin (Shanghai) Co., Ltd.

[0066] Step (3): Add modified camellia seed shell activated carbon to the above purified camellia crude oil, wherein the weight ratio of modified camellia seed shell activated carbon to purified camellia crude oil is 1:45. Adsorb and decolorize at 27℃ and 250rpm for 1 hour, centrifuge, and filter to obtain decolorized camellia crude oil. Add the decolorized camellia crude oil to a deodorizer and deodorize under vacuum at 1.5mbar and 150℃ for 3 hours. After completion, gradually cool and depressurize to room temperature and pressure to obtain the camellia oil.

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

[0068] Camellia seed shells were crushed and passed through a 120-mesh sieve to obtain raw material powder. 25 parts by weight of the raw material powder were added to 70-90 parts by weight of a mixed acid and soaked for 2 hours at 27°C and 250 rpm. After filtration, washing, and drying, the powder was calcined at 550°C under a nitrogen atmosphere for 2 hours to obtain initial activated carbon. The mixed acid consisted of 20 wt% nitric acid, 15 wt% phosphoric acid, and the remainder water.

[0069] Seven parts by weight of initial activated carbon and 70 parts by weight of 35 wt% ethanol aqueous solution were mixed evenly and irradiated for 20 min under irradiation dose rate of 2.5 kGy / h and 60 Co-γ ray conditions. Then, 0.2 parts by weight of lauryl betaine and 0.4 parts by weight of propyl gallate were added and stirred at 60℃ and 350 rpm for 5 h. After filtration, washing and drying, modified camellia seed shell activated carbon was obtained.

[0070] Comparative Example 1

[0071] The difference between this comparative example and Example 2 is that step (I) in the refining process of the camellia oil is different, as follows: Select plump, mold-free, normally colored, and impurity-free camellia seeds, dry them at 50°C to a moisture content of 5%, and then peel off the camellia seed shells using a shelling machine to obtain camellia seed kernels; crush the camellia seed kernels through a 100-mesh sieve, then add an antioxidant, and then perform low-temperature pressing using a press (the feed temperature of low-temperature pressing is controlled at 30°C, and the oil output temperature is controlled at 50°C to obtain crude camellia oil); the antioxidant is vitamin E; the amount of antioxidant added is 0.08 wt% of the weight of the camellia seed kernels.

[0072] Comparative Example 2

[0073] The difference between this comparative example and Example 2 is that step (I) in the refining process of the camellia oil is different, as follows: Select plump, mold-free, normally colored, and impurity-free camellia seeds, dry them at 50°C to a moisture content of 5%, and then peel off the camellia seed shells using a shelling machine to obtain camellia seed kernels; crush the camellia seed kernels through a 100-mesh sieve, then add an antioxidant, and then perform low-temperature pressing using a press (the feed temperature of low-temperature pressing is controlled at 30°C, and the oil output temperature is controlled at 50°C) to obtain crude camellia oil; the antioxidant is saffron flower extract; the amount of antioxidant added is 0.08 wt% of the weight of the camellia seed kernels.

[0074] Comparative Example 3

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

[0076] Comparative Example 4

[0077] The difference between this comparative example and Example 2 is that step (iii) in the refining process of the camellia oil is different, as follows: the purified crude camellia oil is added to a deodorizer and deodorized under vacuum at 1.5 mbar and 150°C for 3 hours. After the deodorization is completed, the pressure is gradually reduced to room temperature and pressure to obtain the camellia oil.

[0078] Comparative Example 5

[0079] The difference between this comparative example and Example 2 is that step (iii) in the refining process of the camellia oil is different, as follows: Camellia seed shell activated carbon is added to the above purified camellia crude oil, the weight ratio of the camellia seed shell activated carbon to the purified camellia crude oil is 1:45, and adsorption and decolorization are carried out at 27°C and 250 rpm for 1 hour, followed by centrifugation and filtration to obtain decolorized camellia crude oil; the decolorized camellia crude oil is added to a deodorizer and vacuum deodorized at 1.5 mbar and 150°C for 3 hours, and after completion, it is gradually cooled and depressurized to room temperature and pressure to obtain the camellia oil.

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

[0081] Camellia seed shells were crushed and passed through a 120-mesh sieve to obtain raw material powder. 25 parts by weight of the raw material powder were added to 70-90 parts by weight of a mixed acid and soaked for 2 hours at 27°C and 250 rpm. After filtration, washing, and drying, the powder was calcined at 550°C under a nitrogen atmosphere for 2 hours to obtain camellia seed shell activated carbon. The mixed acid consisted of 20 wt% nitric acid, 15 wt% 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, as follows: The modified camellia seed shell activated carbon is prepared by the following method:

[0084] Camellia seed shells were crushed and passed through a 120-mesh sieve to obtain raw material powder. 25 parts by weight of the raw material powder were added to 70-90 parts by weight of a mixed acid and soaked for 2 hours at 27°C and 250 rpm. After filtration, washing, and drying, the powder was calcined at 550°C under a nitrogen atmosphere for 2 hours to obtain initial activated carbon. The mixed acid consisted of 20 wt% nitric acid, 15 wt% phosphoric acid, and the remainder water.

[0085] Seven parts by weight of initial activated carbon and 70 parts by weight of 35 wt% ethanol aqueous solution were mixed evenly, and then 0.4 parts by weight of propyl gallate were added. The mixture was stirred at 60℃ 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 oils obtained in Examples 1-3 and Comparative Examples 1-6 were stored at room temperature and in a cool environment for 2 weeks. Then, the odor, transparency, insoluble impurities, and color of the camellia oils were measured. Among them, the insoluble impurities were measured according to the national standard GB / T15688-2008, and the color (Lovibond colorimeter 25.4mm) was measured according 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 Tasteless Clarity and transparency ≤0.02 Yellow 0.5 Red 0 Example 2 Tasteless Clarity and transparency ≤0.02 Yellow 0.5 Red 0 Example 3 Tasteless Clarity and transparency ≤0.02 Yellow 0.5 Red 0 Comparative Example 1 Tasteless Clarity and transparency ≤0.02 Yellow 0.5 Red 0 Comparative Example 2 Tasteless Clarity and transparency ≤0.02 Yellow 0.5 Red 0 Comparative Example 3 It has an oily smell Clarity and transparency ≤0.05 Yellow 1.0 Red 0 Comparative Example 4 It has an oily smell Clarity and transparency ≤0.05 Yellow 1.5 Red 0 Comparative Example 5 It has an oily smell Clarity and transparency ≤0.03 Yellow 1.0 Red 0 Comparative Example 6 It has an oily smell Clarity and transparency ≤0.03 Yellow 1.0 Red 0

[0090] 2. The peroxide value of the camellia oils obtained in Examples 1-3 and Comparative Examples 1-6 above was determined according to the national standard GB 5009.227-2016; the acid value of the camellia oils obtained in Examples 1-3 and Comparative Examples 1-6 above was determined according to the national standard GB 5009.229-2016; each example was tested in 5 parallel groups, and the average value was taken. The test results are shown in Table 2.

[0091] Table 2. Results of peroxide value and acid value tests

[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] As can be seen from the above performance test results, the camellia oil prepared in Examples 1-3 has stable storage performance, is odorless, clear and transparent, and has low peroxide value and low acid value. In particular, the camellia oil in Example 2 has the most outstanding comprehensive performance. This is because the present invention uses a non-thermal processing method, which combines low-temperature pressing with the addition of antioxidants, followed by cooling dewaxing, pretreatment with macroporous adsorption resin and modified camellia seed shell activated carbon adsorption, and vacuum deodorization. Under mild conditions, it can quickly remove impurities such as pigments, reduce the acid value of camellia oil, and reduce ketone / aldehyde acid substances produced by peroxidation. This results in camellia oil with low peroxide value and low acid value, stable storage performance, clarity and transparency, and no off-odor.

[0094] In comparison, Comparative Examples 1-6, lacking the necessary technical solutions, showed significantly inferior performance compared to Examples 1-3 in their respective performance tests. Comparative Examples 3-6 did not simultaneously employ pre-treated macroporous adsorption resin and specifically modified camellia seed shell activated carbon for double purification. Comparative Examples 1-2, in their low-temperature pressing, did not simultaneously use vitamin E and saffron flower extract as antioxidants. The results clearly show that this led to a decline in the stability and quality of the camellia oil. These experimental results further demonstrate the importance of the technical solutions defined in this invention for its technical effectiveness. The above description represents the preferred embodiment of this invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications should also be considered within the scope of protection of this invention.

Claims

1. A refining process for camellia oil, characterized in that, Includes the following steps: Step (1): Select plump, mold-free, normally colored, and impurity-free camellia seeds, dry them at 45-60℃ to a moisture content of 4-6%, then peel off the camellia seed shells using a shelling machine to obtain camellia seed kernels; crush and sieve the camellia seed kernels, then add an antioxidant aid, and then press them at low temperature using a press to obtain crude camellia oil; the antioxidant aid is a mixture of vitamin E and saffron flower extract; Step (II): Cool and dewax the crude camellia oil for 16-20 hours, filter it using a plate and frame filter to remove the filter residue, and obtain crude camellia oil; soak the macroporous adsorption resin in 92-96wt% ethanol aqueous solution for 32-38 hours, and then wash it with water 4-6 times to obtain pretreated macroporous adsorption resin; pack the pretreated macroporous adsorption resin into a column, and then add the crude camellia oil to the pretreated macroporous adsorption resin column at a flow rate of 3-5 BV / h for sample loading, and then elute with 55-65wt% ethanol aqueous solution at a flow rate of 3-5 BV / h until no oil flows out, centrifuge to break the emulsion, extract with ethyl acetate, and recover the solvent by vacuum distillation to obtain purified crude camellia oil; Step (3): Add the modified camellia seed shell activated carbon to the above purified camellia crude oil, adsorb and decolorize for 1-2 hours, centrifuge, filter to obtain decolorized camellia crude oil; add the decolorized camellia crude oil to a deodorizer, vacuum deodorize for 1-3 hours, cool and depressurize to room temperature and pressure after completion to obtain the camellia oil. The preparation method of modified camellia seed shell activated carbon includes: Camellia seed shells are crushed and sieved to obtain raw material powder; 15-25 parts by weight of raw material powder are added to 70-90 parts by weight of 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. Mix 5-7 parts by weight of initial activated carbon and 50-70 parts by weight of ethanol aqueous solution evenly, irradiate with 60Co-γ rays for 20-40 min, then add 0.1-0.2 parts by weight of lauryl betaine and 0.3-0.4 parts by weight of propyl gallate, heat and stir for 5-7 h, filter, wash and dry to obtain modified camellia seed shell activated carbon; The conditions for vacuum deodorization are: pressure 0.5-1.5 mbar and temperature 150-180℃; The antioxidant aid mentioned in step (I) is a mixture of vitamin E and saffron flower extract in a weight ratio of 1-3:1; The amount of antioxidant added in step (1) is 0.06-0.1 wt% of the weight of camellia seed kernel.

2. The refining process for camellia oil according to claim 1, characterized in that, The mixed acid consists of 10-20 wt% nitric acid, 15-25 wt% phosphoric acid, and the balance being water.

3. The refining process for camellia oil according to claim 1, characterized in that, The conditions for low-temperature pressing in step (1) are: the feed temperature is controlled within 35℃ and the oil output temperature is controlled within 55℃.

4. The refining process for camellia oil according to claim 1, characterized in that, In step (ii), the macroporous adsorption resin used is DM130 macroporous adsorption resin.

5. A camellia oil, characterized in that, Prepared using the refining process according to any one of claims 1-4.

6. The application of camellia oil according to claim 5 in the preparation of cosmetics.