A simple method for separating components of oil-tea camellia cake
By using a simple separation method to separate tea saponin, tea protein, and lignocellulose from camellia seed cake, the problem of resource waste in existing technologies is solved, and efficient, simple, and high-value utilization is achieved. The tea saponin has high purity and is suitable for detergents and animal feed, while the lignocellulose can be used to prepare natural colored nanocellulose.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HUAYAN INT COSMETICS RES INST BAIYUN MEIWAN BAIYUN DISTRICT GUANGZHOU
- Filing Date
- 2023-09-20
- Publication Date
- 2026-07-31
AI Technical Summary
Existing technologies are unable to effectively utilize the high-value-added components in camellia oil meal, and the processing technology is complex or dangerous, leading to resource waste and increased environmental pressure.
The separation of tea saponin, tea protein, and lignocellulose is achieved by freezing tea oil meal powder in an alkaline aqueous solution, thawing it, mechanically crushing it, heating and centrifuging it, then adding an alkaline precipitant and chitosan solution and centrifuging it after standing. Finally, the tea saponin calcium precipitate is treated with ammonium bicarbonate solution.
This method achieves efficient separation and high-value utilization of tea saponin, tea protein, and lignocellulose in camellia seed cake. The tea saponin has high purity and light color, the tea protein is suitable for animal feed, and the lignocellulose can be used to prepare natural colored nanocellulose. The process is simple and easy to industrialize.
Smart Images
Figure CN117443015B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of agricultural and forestry waste processing technology, specifically involving a simple method for separating the components of camellia seed meal. Background Technology
[0002] Camellia oil meal is the residue left after pressing camellia seeds for oil after the camellia fruit has been shelled. Because it is bitter and slightly toxic, most of the camellia oil meal is discarded, and its value is not fully utilized.
[0003] Camellia oleifera Abel, belonging to the genus Camellia in the family Theaceae, is an evergreen small tree or shrub. It is a unique woody oilseed tree species in my country, with a cultivation and utilization history of over 2000 years. Along with olive, oil palm, and coconut, it is considered one of the world's four major woody oilseed plants. In 2020, my country's Camellia oleifera planting area reached 68 million mu (approximately 4.9 million hectares), with Camellia seed and Camellia oil production reaching 3.14 million tons and 720,000 tons respectively, and Camellia meal production exceeding 2 million tons. With the increase in Camellia oleifera production, the processing waste—Camellia meal—is placing increasing pressure on the environment.
[0004] Studies have shown that camellia seed meal after oil extraction contains abundant nutrients such as lignocellulose, protein, polysaccharides, phenols, saponins, and flavonoids. To utilize camellia seed meal resources, patent CN201610027047.6 describes a rapid preparation method for flavonoid glycosides from camellia seed meal. This method involves alcohol extraction, enrichment and purification using macroporous adsorption resin, and low-pressure column chromatography purification to separate the flavonoid glycoside monomers from the camellia seed meal. This method requires minimal equipment and is simple to operate, providing a way to utilize camellia seed meal for high-value purposes. However, the use of alcohols during production is hazardous, and a large amount of lignocellulose, protein, and other substances remaining in the camellia seed meal cannot be utilized. Existing technologies also extract tea saponins through ultrasonic alkaline dissolution followed by acid precipitation. This method promotes the high-value utilization of camellia seed meal to some extent, but the utilization rate needs further improvement, and it generates a large amount of wastewater.
[0005] To utilize the rich protein in camellia seed cake, it can be used as a raw material for feed compounding. However, camellia seed cake contains anti-nutritional factors such as saponins and tannins, which have poor palatability as animal feed and can easily cause animal discomfort or poisoning. Therefore, if camellia seed cake is to be used in feed, it must be detoxified. Patent CN200910115556.4, "Method for Fermenting Camellia Seed Cake to Produce Animal Feed by *Variegata robusta*", discloses a method for obtaining protein feed by fermenting camellia seed cake and extracting camellia seed oil and camellia saponins from camellia seed kernels and using them in camellia seed cake feed. However, these methods are complex and require pretreatment of raw materials to remove tea saponins. Summary of the Invention
[0006] In order to overcome the shortcomings of the existing technology, the purpose of this invention is to provide a simple method for separating the components of camellia seed cake, which can fully extract high value-added products from camellia seed cake through a simple process and avoid the cumbersome process of the existing technology.
[0007] The objective of this invention is achieved through the following technical solution:
[0008] A simple method for separating the components of camellia seed cake, the specific steps of which are as follows:
[0009] (1) Add camellia seed meal powder to an alkaline aqueous solution for freezing treatment to obtain frozen camellia seed meal;
[0010] (2) Take out the frozen camellia seed cake, thaw it and add alkaline aqueous solution, then mechanically crush, heat and centrifuge to obtain supernatant A and wood fiber;
[0011] (3) Add an alkaline precipitant to the supernatant A, let it stand and then centrifuge to obtain supernatant B and calcium tea saponate precipitate. Add acetic acid and chitosan solution to supernatant B, let it stand and then centrifuge to obtain tea oil protein.
[0012] The calcium saponate precipitate is added to an ammonium bicarbonate solution for solid-liquid separation. The liquid obtained after solid-liquid separation is concentrated by evaporation to obtain the finished tea saponin product.
[0013] Preferably, the camellia seed meal powder is 40-200 mesh.
[0014] More preferably, the tea seed meal powder is 100 mesh.
[0015] Preferably, the freezing time in step (1) is 4 to 24 hours.
[0016] More preferably, the freezing time is 6 hours.
[0017] Preferably, the alkaline aqueous solution is one of sodium hydroxide, sodium carbonate, trisodium phosphate, sodium citrate, or sodium tetraborate.
[0018] Preferably, the liquid-to-solid ratio of the alkaline aqueous solution to the camellia seed meal powder is 5 to 30:1.
[0019] More preferably, the liquid-to-solid ratio of the alkaline aqueous solution to the camellia seed meal powder is 10:1.
[0020] Preferably, the specific steps of heating in step (2) are as follows:
[0021] The camellia seed meal solution was heated to 30-60℃ and the reaction time was 1-6 hours.
[0022] More preferably, the camellia seed meal solution is heated to 40-60°C and the reaction time is 4 hours.
[0023] Preferably, the mechanical crushing process in step (2) takes 10 to 120 minutes.
[0024] More preferably, the mechanical pulverization process takes 30 to 60 minutes.
[0025] Preferably, the alkaline precipitant in step (3) is calcium oxide or calcium hydroxide.
[0026] Preferably, the concentration of the alkaline precipitant is 1 to 10 wt%.
[0027] More preferably, the concentration of the alkaline precipitant is 5 wt%.
[0028] Preferably, the molar ratio of ammonium bicarbonate solution to alkaline precipitant in step (3) is 1 to 1.5:1.
[0029] More preferably, the molar ratio of ammonium bicarbonate solution to alkaline precipitant in step (3) is 1.05:1.
[0030] Preferably, the concentration of the chitosan solution in step (3) is 0.5–5 wt%.
[0031] More preferably, the concentration of the chitosan solution is 2 wt%.
[0032] More preferably, the chitosan solution is a high-viscosity chitosan solution.
[0033] Preferably, the supernatant A is mainly composed of kernels, and its components are protein, oil, tea saponin, polysaccharide and tannin.
[0034] Preferably, the wood fiber can be used as coarse fiber or for extracting cellulose and light-colored lignin.
[0035] Preferably, the settling time in step (3) is 1 to 24 hours.
[0036] The present invention has the following advantages and beneficial effects compared with the prior art:
[0037] The separation method provided by this invention effectively separates lignin, camellia protein, and tea saponin from camellia oil meal through a simple process, allowing for their high-value utilization. The separation method is simple, efficient, and does not require expensive equipment, making it easy to industrialize. Without using harsh conditions of high temperature and high alkali, the extracted tea saponin has a high yield, light color, and high purity. The method achieves a tea saponin yield of 13.96% and a purity of over 80%, which can be used as a green surfactant after simple purification. The extracted protein retains the original protein efficacy of the camellia oil meal, with low tea saponin content in the crude protein and no characteristic bitterness of tea saponin, making it suitable for animal feed for cattle, sheep, and pigs. It can also be further purified and used as a functional additive in compound foods. The extracted lignin cellulose possesses the original brown pigment of the camellia oil plant and has high cellulose and lignin content, making it suitable for preparing naturally colored nanocellulose, nano-lignin cellulose, and extracting lignin. This light-colored lignin can be used as a raw material for sunscreens.
[0038] The separation method provided by this invention involves freezing an aqueous solution of camellia seed oil meal, which causes the water that has permeated into the meal to freeze, resulting in cell wall expansion and disruption of the microstructure of the meal, making it easier to extract active ingredients. Mechanical pulverization of the camellia seed oil meal solution further facilitates the separation of active ingredients from the lignocellulose. Adding calcium tea saponate precipitate to an ammonium bicarbonate solution causes the calcium tea saponate to react and generate tea saponin and calcium carbonate. The tea saponin dissolves in water, while the calcium carbonate precipitates. Attached Figure Description
[0039] Figure 1 The infrared spectrum of the light-colored tea saponin extracted in Example 1 of this invention;
[0040] Figure 2 The infrared spectrum of lignocellulose extracted in Example 1 of this invention; Detailed Implementation
[0041] The invention's objective will be further described in detail below with reference to the accompanying drawings and specific embodiments. The embodiments cannot be described in detail here, but the implementation of the invention is not limited to the following embodiments.
[0042] Example 1:
[0043] Take 20g of 200-mesh camellia seed meal powder and add it to 100ml of 0.05mol / L sodium hydroxide solution until it is just moistened. Stir well and then place the camellia seed meal aqueous solution in a refrigerator for 4 hours to obtain frozen camellia seed meal.
[0044] Remove the frozen camellia seed meal and allow it to return to room temperature. Add 50 ml of 0.05 mol / L sodium hydroxide solution, then process it using a grinder for 30 minutes to obtain a ground camellia seed meal solution. Heat the solution to 60℃ and react for 1 hour, then centrifuge while hot. Separate the camellia seed meal solution into supernatant A and precipitate using a centrifuge. Collect supernatant A. The precipitate is lignocellulose, which can be used as coarse fiber or for extracting colored nanocellulose and light-colored lignin. The component ratios of supernatant A and lignocellulose are shown in Table 1.
[0045] Add 1g of calcium oxide to the supernatant A, let it stand for 24 hours to precipitate, and then centrifuge to obtain calcium saponate precipitate and supernatant B. Collect the calcium saponate precipitate for later use.
[0046] Acetic acid was added to the supernatant B to adjust the pH to 3-4. 0.4g of high-viscosity chitosan solution was added and the mixture was allowed to stand for 2 hours. After centrifugation, camellia oleifera protein was obtained. Its main components are oil, protein, and water-insoluble polysaccharides. It can be used as roughage.
[0047] Add 1.4g of ammonium bicarbonate solution (50wt%) to the calcium saponate precipitate obtained above, stir for 10min and centrifuge, collect the supernatant, and evaporate the supernatant to dryness using a rotary evaporator to obtain tea saponin solid powder with a purity of up to 80%, which can be used in subsequent cleaning and chemical products.
[0048] Example 2:
[0049] Take 240g of 100-mesh camellia seed meal powder and add 300ml of 0.05mol / L sodium carbonate aqueous solution to just wet it. Stir well and freeze in a freezer for 6 hours to obtain frozen camellia seed meal.
[0050] Remove the frozen camellia seed meal and allow it to return to room temperature. Add 500 ml of 0.05 mol / L sodium carbonate solution, then process it through a colloid mill for 60 min with a 1 mm gap to obtain a pulverized camellia seed meal solution. Heat the solution to 60℃ and react for 2 h, then centrifuge while hot. Separate the camellia seed meal solution into supernatant A and precipitate using a centrifuge. Collect supernatant A, which can be used as crude fiber or for extracting colored cellulose and lignin. The component ratio of supernatant A and lignin is shown in Table 1. Add 19.2 g of calcium hydroxide to supernatant A, stir for 10 min, allow it to stand for 2 h to precipitate, and then centrifuge to obtain calcium saponate precipitate and supernatant B. Collect the calcium saponate precipitate for later use.
[0051] Acetic acid was added to the supernatant B to adjust the pH to 3–4. 4.8g of high-viscosity chitosan solution was added, and after standing for 2 hours, the mixture was centrifuged to obtain camellia oleifera protein. Its main components are oil, protein, and water-insoluble polysaccharides, and it can be used as roughage.
[0052] Add 21.5g of ammonium bicarbonate solution (50wt%) to the calcium saponate precipitate obtained above, stir for 10min and centrifuge, collect the supernatant, and evaporate the supernatant to dryness using a rotary evaporator to obtain solid tea saponin powder with a purity of up to 80%, which can be used in subsequent cleaning and chemical products.
[0053] Example 3:
[0054] Take 4 kg of 40-mesh camellia seed meal powder and add 6 L of 0.01 mol / L sodium hydroxide aqueous solution. Stir well and then freeze the camellia seed meal aqueous solution in a cold storage for 24 hours to obtain frozen camellia seed meal.
[0055] Remove the frozen camellia seed meal and allow it to return to room temperature. Add 30 L of 0.01 mol / L sodium hydroxide aqueous solution and reflux through a disc mill for 60 min with a gap of 1.2 mm to obtain a pulverized camellia seed meal solution. Heat to 40℃ and react for 2 h. Separate the solution into supernatant A and precipitate using a slag remover. Collect supernatant A. The precipitate is lignocellulose, which can be used as coarse fiber or for extracting cellulose and lignin. The component ratios of supernatant A and lignocellulose are shown in Table 1.
[0056] Add 40g of calcium hydroxide to the supernatant A, stir for 30min, and let stand for 2h to precipitate. Centrifuge, collect the calcium saponate precipitate and supernatant B, and set aside for later use.
[0057] Add acetic acid to the supernatant B, adjust the pH to 3-4, add 120g of low-viscosity chitosan solution, let stand for 6 hours, and then treat with a slag remover. The precipitate mainly consists of oils, proteins, and water-insoluble polysaccharides. The precipitate can be used as roughage.
[0058] Add 55g of ammonium bicarbonate (50wt%) to the calcium saponate precipitate obtained above, treat with a slag remover, collect the supernatant, and use a spray dryer to obtain tea saponin powder with a purity of up to 80%, which can be used in subsequent cleaning and chemical products.
[0059] Table 1. Component ratios of supernatant A and wood fibers in each embodiment.
[0060]
[0061] As shown in Table 1, the main components of supernatant A are tea saponin, protein, and oil. Tea saponin can be separated and used as a raw material for personal care products. The protein in supernatant A can be used as animal feed. The lignocellulose, mainly consisting of cellulose, hemicellulose, and lignin, can be used as crude fiber or for extracting cellulose and lignin. The separation method provided by this invention can effectively separate lignocellulose, tea protein, and tea saponin from camellia seed cake through a simple process, allowing for their high-value utilization. The separation method is simple, efficient, does not require expensive equipment, and is easily industrialized.
[0062] Figure 1 The infrared spectrum of the light-colored tea saponin extracted in Example 1 of this invention is shown below. Figure 2 It can be seen that at 3403cm －1 There is a tensile vibration peak of OH at 2925 cm⁻¹. －1 The nearby absorption peak corresponds to the C-H stretching vibration peak at 1720 cm⁻¹. －1 The absorption peak at 1412 cm⁻¹ is the stretching vibration peak of C=O. －1 The peaks on the left and right are unsaturated C-H deformation vibration peaks, at 1266 cm⁻¹. －1 The absorption peak at 1078 cm⁻¹ is due to the in-plane bending vibration of C-O-H. －1 The peak at this location is the COC absorption peak, which is the same as the peak shape of the tea saponin standard. The separation method provided by this invention does not employ harsh conditions of high temperature and high alkali, and the extracted tea saponin has a high yield, light color, and high purity. The tea saponin yield obtained by this method is 13.96%, and the purity is above 80%.
[0063] Figure 2 The infrared spectrum of lignocellulose in Example 1 of this invention is shown below. Figure 2 It can be seen that at 3451cm －1 and 1731cm- 1 The peaks at 2925 cm⁻¹ correspond to the stretching vibration absorption peaks of the hydroxyl and carbonyl groups in cellulose and hemicellulose, respectively. －1 The nearby absorption peak corresponds to the stretching vibration peak of alkanes, at 1633 cm⁻¹. －1 The characteristic peaks at 1627 cm⁻¹ are all attributed to the HOH stretching vibration of adsorbed water. 1 1509cm- 1 and 1250cm- 1 The peaks at 1035 cm⁻¹ correspond to the absorption peaks of the aromatic ring skeleton vibration of lignin. －1 The peaks are attributed to C–O stretching, and these characteristic peaks indicate that the key functional groups in the raw material are similar to those in cellulose, lignin, and hemicellulose. The lignocellulose extracted by this invention has the original brown pigment of the Camellia oleifera plant and is high in cellulose and lignin.
[0064] The above-described specific embodiments are preferred embodiments of the present invention and are not intended to limit the present invention. Any other changes or equivalent substitutions made without departing from the technical solution of the present invention are included within the protection scope of the present invention.
Claims
1. A simple method for separating components of oil tea cake, characterized by, The specific steps are as follows: (1) Add camellia seed meal powder to an alkaline aqueous solution for freezing treatment to obtain frozen camellia seed meal; (2) Take out the frozen camellia seed cake, thaw it, add alkaline aqueous solution, then mechanically crush, heat and centrifuge to obtain supernatant A and lignocellulose; (3) Add an alkaline precipitant to the supernatant A, let it stand and then centrifuge to obtain supernatant B and calcium tea saponate precipitate. Add acetic acid and chitosan solution to supernatant B, let it stand and then centrifuge to obtain tea oil protein. Add the calcium tea saponate precipitate to ammonium bicarbonate solution for solid-liquid separation. After solid-liquid separation, the liquid obtained is concentrated by evaporation to obtain tea saponin product. The specific steps of heating described in step (2) are as follows: The camellia seed meal solution was heated to 30-60℃ and the reaction time was 1-6 h.
2. The simplified method for separating components from camellia seed cake according to claim 1, characterized in that, The camellia seed meal powder has a mesh size of 40-200.
3. The simplified method for separating components from camellia seed cake according to claim 1, characterized in that, The freezing time in step (1) is 4 to 24 hours.
4. The simplified method for separating components from camellia seed cake according to claim 1, characterized in that, The alkaline aqueous solution is one of sodium hydroxide, sodium carbonate, trisodium phosphate, sodium citrate, or sodium tetraborate.
5. The simplified method for separating components from camellia seed cake according to claim 1, characterized in that, The liquid-to-solid ratio of the alkaline aqueous solution to the camellia seed meal powder is 5-30:
1.
6. The simplified method for separating components from camellia seed cake according to claim 1, characterized in that, The mechanical crushing process in step (2) takes 10 to 120 minutes.
7. The simplified method for separating components from camellia seed cake according to claim 1, characterized in that, The alkaline precipitant mentioned in step (3) is calcium oxide or calcium hydroxide, and the concentration of the alkaline precipitant is 1~10. wt%.
8. The simplified method for separating components from camellia seed cake according to claim 1, characterized in that, The molar ratio of ammonium bicarbonate solution to alkaline precipitant in step (3) is 1 ~ 1.5 :
1.
9. The simplified method for separating components from camellia seed cake according to claim 1, characterized in that, The concentration of the chitosan solution in step (3) is 0.5 ~ 5 wt%.