Method for reducing zearalenone in corn oil
By optimizing the mixing of crude corn oil and sodium hydroxide solution through shear homogenization and centrifugal separation technology, the problem of ZEN removal from corn oil was solved, achieving efficient and energy-saving corn oil processing and improving the safety and quality of corn oil.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-09
- Publication Date
- 2026-04-07
AI Technical Summary
In existing technologies, it is difficult to remove zearalenone (ZEN) during corn oil processing, and traditional detoxification processes often require long-term, high-temperature treatment, resulting in energy waste and a decline in corn oil quality.
Crude corn oil was mixed with sodium hydroxide solution using shear homogenization. ZEN removal rate was improved by specific shear homogenization and centrifugation. Specific conditions included optimization of shear speed, time, temperature and sodium hydroxide concentration.
It significantly improves the removal efficiency of ZEN to nearly 100%, avoids the damage of nutrients caused by high temperatures, reduces production energy consumption, and ensures the quality and production efficiency of corn oil.
Smart Images
Figure CN121801634A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of corn oil processing technology, and in particular to a method for reducing zearalenone in corn oil. Background Technology
[0002] Corn is one of the world's major economic crops and an important source of food, feed, and industrial products. Corn is susceptible to Fusarium infection both before and after harvest, producing fungal toxins, secondary metabolites harmful to humans and animals. Zearalenone (ZEN) is one of the most widespread Fusarium toxins affecting crop production and processing. These toxins cause various toxic effects on organisms, including reproductive toxicity, neurotoxicity, immunotoxicity, cytotoxicity, organ and tissue toxicity, and carcinogenicity.
[0003] During corn processing, ZEN continuously accumulates. After sorting, washing, soaking in nitrite, crushing, and separating, corn germ is obtained. This germ is then processed to produce crude corn oil, and ZEN is also present in this process. Crude corn oil is particularly contaminated. Reports indicate that the ZEN content in 45 crude corn oil samples ranged from 200.13 to 8153.33 μg / kg. Of these, 7 samples had ZEN levels below 2000 μg / kg, 30 samples had levels between 2000 and 4000 μg / kg, and 8 samples had levels above 4000 μg / kg.
[0004] ZEN removal from crude corn oil is generally achieved through subsequent processing steps such as degumming, deacidification, decolorization, and deodorization, to reach a safe level of toxins. However, to remove ZEN, subsequent processing often involves extending the processing time and increasing the temperature as much as possible, which can lead to resource waste, reduced economic efficiency, and decreased corn oil quality.
[0005] Removing zearalenone (ZEN) as much as possible in the early stages of processing is of significant practical importance for selecting subsequent processing conditions. In the early processing of corn oil, high-concentration alkali solutions are added for alkali refining, followed by oil sample separation to achieve a certain degree of deacidification and degumming. However, this typically only removes 30% to 40% of the ZEN content. Currently, there is an urgent need to provide a novel method for reducing zearalenone in corn oil. Summary of the Invention
[0006] To address the aforementioned technical problems, this invention provides a method for reducing zearalenone in corn oil. This invention effectively solves the technical difficulties in removing zearalenone (ZEN) during corn oil processing, and the fact that traditional detoxification processes often require long periods of time and high temperatures, leading to energy waste and a decline in corn oil quality. The method for reducing zearalenone in corn oil provided by this invention can achieve efficient ZEN removal while preserving the nutritional components of the corn oil.
[0007] In a first aspect, the method for reducing zearalenone in corn oil provided by the present invention includes the following steps: 1) Mix corn crude oil with sodium hydroxide solution to obtain a mixture; the concentration of the sodium hydroxide solution is 10%~40%.
[0008] 2) The mixture is subjected to shear homogenization, and the homogenized mixture is then centrifuged to obtain the supernatant oil. The rotation speed of the shear homogenization process is 1000~7000 r / min. This invention, by employing a specific shear homogenization process, better mixes and disperses crude corn oil and alkali solution, increasing the contact and mass transfer between the oil and alkali solution, thus improving ZEN removal. Compared to traditional methods, this invention provides better pretreatment of corn oil and significantly increases the ZEN removal rate.
[0009] Preferably, in step 2), the rotational speed of the shear homogenization process is 5000~7000 r / min; more preferably, the rotational speed of the shear homogenization process is 6500~7000 r / min. Using the preferred rotational speed range (especially 7000 r / min) can improve the water-oil emulsification effect and further enhance the migration efficiency of ZEN.
[0010] Preferably, in step 2), the shearing and homogenizing treatment time is 0.5~10 min; more preferably, the shearing and homogenizing treatment time is 0.5~5 min. Compared with the 20-30% ZEN removal rate in the traditional alkali refining process, the present invention can significantly reduce the processing time and improve efficiency while increasing the removal rate to over 98%.
[0011] Preferably, in step 2), the temperature of the shearing homogenization treatment is 20~80℃; more preferably, the temperature of the shearing homogenization treatment is 20~25℃. Using the preferred treatment temperature not only significantly improves the removal rate but also avoids the damage of heat-sensitive nutrients in corn oil caused by high temperatures, while significantly reducing production energy consumption.
[0012] Preferably, in step 2), the concentration of the sodium hydroxide solution is 30%~35%, more preferably 30%~32%. This provides a better alkaline environment, which is beneficial for ZEN removal, and the removal effect is better at the preferred concentration.
[0013] Preferably, in step 1), the mass content of sodium hydroxide in the mixture is 1.2% or more; more preferably, the mass content of sodium hydroxide in the mixture is 1.8% to 2%. When the mass content of sodium hydroxide in the mixture reaches the preferred range, a better ZEN removal effect can be achieved by combining it with a specific shearing process.
[0014] Preferably, in step 1), the water-to-oil ratio is 1% to 10%; more preferably, the water-to-oil ratio is 9% to 10%. Using the preferred water-to-oil ratio can further improve the removal rate of ZEN.
[0015] Further preferably, the centrifugal separation speed is 7500~8000 r / min and the time is 10~15 min.
[0016] Secondly, the present invention provides the application of the above-mentioned method for reducing zearalenone in corn oil in corn oil processing.
[0017] Thirdly, the present invention provides a corn oil product obtained by the above-described method for reducing zearalenone in corn oil.
[0018] The beneficial effects of this invention are at least as follows: The method for reducing zearalenone in corn oil provided by this invention significantly improves the removal efficiency of ZEN. Under certain conditions (such as an addition of 1.8%, a water-to-oil ratio of 10%, a 30% concentration of alkaline solution, and shearing at 20°C), the removal rate of ZEN in corn oil approaches 100%, greatly improving the safety of edible oil. The reaction conditions of this invention are mild, preserving quality and saving energy. It overcomes the need for high-temperature, long-duration processing in traditional processes, not only avoiding oxidation and nutrient loss in corn oil caused by high temperatures, thus ensuring the quality of the finished oil, but also reducing heating energy consumption and saving production costs. The process of this invention is highly efficient and rapid, with a short shearing time. Compared to traditional long-duration processing, it improves production efficiency. This method is simple to operate, easy to promote, and suitable for continuous industrial production. Attached Figure Description
[0019] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0020] Figure 1 This describes the removal of ZEN at different shearing times in this embodiment of the invention.
[0021] Figure 2 This describes the removal of ZEN at different shearing speeds in this embodiment of the invention.
[0022] Figure 3 This illustrates the removal of ZEN at different shear temperatures in embodiments of the present invention.
[0023] Figure 4 This illustrates the removal of ZEN at different sodium hydroxide concentrations in this embodiment of the invention.
[0024] Figure 5 This invention relates to the removal of ZEN under different water-oil ratios in various embodiments. Detailed Implementation
[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.
[0026] The endpoints and any values of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.
[0027] Unless otherwise specified, the techniques or conditions described in the embodiments of this invention shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Devices, instruments, reagents, etc., without specified manufacturers, are all conventional products that can be purchased through legitimate channels. All experimental reagents and raw materials involved are commercially available products, and all reagents are analytical grade products.
[0028] Example 1 This embodiment provides a method for reducing zearalenone in corn oil. The removal effect of different shear times on the ZEN content in alkali-refined oil is investigated, including: 1. Preparation of alkali-refined oil: Take 40 g of crude corn oil and add sodium hydroxide solution (30%, w / v) at a water-to-oil ratio of 1.5% (w / w). Homogenize the mixture at room temperature at 4000 r / min for different times (0, 0.5, 1, 3, and 5 min). After homogenization, centrifuge at 8000 r / min for 10 min, and take the supernatant oil to determine the ZEN toxin content.
[0029] 2. ZEN Extraction: Weigh 10 g of treated alkali-refined oil, add 10 times its volume of 70% acetonitrile, and shake at 200 r / min for 30 min. Then centrifuge and filter the supernatant using rapid qualitative filter paper. Add 10 mL of the filtrate to 40 mL of 0.01 mol / L PBST solution, mix well, and filter again using glass fiber filter paper. Pass 25 mL of the filtrate through a ZEN immunoaffinity column, adjusting the flow rate to 1-2 drops / s until the liquid has completely passed through the column. Wash the column with 10 mL of pure water at a flow rate of 1-2 drops / s. Finally, rinse the column with 1 mL of anhydrous methanol at a flow rate of 1-2 drops / s. Collect the eluent in a 1.5 mL centrifuge tube, filter through a 0.22 µm organic phase nylon membrane, and transfer to a 2 mL chromatographic vial to obtain the sample solution.
[0030] 3. Determination of ZEN: ZEN was detected by HPLC under the following conditions: mobile phase acetonitrile:water = 7:3; flow rate 1 mL / min; column C18 (250 mm × 4.6 mm, 5 µm); excitation wavelength 274 nm; detection wavelength 440 nm; column temperature 30℃; injection volume 20 µL.
[0031] The results are as follows Figure 1 As shown, using a shearing machine during the alkali refining process can significantly remove ZEN content from corn oil. The removal rate increases from 96.58% to 98.18% depending on the shearing time, which ranges from 0.5 min to 5 min.
[0032] Example 2 This embodiment provides a method for reducing zearalenone in corn oil. The removal effect of different shear speeds on the ZEN content in alkali-refined oil is investigated, including: 1. Preparation of alkali-refined oil: Take 40 g of crude corn oil and add sodium hydroxide solution (30%, w / v) at a water-to-oil ratio of 1.5% (w / w). Homogenize the mixture at room temperature at different speeds (0, 1000, 4000, and 7000 r / min) for 1 min. After homogenization, centrifuge at 8000 r / min for 10 min, and take the supernatant oil to determine the ZEN toxin content.
[0033] 2. ZEN Extraction: Weigh 10 g of treated alkali-refined oil, add 10 times its volume of 70% acetonitrile, and shake at 200 r / min for 30 min. Then centrifuge and filter the supernatant using rapid qualitative filter paper. Add 10 mL of the filtrate to 40 mL of 0.01 mol / L PBST solution, mix well, and filter again using glass fiber filter paper. Pass 25 mL of the filtrate through a ZEN immunoaffinity column, adjusting the flow rate to 1-2 drops / s until the liquid has completely passed through the column. Wash the column with 10 mL of pure water at a flow rate of 1-2 drops / s. Finally, rinse the column with 1 mL of anhydrous methanol at a flow rate of 1-2 drops / s. Collect the eluent in a 1.5 mL centrifuge tube, filter through a 0.22 µm organic phase nylon membrane, and transfer to a 2 mL chromatographic vial to obtain the sample solution.
[0034] 3. Determination of ZEN: ZEN was detected by HPLC under the following conditions: mobile phase acetonitrile:water = 7:3; flow rate 1 mL / min; column C18 (250 mm × 4.6 mm, 5 µm); excitation wavelength 274 nm; detection wavelength 440 nm; column temperature 30℃; injection volume 20 µL.
[0035] The results are as follows Figure 2 As shown, the shear rate has a significant effect on the removal of ZEN from corn oil. At a shear rate of 7000 r / min, 98.41% of ZEN in corn oil can be removed, and at a shear rate of 1000 r / min, the removal rate of ZEN in corn oil is 93.15%.
[0036] Example 3 This embodiment provides a method for reducing zearalenone in corn oil. The removal effect of different shear temperatures on the ZEN content in alkali-refined oil is investigated, including: 1. Preparation of alkali-refined oil: Take 40 g of crude corn oil and add sodium hydroxide solution (30%, w / v) at a water-to-oil ratio of 1.5% (w / w). Homogenize the mixture at 4000 r / min for 1 min at different temperatures (20, 40, 60, and 80 °C). After homogenization, centrifuge at 8000 r / min for 10 min, and take the supernatant oil to determine the ZEN toxin content.
[0037] 2. ZEN Extraction: Weigh 10 g of treated alkali-refined oil, add 10 times its volume of 70% acetonitrile, and shake at 200 r / min for 30 min. Then centrifuge and filter the supernatant using rapid qualitative filter paper. Add 10 mL of the filtrate to 40 mL of 0.01 mol / L PBST solution, mix well, and filter again using glass fiber filter paper. Pass 25 mL of the filtrate through a ZEN immunoaffinity column, adjusting the flow rate to 1-2 drops / s until the liquid has completely passed through the column. Wash the column with 10 mL of pure water at a flow rate of 1-2 drops / s. Finally, rinse the column with 1 mL of anhydrous methanol at a flow rate of 1-2 drops / s. Collect the eluent in a 1.5 mL centrifuge tube, filter through a 0.22 µm organic phase nylon membrane, and transfer to a 2 mL chromatographic vial to obtain the sample solution.
[0038] 3. Determination of ZEN: ZEN was detected by HPLC under the following conditions: mobile phase acetonitrile:water = 7:3; flow rate 1 mL / min; column C18 (250 mm × 4.6 mm, 5 µm); excitation wavelength 274 nm; detection wavelength 440 nm; column temperature 30℃; injection volume 20 µL.
[0039] The results are as follows Figure 3 As shown, shear temperature has an effect on the removal of ZEN from corn oil, but it is not significant. Increasing the shear temperature will reduce the ZEN removal rate from corn oil. The highest removal rate is 98.41% at 20℃. At shear temperatures of 40℃, 60℃ and 80℃, the ZEN removal rates from corn oil are 94.11%, 94.64% and 95.27%, respectively.
[0040] Example 4 This embodiment provides a method for reducing zearalenone in corn oil. The removal effect of sodium hydroxide solutions of different concentrations on ZEN in alkaline refined oil is investigated, including: 1. Preparation of alkali-refined oil: Take 40 g of crude corn oil and add sodium hydroxide solution at a water-to-oil ratio of 2% (w / w) to achieve final sodium hydroxide concentrations of 0%, 0.5%, 1%, 1.2%, 1.5%, 1.8%, and 2%. Homogenize the mixture at 4000 r / min for 1 min at room temperature. After homogenization, centrifuge at 8000 r / min for 10 min, and take the supernatant oil to determine the ZEN toxin content.
[0041] 2. ZEN Extraction: Weigh 10 g of treated alkali-refined oil, add 10 times its volume of 70% acetonitrile, and shake at 200 r / min for 30 min. Then centrifuge and filter the supernatant using rapid qualitative filter paper. Add 10 mL of the filtrate to 40 mL of 0.01 mol / L PBST solution, mix well, and filter again using glass fiber filter paper. Pass 25 mL of the filtrate through a ZEN immunoaffinity column, adjusting the flow rate to 1-2 drops / s until the liquid has completely passed through the column. Wash the column with 10 mL of pure water at a flow rate of 1-2 drops / s. Finally, rinse the column with 1 mL of anhydrous methanol at a flow rate of 1-2 drops / s. Collect the eluent in a 1.5 mL centrifuge tube, filter through a 0.22 µm organic phase nylon membrane, and transfer to a 2 mL chromatographic vial to obtain the sample solution.
[0042] 3. Determination of ZEN: ZEN was detected by HPLC under the following conditions: mobile phase acetonitrile:water = 7:3; flow rate 1 mL / min; column C18 (250 mm × 4.6 mm, 5 µm); excitation wavelength 274 nm; detection wavelength 440 nm; column temperature 30℃; injection volume 20 µL.
[0043] The results are as follows Figure 4 As shown, the final concentration of sodium hydroxide in corn oil has a significant impact on the removal rate of ZEN. When the final concentration of sodium hydroxide is 0.5%-1%, it has virtually no effect on the removal of ZEN from corn oil. At a final concentration of 1.2%, the ZEN removal rate reaches 89.58%. Furthermore, as the final concentration of sodium hydroxide increases, the ZEN removal rate from corn oil increases significantly, reaching 100% when the final concentration exceeds 1.8%.
[0044] Example 5 This embodiment provides a method for reducing zearalenone in corn oil. The removal effect of different water-to-oil ratios on the ZEN content in alkali-refined oil is assessed, including: 1. Preparation of alkali-refined oil: Take 40 g of crude corn oil and add sodium hydroxide solution according to different water-oil ratios (0%, 1%, 2%, 5%, 7%, and 10%), with a final sodium hydroxide concentration of 1.5%. Homogenize the mixture at 4000 r / min for 1 min at room temperature. After homogenization, centrifuge at 8000 r / min for 10 min, and take the supernatant oil to determine the ZEN toxin content.
[0045] 2. ZEN Extraction: Weigh 10 g of treated alkali-refined oil, add 10 times its volume of 70% acetonitrile, and shake at 200 r / min for 30 min. Then centrifuge and filter the supernatant using rapid qualitative filter paper. Add 10 mL of the filtrate to 40 mL of 0.01 mol / L PBST solution, mix well, and filter again using glass fiber filter paper. Pass 25 mL of the filtrate through a ZEN immunoaffinity column, adjusting the flow rate to 1-2 drops / s until the liquid has completely passed through the column. Wash the column with 10 mL of pure water at a flow rate of 1-2 drops / s. Finally, rinse the column with 1 mL of anhydrous methanol at a flow rate of 1-2 drops / s. Collect the eluent in a 1.5 mL centrifuge tube, filter through a 0.22 µm organic phase nylon membrane, and transfer to a 2 mL chromatographic vial to obtain the sample solution.
[0046] 3. Determination of ZEN: ZEN was detected by HPLC under the following conditions: mobile phase acetonitrile:water = 7:3; flow rate 1 mL / min; column C18 (250 mm × 4.6 mm, 5 µm); excitation wavelength 274 nm; detection wavelength 440 nm; column temperature 30℃; injection volume 20 µL.
[0047] The results are as follows Figure 5 As shown, the water-to-oil ratio significantly affects the ZEN removal rate in corn oil. With increasing water-to-oil ratio, the ZEN removal rate in corn oil increases significantly. During alkali refining of corn oil, the water-to-oil ratio is typically between 1% and 2%. At water-to-oil ratios of 1% and 2%, the ZEN removal rates in corn oil reach 90.60% and 93.48%, respectively. When the water-to-oil ratio is increased to 10%, the ZEN removal rate in corn oil reaches 100%. However, a high water-to-oil ratio increases the yield of soapberry, significantly affecting the oil yield, reducing the quality of refined oil, and increasing production costs.
[0048] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for reducing zearalenone in corn oil, characterized in that, Includes the following steps: 1) Mix crude corn oil with sodium hydroxide solution to obtain a mixture; the concentration of the sodium hydroxide solution is 10%~40%; 2) The mixture is subjected to shear homogenization, and the mixture after shear homogenization is centrifuged to separate the supernatant oil; the rotation speed of the shear homogenization is 1000~7000 r / min.
2. The method according to claim 1, characterized in that, In step 2), the rotation speed of the shearing homogenization process is 5000~7000 r / min; preferably, the rotation speed of the shearing homogenization process is 6500~7000 r / min.
3. The method according to claim 2, characterized in that, In step 2), the shearing and homogenizing process takes 0.5 to 10 minutes; preferably, the shearing and homogenizing process takes 0.5 to 5 minutes.
4. The method according to any one of claims 1-3, characterized in that, In step 2), the temperature of the shearing homogenization process is 20~80℃; preferably, the temperature of the shearing homogenization process is 20~25℃.
5. The method according to any one of claims 1-4, characterized in that, In step 2), the concentration of the sodium hydroxide solution is 10% to 40%; preferably, the concentration of the sodium hydroxide solution is 30% to 35%.
6. The method according to claim 5, characterized in that, In step 1), the mass content of sodium hydroxide in the mixture is 1.2% or more; preferably, the mass content of sodium hydroxide in the mixture is 1.8% to 2%.
7. The method according to any one of claims 1-6, characterized in that, In step 1), the water-oil ratio is 1% to 10%; preferably, the water-oil ratio is 9% to 10%.
8. The method according to any one of claims 1-7, characterized in that, The centrifugation speed is 7500~8000 r / min, and the time is 10~15 min.
9. The application of the method for reducing zearalenone in corn oil according to any one of claims 1-8 in corn oil processing.
10. The corn oil product obtained by the method for reducing zearalenone in corn oil according to any one of claims 1-8.