Special anti-oxidation composition for rice bran oil as well as preparation method and application of special anti-oxidation composition

Abstract

The invention discloses a special antioxidant composition for rice bran oil as well as a preparation method and application thereof, and relates to the technical field of oil oxidation resistance. The special antioxidant composition for the rice bran oil comprises the following components: ferulate, ascorbyl palmitate, a VE (Vitamin E) derivative and a composite auxiliary material, the VE derivative is selected from VE acetate and / or VE succinate; the composite auxiliary material is selected from citric acid and / or disodium EDTA (Ethylene Diamine Tetraacetic Acid). According to the special anti-oxidation composition for the rice bran oil as well as the preparation method and the application of the special anti-oxidation composition, the ferulate, the ascorbyl palmitate and the VE derivative are compounded, so that the oxidation pain point of the rice bran oil is solved in a targeted manner, the chelating rate of metal ions in the rice bran oil reaches 85% or above, the scavenging rate of peroxy free radicals reaches 93%, and the normal-temperature shelf life of the rice bran oil is prolonged from 60 days to 360 days or above.

Description

Technical Field

[0001] This invention relates to the field of oil and fat antioxidant technology, and in particular to an antioxidant composition for rice bran oil, its preparation method, and its application. Background Technology

[0002] Rice bran oil is an edible oil with extremely high nutritional value, rich in linoleic acid, alpha-linolenic acid and phytosterols. However, due to its high content of unsaturated fatty acids, it is easy to introduce metal ions such as iron and copper residues from rice bran during processing, resulting in extremely poor oxidative stability of rice bran oil. When stored at room temperature, its shelf life is only 30 to 60 days, and it is prone to producing harmful aldehydes when cooked at high temperatures, which seriously limits its commercial application.

[0003] Existing rice bran oil antioxidant solutions have significant drawbacks: Single antioxidants: When vitamin E (such as α-tocopherol) is used alone, its dispersibility in rice bran oil is poor and it is easily catalyzed and oxidized by metal ions, with a retention rate of less than 50% after 3 months; when ascorbate palmitate (AP) is used, although it can act on the oil-water interface, it cannot deal with the high concentration of peroxide free radicals in rice bran oil, and more than 0.3% needs to be added to be effective, which can easily lead to increased costs; Compound system: Although the binary compound of ferulic acid ester and AP can improve antioxidant efficiency, it cannot inhibit the catalytic effect of metal ions, and it is easily degraded in the high-temperature addition process (60~70℃) after rice bran oil refining, with an activity retention rate of only 65%~75%; Limitations of derivative applications: In existing technologies, VE derivatives (such as VE acetate) are mostly used alone and do not form a synergistic effect with ferulic acid esters and AP. Their antioxidant cycle in rice bran oil is only 90-120 days, which still cannot meet the needs of commercial storage.

[0004] Therefore, developing a highly efficient synergistic antioxidant composition based on ferulic acid ester, ascorbate palmitate and VE derivative that can adapt to the characteristics of rice bran oil being "highly unsaturated, high in metal ions, and added at high temperatures" is key to solving the oxidation problem of rice bran oil. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing rice bran oil antioxidant solutions and provide a rice bran oil-specific antioxidant composition, its preparation method, and its application. Through the synergistic effect of ferulic acid esters, AP, and VE derivatives, this invention specifically addresses three major challenges in rice bran oil oxidation: easy oxidation of highly unsaturated fatty acids, metal ion-catalyzed oxidation, and degradation of active ingredients due to high-temperature addition. This achieves a dual improvement in the shelf life and processing tolerance of rice bran oil. Specifically, the technical solutions include the following: In a first aspect, an antioxidant composition for rice bran oil is provided, comprising the following components: ferulic acid ester, ascorbate palmitate (AP), VE derivative and compound excipients; wherein the VE derivative is selected from VE acetate and / or VE succinate; and the compound excipients are selected from citric acid and / or disodium EDTA.

[0006] Among them, the combination of ferulic acid esters, AP and VE derivatives has the advantage of synergistic mechanism upgrade (adapting to the characteristics of rice bran oil): 1. Targeted Scavenging Enhancement: Ferulic acid esters preferentially scavenge hydroxyl radicals (・OH) generated by metal ion catalysis in rice bran oil, blocking the oxidation chain reaction of "metal ion-free radical" at its source; VE derivatives anchor the oil phase core of rice bran oil, efficiently scavenging peroxide radicals (ROO・) generated by the oxidation of linoleic acid and α-linolenic acid. Its ester structure is more heat-resistant than VE, maintaining an activity retention rate of over 90% when added at 60-70℃; AP acts on the inner wall of the rice bran oil storage container (oil-water interface), scavenging singlet oxygen (…). 1 O2), while also assisting in the chelation of trace metal ions, making up for the chelation blind spots of traditional excipients.

[0007] 2. Multi-level regeneration adaptation: forming a reverse regeneration chain of "VE derivative → AP → ferulic acid ester": AP reduces the oxidized and deactivated VE derivative free radical (TOO・) through the enediol structure, restoring its activity; ferulic acid ester releases phenolic hydroxyl hydrogen, reducing the deactivated dehydroascorbate palmitate (DAP); finally, the ferulic acid ester free radical (F・) is stabilized by forming hydrogen bonds with phytosterols in rice bran oil, avoiding reverse damage. The effective concentration half-life of the three is 1.5 times longer than that of the binary system.

[0008] 3. Synergistic chelation of metal ions: The compound excipients and AP form a "double chelation": Citric acid rapidly chelates free metal ions, and disodium EDTA long-term chelates bound metal ions, solving the core pain point of catalytic oxidation of metal ions in rice bran oil and reducing the oxidation rate by 40%~50%.

[0009] Furthermore, the rice bran oil-specific antioxidant composition comprises the following components in parts by weight: 80-100 parts of ferulic acid ester, 180-250 parts of ascorbyl palmitate, 90-170 parts of vitamin E derivative, and 35-52 parts of compound excipients.

[0010] Furthermore, the mass of the composite excipient is 8-12% of the total mass of ferulic acid ester, ascorbate palmitate, and VE derivative.

[0011] Furthermore, the VE derivative is selected from VE acetate and VE succinate, wherein the mass ratio of VE acetate to VE succinate is 1:(0.8-1.2).

[0012] Preferably, the VE derivative is selected from VE acetate and VE succinate (mass ratio 1:1): VE acetate is heat resistant (85% activity retention rate after 2 hours at 120℃), and is suitable for high-temperature addition after rice bran oil refining; VE succinate has slightly better water solubility, and is suitable for the trace moisture environment during the storage of rice bran oil. The two work together to improve high-temperature stability by 30%.

[0013] Furthermore, the composite excipient is selected from citric acid and disodium EDTA, and the mass ratio of citric acid to disodium EDTA is (1.5-2.5):1.

[0014] Preferably, the compound excipients are citric acid (rapid chelation) and disodium EDTA (long-lasting chelation) mixed in a mass ratio of 2:1. The amount of compound excipients added is 8% to 12% of the total mass of the active ingredients (ferulate, ascorbate palmitate and VE derivatives), which ensures the chelation effect while avoiding affecting the flavor of rice bran oil.

[0015] Furthermore, the mass ratio of the ferulic acid ester, ascorbate palmitate, and VE derivative is 1:(1.8-2.2):(1.2-1.6).

[0016] Furthermore, the ferulic acid ester is selected from octyl ferulic acid or propyl ferulic acid.

[0017] The ferulic acid ester has a LogP of ≈5.5~6.0, which is more compatible with rice bran oil than ethyl ferulic acid ester, and improves the dispersion uniformity in rice bran oil by 20%.

[0018] Furthermore, the mass ratio of the ferulic acid ester, ascorbate palmitate, and VE derivative is 1:2:1.5.

[0019] The rationale behind this compound ratio (specifically for rice bran oil) is as follows: Rice bran oil has a high concentration of peroxide free radicals (1.8 times that of soybean oil), requiring an increased proportion of VE derivatives to enhance ROO scavenging; Rice bran oil also has a high content of metal ions (iron ion content approximately 0.1~0.3 mg / kg), necessitating an optimized AP ratio to aid chelation; When the ratio is below 1:1.8:1.2, insufficient amounts of VE derivatives and AP result in poor metal ion chelation and a 30% increase in oxidation rate; When the ratio is above 1:2.2:1.6, excessive VE derivatives compete with ferulic acid esters for AP regeneration resources, leading to a 25% reduction in ferulic acid ester retention, which in turn affects the antioxidant effect.

[0020] Preferably, the rice bran oil-specific antioxidant composition comprises the following components in parts by weight: 100 parts ferulic acid ester, 200 parts ascorbyl palmitate, 150 parts vitamin E derivative, and 45 parts compound excipients.

[0021] In a second aspect, a method for preparing the rice bran oil-specific antioxidant composition according to the first aspect is provided, comprising the following steps: (1) In a nitrogen-protected double-layered stirred container, add ferulic acid ester, ascorbate palmitate and VE derivative, and circulate 30°C circulating water through the outer layer of the double-layered stirred container to control the temperature. (2) Add the composite additives to the double-layer stirring container, heat to 50°C, stir at 250 r / min for 22 minutes until the material is completely dissolved and forms a uniform and transparent liquid; (3) Maintain a nitrogen atmosphere and cool to 26°C to obtain a rice bran oil-specific antioxidant composition.

[0022] The preparation process employs nitrogen protection and stirring at a low temperature of 45-55℃, which not only prevents the active ingredients from oxidizing during preparation but also ensures that the composite excipients are completely dissolved to form a homogeneous system.

[0023] Thirdly, the application of the rice bran oil-specific antioxidant composition according to the first aspect in the preparation of rice bran oil is provided.

[0024] Preferably, the application includes the following steps: (1) The antioxidant composition for rice bran oil is added to 1 kg of refined rice bran oil at a mass percentage of 0.08-0.2%; (2) Stir at a stirring speed of 150 r / min for 15 minutes to ensure that the rice bran oil-specific antioxidant composition is evenly dispersed; (3) After stirring, cool the refined rice bran oil to below 30°C and then fill and store it.

[0025] Preferably, the refined rice bran oil is deodorized at a temperature of 65°C, has an iron ion content of 0.2 mg / kg, and an initial POV of 2 mmol / kg.

[0026] The specific antioxidant composition for rice bran oil is added after the deodorization process of rice bran oil is completed and the temperature drops to 60-70℃. At this time, the rice bran oil has been free of odor substances, and this temperature is suitable for the retention of the activity of VE derivatives (the activity retention rate of VE derivatives reaches 92% at 60-70℃), which can avoid the problem of uneven dispersion caused by traditional "low-temperature addition".

[0027] The beneficial effects of this invention are as follows: 1. Targeted solution to the oxidation problem of rice bran oil: The chelation rate of metal ions in rice bran oil reaches more than 85%, and the scavenging rate of peroxide free radicals reaches 93%, which extends the shelf life of rice bran oil at room temperature from 60 days to more than 360 days; 2. Excellent high-temperature stability: When added at 60-70℃ after refining rice bran oil, the retention rate of active ingredients reaches over 90%, which is 25% higher than that of the binary system; 3. Safety and flavor compatibility: All ingredients are food grade. After addition, the acid value and peroxide value of the rice bran oil meet the GB 2716-2018 standard, and there is no off-odor, which does not affect the natural rice aroma of the rice bran oil. 4. Low application cost: The addition amount is only 0.08%~0.2%, which reduces the cost by 40%~50% compared with the traditional single antioxidant solution (addition amount 0.3%~0.5%), making it suitable for industrial applications. Attached Figure Description

[0028] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 The peroxide value of rice bran oil prepared in Examples 1-3 and Comparative Examples 1-6 of this invention changes with storage time. Detailed Implementation

[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. 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.

[0031] It should be understood that, when used in this specification and the appended claims, the terms "comprising" and "including" indicate the presence of the described features, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components and / or collections thereof.

[0032] It should also be understood that the terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms unless the context clearly indicates otherwise.

[0033] It should also be further understood that the term "and / or" as used in this specification and the appended claims refers to any combination of one or more of the associated listed items and all possible combinations, and includes such combinations.

[0034] To better understand the technical content of the present invention, the technical solution of the present invention will be further introduced and explained below with reference to specific embodiments.

[0035] Example 1 An antioxidant composition specifically for rice bran oil, comprising the following raw materials: 100g of ferulic acid ester (octyl ferulic acid ester), 200g of AP, 150g of VE derivative (composed of VE acetate and VE succinate in a mass ratio of 1:1), and 45g of compound excipients (composed of citric acid and disodium EDTA in a mass ratio of 2:1).

[0036] The preparation method of the aforementioned rice bran oil-specific antioxidant composition includes the following steps: (1) In a nitrogen-protected double-layered stirred container, add ferulic acid ester, ascorbate palmitate and VE derivative, and circulate 30°C circulating water through the outer layer of the double-layered stirred container to control the temperature. (2) Add the composite additives to the double-layer stirring container, heat to 50°C, stir at 250 r / min for 22 minutes until the material is completely dissolved and forms a uniform and transparent liquid; (3) Maintain a nitrogen atmosphere and cool to 26°C to obtain a rice bran oil-specific antioxidant composition.

[0037] The preparation methods of Examples 2-3 and Comparative Examples 1-6 are the same as those of Example 1.

[0038] Example 2 An antioxidant composition specifically for rice bran oil, comprising the following raw materials: 100g of ferulic acid ester (octyl ferulic acid ester), 190g of AP, 160g of VE derivative (composed of VE acetate and VE succinate in a mass ratio of 1:1), and 45g of compound excipients (composed of citric acid and disodium EDTA in a mass ratio of 2:1).

[0039] Example 3 An antioxidant composition specifically for rice bran oil, comprising the following raw materials: 100g of ferulic acid ester (octyl ferulic acid ester), 220g of AP, 130g of VE derivative (composed of VE acetate and VE succinate in a mass ratio of 1:1), and 45g of compound excipients (composed of citric acid and disodium EDTA in a mass ratio of 2:1).

[0040] Comparative Example 1 Comparative Example 1 is a blank example, using the same mass of deionized water as in Example 1.

[0041] Comparative Example 2 An antioxidant composition specifically for rice bran oil, comprising the following raw materials: 100g of ferulic acid ester (octyl ferulic acid ester), 140g of VE derivative (composed of VE acetate and VE succinate in a mass ratio of 1:1), and 24g of compound excipients (composed of citric acid and disodium EDTA in a mass ratio of 2:1).

[0042] Comparative Example 3 An antioxidant composition specifically for rice bran oil, comprising the following raw materials: 100g of ferulic acid ester (octyl ferulic acid ester), 200g of AP, and 30g of compound excipients (composed of citric acid and disodium EDTA in a mass ratio of 2:1).

[0043] Comparative Example 4 An antioxidant composition specifically for rice bran oil, comprising the following raw materials: AP 200g, VE derivative (composed of VE acetate and VE succinate in a mass ratio of 1:1) 160g, and compound excipients (composed of citric acid and disodium EDTA in a mass ratio of 2:1) 36g.

[0044] Comparative Example 5 An antioxidant composition specifically for rice bran oil, comprising the following raw materials: 100g of ferulic acid ester (octyl ferulic acid ester), 240g of AP, 110g of VE derivative (composed of VE acetate and VE succinate in a mass ratio of 1:1), and 45g of compound excipients (composed of citric acid and disodium EDTA in a mass ratio of 2:1).

[0045] Comparative Example 6 An antioxidant composition specifically for rice bran oil, comprising the following raw materials: 100g of ferulic acid ester (octyl ferulic acid ester), 175g of AP, 175g of VE derivative (composed of VE acetate and VE succinate in a mass ratio of 1:1), and 45g of compound excipients (composed of citric acid and disodium EDTA in a mass ratio of 2:1).

[0046] Performance testing First, the aforementioned antioxidant composition for rice bran oil is applied in the preparation of rice bran oil, including the following steps: (1) The antioxidant composition for rice bran oil is added to 1 kg of refined rice bran oil at a mass percentage of 0.15% (the refined rice bran oil is at a temperature of 65°C after deodorization, has an iron ion content of 0.2 mg / kg, and an initial POV of 2 mmol / kg). (2) Stir at a stirring speed of 150 r / min for 15 minutes to ensure that the rice bran oil-specific antioxidant composition is evenly dispersed (no visible particles were found in the sample). (3) After stirring, cool the refined rice bran oil to below 30°C and then fill and store it.

[0047] The prepared rice bran oil was subjected to an antioxidant test.

[0048] Antioxidant test: The antioxidant effect of rice bran oil was tested, including its stability at room temperature (shelf life at room temperature, d), metal ion chelation effect (free iron ion content, mg / kg) and free radical scavenging effect (%).

[0049] Stability at room temperature: Store at 25℃ away from light, measure POV value monthly, and record the time when POV reaches 10 mmol / kg; Metal ion chelation effect: The content of free iron ions in the sample was determined by atomic absorption spectrophotometry.

[0050] Peroxy radical scavenging effect: The scavenging ability of peroxy radicals (ROO•) in the sample was determined by the pyrogallol auto-oxidation method.

[0051] Antioxidant tests were conducted on Examples 1-3 and Comparative Examples 1-6, and the results are shown in Table 1 below: Table 1. Antioxidant test results of Examples 1-3 and Comparative Examples 1-6 As shown in Table 1, the antioxidant composition for rice bran oil in this embodiment of the invention is significantly better than the binary system in terms of storage stability, free radical scavenging effect and metal ion chelation effect of rice bran oil, and is fully adapted to the application requirements of the oil.

[0052] Figure 1 The graph shows the change in peroxide value over storage time after rice bran oil was prepared according to Examples 1-3 and Comparative Examples 1-6 of this invention. Figure 1 As can be seen directly, the peroxide value of Examples 1-3 increased the slowest, and did not exceed 10 mmol / kg after 360 days, indicating the best storage stability.

[0053] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in the present invention, and these modifications or substitutions should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. An antioxidant composition specifically for rice bran oil, characterized in that, It comprises the following components: ferulic acid ester, ascorbate palmitate, vitamin E derivative and compound excipients; the vitamin E derivative is selected from vitamin E acetate and / or vitamin E succinate; the compound excipients are selected from citric acid and / or disodium EDTA.

2. The antioxidant composition for rice bran oil according to claim 1, characterized in that, It includes the following components by weight: 80-100 parts of ferulic acid ester, 180-250 parts of ascorbyl palmitate, 90-170 parts of vitamin E derivative, and 35-52 parts of compound excipients.

3. The antioxidant composition for rice bran oil according to claim 1, characterized in that, The mass of the composite excipient is 8-12% of the total mass of ferulic acid ester, ascorbate palmitate, and vitamin E derivative.

4. The antioxidant composition for rice bran oil according to claim 1, characterized in that, The VE derivative is selected from VE acetate and VE succinate, and the mass ratio of VE acetate to VE succinate is 1:(0.8-1.2).

5. The antioxidant composition for rice bran oil according to claim 1, characterized in that, The composite excipients are selected from citric acid and disodium EDTA, and the mass ratio of citric acid to disodium EDTA is (1.5-2.5):

1.

6. The antioxidant composition for rice bran oil according to claim 1, characterized in that, The mass ratio of ferulic acid ester, ascorbate palmitate and VE derivative is 1:(1.8-2.2):(1.2-1.6).

7. The antioxidant composition for rice bran oil according to claim 6, characterized in that, The mass ratio of ferulic acid ester, ascorbate palmitate, and VE derivative is 1:2:1.

5.

8. The antioxidant composition for rice bran oil according to claim 1, characterized in that, The ferulic acid ester is octyl ferulic acid or propyl ferulic acid.

9. A method for preparing a rice bran oil-specific antioxidant composition according to any one of claims 1-8, characterized in that, Includes the following steps: (1) In a nitrogen-protected double-layered stirred container, add ferulic acid ester, ascorbate palmitate and VE derivative, and circulate 30°C circulating water through the outer layer of the double-layered stirred container to control the temperature. (2) Add the composite additives to the double-layer stirring container, heat to 50°C, stir at 250 r / min for 22 minutes until the material is completely dissolved and forms a uniform and transparent liquid; (3) Maintain a nitrogen atmosphere and cool to 26°C to obtain a rice bran oil-specific antioxidant composition.

10. The use of the antioxidant composition for rice bran oil according to any one of claims 1-8 in the preparation of rice bran oil.

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