Detoxification agent, preparation method and application thereof

Abstract

The application discloses a detoxification agent and a preparation method and application thereof, and relates to the technical field of detoxification agents, and particularly relates to a detoxification agent and a preparation method and application thereof. The preparation method comprises the following steps: (1) performing crushing treatment on shelled shrimp and / or shelled crab which are cleaned and dried, then performing hydrochloric acid immersion and centrifugal treatment to obtain first precipitates, and finally performing washing and drying on the first precipitates to obtain first dried matters; (2) performing calcination, grinding, ultrasonic treatment and centrifugal treatment on the first dried matters to obtain second precipitates, then performing washing and drying on the second precipitates to obtain second dried matters; (3) performing calcination, ultrasonic treatment and centrifugal treatment on the second dried matters to obtain third precipitates, then performing washing and drying on the third precipitates to obtain the detoxification agent. The detoxification agent disclosed by the application can efficiently remove harmful substances such as zearalenone and / or benzo[a]pyrene.

Description

Technical Field

[0001] This invention belongs to the field of grain and oil processing technology, and more specifically, relates to a detoxifying agent, its preparation method, and its application. Background Technology

[0002] During the production of edible oils, the inconsistent quality of raw materials, coupled with high-temperature seed roasting, can easily lead to excessive levels of harmful substances (benzo[a]pyrene) in the pressed products. Benzo[a]pyrene (BaP, C 20 H 12 Benzo[a]pyrene is a polycyclic aromatic hydrocarbon composed of five benzene rings and has been proven to be highly carcinogenic, causing cancers of the skin, lungs, and digestive tract. In 2006, the World Health Organization upgraded its carcinogenicity level from "probably carcinogenic to humans" to the highest level, "determined human carcinogen." International standards stipulate that the content of benzo[a]pyrene in oils and their products must not exceed 10 μg / kg. Corn oil production relies on corn germ as raw material. If the raw material is not properly screened, contaminated corn germ may directly enter the pressing process, and the fat-soluble zearalenone will migrate into the crude oil. Although refining processes (such as degumming and deacidification) can partially remove zearalenone, if the initial contamination of the raw material is severe or the process parameters are not up to standard, residues may still occur. The limit for zearalenone in corn oil in the European Union is 200 ppb. Benzo[a]pyrene and zearalenone are prone to accumulation in contaminated oilseeds due to their strong lipophilicity, or improper processing can easily lead to excessive levels in oils. In existing technologies, activated clay is commonly used to remove zearalenone and benzo[a]pyrene, but the results are not ideal. How to efficiently remove harmful substances from oils and fats is a technical problem that urgently needs to be solved. Summary of the Invention

[0003] The purpose of this invention is to provide a detoxifying agent, its preparation method and application. The detoxifying agent of this invention can efficiently remove zearalenone and / or benzo[a]pyrene.

[0004] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a detoxifying agent, the method comprising:

[0005] (1) The shrimp shells and / or crab shells that have been cleaned and dried are crushed, then soaked in hydrochloric acid and centrifuged to obtain the first precipitate. Finally, the first precipitate is washed and dried to obtain the first dried product.

[0006] (2) The first dried material is subjected to calcination, grinding, ultrasonic treatment and centrifugation to obtain a second precipitate. Then the second precipitate is washed and dried to obtain a second dried material.

[0007] (3) The second dried material is calcined, ultrasonically treated and centrifuged to obtain a third precipitate. The third precipitate is then washed and dried to obtain a detoxifying agent.

[0008] According to the present invention, preferably, in step (1), the hydrochloric acid is a dilute hydrochloric acid with a mass concentration of 5-12%;

[0009] The soaking temperature is 45-80℃, and the soaking time is 4-8 hours.

[0010] According to the present invention, preferably, in step (1), the pulverization process is to crush the material using a pulverizer and pass it through a 150-250 mesh sieve;

[0011] The washing condition is to wash until neutral;

[0012] The solvent used for washing is a low-melting-point organic solvent, preferably at least one of methanol, ethanol, diethyl ether, petroleum ether, and acetone.

[0013] According to the present invention, preferably, in step (2), the calcination temperature is 180-300°C and the time is 3-8 hours;

[0014] The conditions for ultrasonic treatment include: an environment with a pH of 8-12, an ultrasonic power of 450-1000W, and an ultrasonic time of 60-120min.

[0015] The centrifugation conditions include: a centrifugation speed of 2800-5000 rpm / min and a centrifugation time of 8-25 min.

[0016] According to the present invention, preferably, in step (2), a muffle furnace is used for the burning;

[0017] The particle size of the grinding process is less than 150-250 mesh;

[0018] The washing condition is to wash until neutral;

[0019] The solvent used for washing is a low-melting-point organic solvent, preferably at least one of methanol, ethanol, diethyl ether, petroleum ether, and acetone;

[0020] The drying temperature is 30-50℃.

[0021] According to the present invention, preferably, in step (3), the calcination temperature is 400-800°C and the time is 3-7 hours;

[0022] The conditions for ultrasonic treatment include: an environment with a pH of 8-12, an ultrasonic power of 450-1000W, and an ultrasonic time of 60-120min.

[0023] The centrifugation conditions include: a centrifugation speed of 2800-5000 rpm / min and a centrifugation time of 8-25 min.

[0024] According to the present invention, preferably, in step (3), a muffle furnace is used for the calcination;

[0025] The washing condition is to wash until neutral;

[0026] The solvent used for washing is a low-melting-point organic solvent, preferably at least one of methanol, ethanol, diethyl ether, petroleum ether, and acetone;

[0027] The drying temperature is 30-50℃.

[0028] A second aspect of the present invention provides a detoxifying agent prepared by the above-described preparation method.

[0029] A third aspect of the present invention provides the application of the above-mentioned detoxifying agent for the removal of benzo[a]pyrene and / or zearalenone; preferably, the application for the removal of benzo[a]pyrene and / or zearalenone from edible oils.

[0030] According to the present invention, preferably, the amount of the detoxifying agent added is 0.05-2 wt% based on the total weight of the sample to be treated;

[0031] The detoxifying agent is removed at a temperature of 50-110℃ for 15-35 minutes.

[0032] In one specific embodiment of the present invention, the removal treatment method includes: adding the detoxifying agent to the sample to be treated, and stirring at 45-60 rpm / min (or shaking on a shaker at 100-200 rpm / min) for 15-35 min at a temperature of 50-110℃; wherein, the amount of the detoxifying agent added is 0.05-2 wt% based on the total weight of the sample to be treated.

[0033] The technical solution of the present invention has the following beneficial effects:

[0034] The detoxifying agent of the present invention can efficiently remove harmful substances such as zearalenone and / or benzo[a]pyrene.

[0035] The detoxifying agent of this invention uses shrimp and crab shells as raw materials, thereby increasing the economic value of shrimp and crab shells and broadening their application scope.

[0036] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0037] Preferred embodiments of the invention will now be described in more detail. While preferred embodiments of the invention are described below, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that the invention will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

[0038] The present invention is further illustrated by the following examples:

[0039] The formulas for calculating the removal rate in the following test examples are as follows:

[0040] Removal rate (%) = 100*(C0-C1) / C0; where C0 and C1 are the concentrations of hazardous substances in the sample before and after removal, respectively.

[0041] Example 1

[0042] Raw material pretreatment: Wash and dry the shrimp shells, crush them with a crusher, pass them through a 200-mesh sieve, soak them in 10% dilute hydrochloric acid at 50°C for 6 hours, collect the precipitate by centrifugation, wash the precipitate with ethanol until neutral and dry it to obtain the first dried product.

[0043] Preparation of detoxifying agent: The first dried material was calcined in a muffle furnace at 200℃ for 4 hours. The calcined material was ground through a 200-mesh sieve, and the sieve-filled material was ultrasonically treated in an environment with pH 10 (ultrasonic power 500W, ultrasonic time 90min). After ultrasonic treatment, it was centrifuged (centrifugation speed 3000rpm / min, centrifugation time 10min). The precipitate was collected, washed with ethanol until neutral, and then dried at 40℃. After drying, it was placed in a muffle furnace and calcined again at 700℃ for 4 hours. The calcined material was collected and ultrasonically treated in an environment with pH 10 (ultrasonic power 500W, ultrasonic time 90min). After ultrasonic treatment, it was centrifuged (centrifugation speed 3000rpm / min, centrifugation time 10min). The precipitate was collected, washed with ethanol until neutral, and then dried at 50℃ to obtain detoxifying agent A.

[0044] Comparative Example 1

[0045] Raw material pretreatment and detoxification agent preparation: Wash and dry the shrimp shells, crush them with a crusher, pass them through a 200-mesh sieve, soak them in 10% dilute hydrochloric acid at 50°C for 6 hours, collect the precipitate by centrifugation, wash the precipitate with ethanol until neutral and dry it to obtain detoxification agent B.

[0046] Comparative Example 2

[0047] Raw material pretreatment: Wash and dry the shrimp shells, crush them with a crusher, pass them through a 200-mesh sieve, soak them in 10% dilute hydrochloric acid at 50°C for 6 hours, collect the precipitate by centrifugation, wash the precipitate with ethanol until neutral and dry it to obtain the first dried product.

[0048] Preparation of detoxifying agent: The first dried product was calcined in a muffle furnace at 200℃ for 4 hours. The calcined product was ground through a 200-mesh sieve, and the sieve-filled material was ultrasonically treated in an environment with a pH of 10 (ultrasonic power of 500W, ultrasonic time of 90min). After ultrasonic treatment, it was centrifuged (centrifugation speed of 3000rpm / min, centrifugation time of 10min). The precipitate was collected, washed with ethanol until neutral, and then dried at 40℃ to obtain detoxifying agent C.

[0049] Comparative Example 3

[0050] Raw material pretreatment: Wash and dry the shrimp shells, crush them with a crusher, pass them through a 200-mesh sieve, soak them in 10% dilute hydrochloric acid at 50°C for 6 hours, collect the precipitate by centrifugation, wash the precipitate with ethanol until neutral and dry it to obtain the first dried product.

[0051] Preparation of detoxifying agent: The first dried product was calcined in a muffle furnace at 200℃ for 4 hours. The calcined product was ground through a 200-mesh sieve. The undersize material was soaked in an environment with pH 10 for 90 minutes, washed with ethanol until neutral, and then dried at 40℃. After drying, it was placed in a muffle furnace again for calcination at 700℃ for 4 hours. The calcined product was collected, soaked in an environment with pH 10 for 90 minutes, washed with ethanol until neutral, and then dried at 50℃ to obtain detoxifying agent D.

[0052] Test Example 1

[0053] The detoxifying agents prepared in the above examples and comparative examples were added at 0.2 wt% of the oil sample to a rapeseed oil sample containing 42 ng / mL benzo(a)pyrene. The mixture was stirred under vacuum at 50 rpm / min for 35 min at 90°C. The clarified oil sample was then collected by filtration. The concentration of the hazardous substance benzo(a)pyrene in the treated oil sample was determined according to the national standard GB 5009.27-2016, "Determination of Benzo(a)pyrene in Food". The specific test results are shown in the table below.

[0054] Table 1. Effect of the detoxifying agent on the removal of benzo(α)pyrene

[0055] Detoxifier Sample A B C D Removal rate (%) 92.3％ 5％ 1.2％ 17.5％

[0056] Test Example 2

[0057] The detoxifying agents prepared in the above examples and comparative examples were added at 0.2 wt% of the sample weight to a methanol solution containing 536.89 ng / mL zearalenone. The solutions were shaken on a shaker at 150 rpm / min for 30 min at 50°C. The samples were then filtered and collected. The concentration of the hazardous substance zearalenone in the treated samples was determined according to the method specified in the national standard GB 5009.209-2016, "Determination of Zearalenone in Food". The specific test results are shown in the table below.

[0058] Table 2. Effect of the detoxifying agent on the removal of zearalenone.

[0059] Detoxifier Sample A B C D Removal rate (%) 86.43％ 0 0 6.56％

[0060] Test Example 3

[0061] The detoxifying agents prepared in the above examples and comparative examples were added at 0.8 wt% of the sample weight to corn oil containing 523.06 ng / mL zearalenone. The mixture was stirred under vacuum at 50 rpm / min for 30 min at 90°C. The samples were then filtered and collected. The concentration of the hazardous substance zearalenone in the treated samples was determined according to the national standard GB 5009.209-2016, "Determination of Zearalenone in Food". The specific test results are shown in the table below.

[0062] Table 3. Effect of detoxifying agents on the removal of zearalenone from corn oil.

[0063] Detoxifier Sample A B C D Removal rate (%) 92.84％ 19.12％ 1.74％ 26.22％

[0064] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A method for preparing a detoxifying agent for removing benzo[a]pyrene and / or zearalenone, characterized in that, The preparation method includes: (1) The shrimp shells and / or crab shells that have been cleaned and dried are crushed, then soaked in hydrochloric acid and centrifuged to obtain the first precipitate. Finally, the first precipitate is washed and dried to obtain the first dried product. (2) The first dried material is subjected to calcination, grinding, ultrasonic treatment and centrifugation to obtain a second precipitate, and then the second precipitate is washed and dried to obtain a second dried material; (3) The second dried material is subjected to calcination, ultrasonic treatment and centrifugation to obtain a third precipitate, and then the third precipitate is washed and dried to obtain a detoxifying agent; In step (3), the burning temperature is 400-800℃ and the time is 3-7h; The conditions for ultrasonic treatment include: an environment with a pH of 8-12, an ultrasonic power of 450-1000W, and an ultrasonic time of 60-120min.

2. The preparation method according to claim 1, wherein, In step (1), the hydrochloric acid is a dilute hydrochloric acid with a mass concentration of 5-12%; The soaking temperature is 45-80℃, and the soaking time is 4-8 hours.

3. The preparation method according to claim 1, wherein, In step (1), the crushing process involves crushing the material with a crusher and passing it through a 150-250 mesh sieve. The washing condition is to wash until neutral; The solvent used for washing is at least one of methanol, ethanol, diethyl ether, petroleum ether, and acetone.

4. The preparation method according to claim 1, wherein, In step (2), the burning temperature is 180-300℃ and the time is 3-8h; The conditions for ultrasonic treatment include: an environment with a pH of 8-12, an ultrasonic power of 450-1000W, and an ultrasonic time of 60-120min. The centrifugation conditions include: a centrifugation speed of 2800-5000 rpm / min and a centrifugation time of 8-25 min.

5. The preparation method according to claim 1, wherein, In step (2), a muffle furnace is used for the burning process; The particle size of the grinding process is less than 150-250 mesh; The washing condition is to wash until neutral; The solvent used for washing is a low-melting-point organic solvent; The drying temperature is 30-50℃.

6. The preparation method according to claim 5, wherein, In step (2), the solvent used for washing is at least one of methanol, ethanol, diethyl ether, petroleum ether and acetone.

7. The preparation method according to claim 1, wherein, In step (3), The centrifugation conditions include: a centrifugation speed of 2800-5000 rpm / min and a centrifugation time of 8-25 min.

8. The preparation method according to claim 1, wherein, In step (3), a muffle furnace is used for the burning process; The washing condition is to wash until neutral; The solvent used for washing is a low-melting-point organic solvent; The drying temperature is 30-50℃.

9. The preparation method according to claim 8, wherein, In step (3), the solvent used for washing is at least one of methanol, ethanol, diethyl ether, petroleum ether and acetone.

10. The detoxifying agent prepared by the preparation method according to any one of claims 1-9.

11. The application of the detoxifying agent according to claim 10 for the removal of benzo[a]pyrene and / or zearalenone.

12. The application according to claim 11, wherein, Application for removing benzo[a]pyrene and / or zearalenone from edible oils.

13. The application according to claim 11 or 12, wherein, The amount of the detoxifying agent added is 0.05-2 wt% based on the total weight of the sample to be treated; The detoxifying agent is removed at a temperature of 50-110℃ for 15-35 minutes.