Method for reducing phthalate plasticizer content in natural plant extracts

Abstract

The application discloses a method for reducing the content of phthalate plasticizer in natural plant extract, which comprises the following steps: mixing natural plant extract powder and an aqueous solution of ethanol with a volume concentration of 95% or anhydrous ethanol according to a ratio of 1g:2-10mL, stirring and dissolving under the condition of 20-80 DEG C, then adding water with a mass of 2-10 times that of the natural plant extract, mixing, standing for 10-20min, and centrifuging or filtering; and washing the obtained solid with pure water, drying at 40-80 DEG C, and obtaining the natural plant extract with low content of phthalate plasticizer. The method is simple, non-toxic, and free of discharge of organic pollutants. The method can effectively reduce the content of phthalate plasticizer in the natural plant extract, so that the content of the plasticizer reaches below the limited value, and the content of effective components also meets the quantitative standard, and the plasticizer removal rate is greater than or equal to 82%.

Description

Technical Field

[0001] This invention belongs to the field of chemical separation, specifically relating to a method for reducing the content of phthalate plasticizers in natural plant extracts. Background Technology

[0002] Due to factors such as soil pollution during the plant cultivation process and lax management of plastic film used in planting, as well as the use of production equipment containing plastic materials, the final products often contain excessive levels of plasticizers, causing great trouble to the company's normal production and product quality.

[0003] Phthalate esters (PAEs) are a class of recalcitrant organic compounds widely used as plasticizers in polyvinyl chloride (PVC) plastics. PAEs can bioaccumulate through the animal food chain and are classified as hormone-like pollutants, disrupting the endocrine system and leading to reproductive disorders, teratogenicity, and carcinogenicity. They also affect the body's immune function, and even low concentrations can have adverse effects on organisms. Therefore, plasticizers not only seriously affect food quality and safety but also further arouse public concern about food safety. Currently, GB 9685-2016 sets limits for three plasticizers: di(α-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DBP), and diisononyl phthalate (DINP) (DEHP < 1.5 mg / kg, DBP < 0.3 mg / kg, DINP < 9 mg / kg). Therefore, the content of phthalate plasticizers in natural plant extracts must meet the standards.

[0004] Existing methods for reducing phthalate plasticizer content include adsorption, macroporous resin elution, molecular distillation, solvent extraction, and strong oxidant methods. Molecular distillation requires sophisticated equipment and is energy-intensive due to the need for vacuum conditions. Solvent extraction easily introduces organic solvents, increasing the risk of secondary contamination. Macroporous resin elution offers good selectivity, but its production cost is high, and the resulting product cannot be used in the production of ordinary or functional foods. Adsorption is a relatively simple and flexible traditional chemical separation method, but it results in the loss of active ingredients while adsorbing plasticizers, and the recovery and processing of the adsorbed material is difficult. Strong oxidant methods may affect the activity of plant extracts. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for reducing the content of phthalate plasticizers in natural plant extracts.

[0006] The technical solution of this invention is summarized as follows:

[0007] A method for reducing the content of phthalate plasticizers in natural plant extracts includes the following steps:

[0008] Mix the natural plant extract powder with an ethanol aqueous solution or anhydrous ethanol with a volume concentration of ≥95% at a ratio of 1g:2-10mL, stir and dissolve at 20℃-80℃, then add 2-10 times the mass of water of the natural plant extract, mix, let stand for 10-20min, centrifuge or filter; wash the solid obtained by centrifugation or filtration with pure water, and dry at 40-80℃ to obtain a natural plant extract with low phthalate plasticizer content.

[0009] Preferably, the natural plant extract is soybean extract, milk thistle extract, peppermint extract, marigold extract, sesame extract, or celery extract; other natural plant extracts may also be selected.

[0010] Preferably, the centrifugation speed is 2000-10000 r / min and the centrifugation time is 10-15 min.

[0011] Preferably, the filter cloth used for filtration is 100-600 mesh.

[0012] The phthalate plasticizer is at least one selected from diethyl phthalate, di-n-butyl phthalate, di(α-ethylhexyl) phthalate, diisononyl phthalate, and butyl benzyl phthalate.

[0013] Advantages of this invention:

[0014] The method of this invention is simple, non-toxic, and produces no organic pollutants. This method can effectively reduce the content of phthalate plasticizers in natural plant extracts, bringing the plasticizer content below the limit value, and also ensuring that the content of its active ingredients meets quantitative standards, with a plasticizer removal rate ≥82%. Attached Figure Description

[0015] Figure 1 The content of phthalate plasticizers in samples before and after treatment using the method of the present invention is used. Detailed Implementation

[0016] The present invention will be further described below through specific embodiments.

[0017] Natural plant extract powders can also be selected as natural plant extract pastes.

[0018] Preparation of soybean extract: Wash and dry soybeans, crush them, put them into cans, add an 80% ethanol aqueous solution with a volume concentration of 8 times that of soybeans, heat and reflux to extract three times, 2 hours each time; filter while hot, combine the three extracts, concentrate and evaporate to an extract with a specific gravity d=1.20, dry the extract and crush it to obtain soybean extract powder.

[0019] The preparation of milk thistle extract, peppermint extract, marigold extract, sesame extract, or celery extract is the same as that for soybean extract.

[0020] Example 1

[0021] Detection: The specific type of phthalate plasticizer in soybean extract was qualitatively detected and identified as di-n-butyl phthalate.

[0022] To test the effectiveness of the present invention, in this embodiment, 1 mg of di-n-butyl phthalate was added to 1 kg of soybean extract powder in advance.

[0023] A method for reducing the content of phthalate plasticizers in natural plant extracts includes the following steps:

[0024] Soybean extract powder (with the above-mentioned plasticizer added) and anhydrous ethanol were mixed at a ratio of 1g:4mL and stirred and dissolved at 70℃. Then, water with a mass of 8 times that of soybean extract was added, mixed, and allowed to stand for 15min. The mixture was then filtered through a 100-mesh (or 200-mesh) filter cloth. The solid obtained by filtration was washed three times with pure water and dried at 70℃ to obtain soybean extract with low phthalate plasticizer content.

[0025] To establish a standard curve for di-n-butyl phthalate, the specific steps are as follows: Accurately weigh di-n-butyl phthalate (standard) and add it to a volumetric flask. Dilute to volume with n-hexane and vortex to mix thoroughly; this is the mother liquor. Then, serially dilute with n-hexane to obtain standard samples of different concentrations. Perform gas chromatography analysis to establish a standard curve for di-n-butyl phthalate and derive the regression equation.

[0026] The determination of the di-n-butyl phthalate (DBP) content in the raw materials and product of this embodiment included the following steps: Accurately weigh 0.5 g each of the dried soybean extract and product into 15 mL centrifuge tubes, add 2 mL of distilled water, sonicate to mix, then accurately add 8 mL of n-hexane, sonicate for 30 min, centrifuge at 2000 r / min for 10 min, collect the supernatant, and dry it under nitrogen at 40℃. Accurately dilute the n-hexane to 2 mL for GC analysis. Gas chromatography analysis showed that the DBP content in the product obtained in this embodiment was 0.20 mg / kg, with a plasticizer removal rate of 84%, meeting the national standard (DBP < 0.3 mg / kg). (See [link to relevant documentation]). Figure 1 .

[0027] Example 2

[0028] Detection: The specific types of phthalate plasticizers in sesame extract were qualitatively detected and identified as di(α-ethylhexyl) phthalate and diisononyl phthalate.

[0029] Add 1 mg of di(α-ethylhexyl) phthalate and 1 mg of diisononyl phthalate to 1 kg of sesame extract powder.

[0030] A method for reducing the content of phthalate plasticizers in natural plant extracts includes the following steps:

[0031] Sesame extract powder (with the two plasticizers mentioned above added) was mixed with a 95% ethanol aqueous solution at a ratio of 1g:2mL. The mixture was stirred and dissolved at 60℃. Then, water with a mass twice that of the sesame extract was added, mixed, and allowed to stand for 10 minutes. The mixture was then centrifuged at 2000r / min (or 3000r / min) for 15 minutes. The solid obtained by centrifugation was washed twice with pure water and dried at 80℃ to obtain a sesame extract with low phthalate plasticizer content.

[0032] Establish a standard curve for di(α-ethylhexyl) phthalate. For specific steps, please refer to Example 1, Establishment of the standard curve for di-n-butyl phthalate.

[0033] The content of di(α-ethylhexyl) phthalate in the raw materials and products of this embodiment was determined, and the steps are the same as in Example 1.

[0034] The product obtained in this embodiment contains 0.14 mg / kg of di(α-ethylhexyl) phthalate, and the removal rate of di(α-ethylhexyl) phthalate reaches 90%, which meets the national standard (DEHP < 1.5 mg / kg).

[0035] Establish a standard curve for diisononyl phthalate. For specific steps, please refer to Example 1, "Establishment of the standard curve for di-n-butyl phthalate".

[0036] The content of diisononyl phthalate in the raw materials and products of this embodiment was determined, and the steps are the same as in Example 1.

[0037] The product obtained in this embodiment contains 0.3 mg / kg of diisononyl phthalate, and the removal rate of diisononyl phthalate reaches 89%, which meets the national standard (DINP < 9 mg / kg).

[0038] Example 3

[0039] Detection: The specific types of phthalate plasticizers in peppermint extract were qualitatively detected and identified as di(α-ethylhexyl) phthalate and diisononyl phthalate.

[0040] Add 1 mg of di(α-ethylhexyl) phthalate and 1 mg of diisononyl phthalate to 1 kg of peppermint extract powder.

[0041] A method for reducing the content of phthalate plasticizers in natural plant extracts includes the following steps:

[0042] Peppermint extract powder (with the two plasticizers mentioned above added) was mixed with a 96% ethanol aqueous solution at a ratio of 1g:4mL. The mixture was stirred and dissolved at 20°C. Then, 10 times the weight of water was added to the peppermint extract, and the mixture was mixed and allowed to stand for 10 minutes. The mixture was then filtered through a 600-mesh filter cloth. The solid obtained from the filtration was washed twice with pure water and dried at 40°C to obtain a peppermint extract with low phthalate plasticizer content.

[0043] Establish a standard curve for di(α-ethylhexyl) phthalate, see Example 1 for the establishment of the standard curve for di-n-butyl phthalate.

[0044] The content of di(α-ethylhexyl) phthalate in the raw materials and products of this embodiment was determined, and the steps are the same as in Example 1.

[0045] The peppermint extract obtained in this embodiment contained 0.10 mg / kg of di(α-ethylhexyl) phthalate, and the removal rate of di(α-ethylhexyl) phthalate reached 87%, which meets the national standard (DEHP < 1.5 mg / kg).

[0046] Establish a standard curve for diisononyl phthalate. For specific steps, please refer to Example 1, "Establishment of the standard curve for di-n-butyl phthalate".

[0047] The content of diisononyl phthalate in the raw materials and products of this embodiment was determined, and the steps are the same as in Example 1.

[0048] The product obtained in this embodiment contains 0.28 mg / kg of diisononyl phthalate, and the removal rate of diisononyl phthalate reaches 90%, which meets the national standard (DINP < 9 mg / kg).

[0049] Example 4

[0050] Detection: The specific type of phthalate plasticizer in milk thistle extract was qualitatively detected and identified as di-n-butyl phthalate.

[0051] Add 1 mg of di-n-butyl phthalate to 1 kg of milk thistle extract powder.

[0052] A method for reducing the content of phthalate plasticizers in natural plant extracts includes the following steps:

[0053] Milk thistle extract powder (with the above-mentioned plasticizer added) was mixed with 97% ethanol aqueous solution at a ratio of 1g:10mL. The mixture was stirred and dissolved at 80℃. Then, 10 times the weight of water of milk thistle extract was added, mixed, and allowed to stand for 20min. The mixture was then centrifuged at 10000r / min for 10min. The solid obtained by centrifugation was washed three times with pure water and dried at 80℃ to obtain milk thistle extract with low phthalate plasticizer content.

[0054] Establish a standard curve for di-n-butyl phthalate. For specific steps, please refer to Example 1, "Establishment of the Standard Curve for Di-n-butyl Phthalate".

[0055] The content of di-n-butyl phthalate in the raw materials and products of this embodiment was determined, following the same steps as in Example 1.

[0056] The product obtained in this embodiment contains 0.21 mg / kg of di-n-butyl phthalate and has a plasticizer removal rate of 82%, which meets the national standard (DBP < 0.3 mg / kg).

[0057] Experiments have shown that by replacing milk thistle extract with marigold extract or celery extract in this embodiment, while keeping other aspects the same as in this embodiment, marigold extract and celery extract with low phthalate plasticizer content can be obtained.

Claims

1. A method for reducing the content of phthalate plasticizers in natural plant extracts, characterized by: Includes the following steps: Mix the natural plant extract powder with an ethanol aqueous solution or anhydrous ethanol with a volume concentration of ≥95% at a ratio of 1g:2-10mL, stir and dissolve at 20℃-80℃, then add 2-10 times the mass of water of the natural plant extract, mix, let stand for 10-20min, centrifuge or filter; wash the solid obtained by centrifugation or filtration with pure water, and dry at 40-80℃ to obtain a natural plant extract with low phthalate plasticizer content.

2. The method according to claim 1, characterized in that... The natural plant extracts are soybean extract, milk thistle extract, peppermint extract, marigold extract, sesame extract, or celery extract.

3. The method according to claim 1, characterized in that... The centrifugation speed is 2000-10000 r / min, and the centrifugation time is 10-15 min.

4. The method according to claim 1, characterized in that... The filter cloth used for filtration is 100-600 mesh.

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