阅读说明：本技术 邻苯二甲酸二丁酯的消减方法 (Method for reducing dibutyl phthalate ) 是由 方海琴 刘爱东 章程 王雪 马小开 王恒 刘珊 张彤薇 曹瀚文 方业鑫 丛良滋 于 2020-12-01 设计创作，主要内容包括：本发明涉及邻苯二甲酸酯类物质的治理领域,具体而言,涉及一种邻苯二甲酸二丁酯的消减方法。该方法利用基于介质阻挡放电技术的平板-平板电极低温等离子体激发源产生低温等离子体对邻苯二甲酸二丁酯进行消减。本方法对邻苯二甲酸二丁酯的消减率可达约60％以上,且消解效果好,对细胞毒性更小。(The invention relates to the field of treatment of phthalate substances, in particular to a method for reducing dibutyl phthalate. The method utilizes a plate-plate electrode low-temperature plasma excitation source based on a dielectric barrier discharge technology to generate low-temperature plasma to reduce the dibutyl phthalate. The method has the advantages of high dibutyl phthalate reduction rate of over 60 percent, good digestion effect and low cytotoxicity.)

1. A method for reducing dibutyl phthalate is characterized in that a low-temperature plasma is generated by using a flat plate-flat plate electrode low-temperature plasma excitation source based on a dielectric barrier discharge technology to reduce dibutyl phthalate.

2. The dibutyl phthalate reduction method according to claim 1, characterised in that the effective electrode area at the time of discharge is 18cm²～22cm²。

3. The dibutyl phthalate reduction method according to claim 2, wherein the power supply has a voltage amplitude of 3kHz to 8kV and a frequency of 10kHz to 50kHz at the time of reduction.

4. The dibutyl phthalate reduction method according to claim 3, wherein a glass carrier is placed as a blocking medium on the lower electrode, and the thickness of the glass carrier is 1.5mm to 2.5 mm.

5. The method according to claim 4, wherein the dibutyl phthalate sample is placed in the glass carrier for subtraction, plasma is generated between the upper electrode and the sample, and the air gap is 1mm to 3 mm.

6. The dibutyl phthalate reduction method according to any one of claims 1 to 5, characterized in that the atmosphere in which the low-temperature plasma is generated is any one or more of air, an oxygen-containing gas, nitrogen, a rare gas.

7. The dibutyl phthalate reduction method according to any one of claims 1 to 5, characterized in that the reduction time is 3min or more.

8. The method according to any one of claims 1 to 5, wherein the output of the power supply for the dielectric barrier discharge is a sinusoidal voltage.

9. The method according to any one of claims 1 to 5, wherein the upper and lower electrodes are circular aluminum flat plate electrodes.

10. Use of the method according to any one of claims 1 to 9 for the reduction of dibutyl phthalate in foodstuffs, food packaging materials, toys, plastic gaskets and hoses on machinery, medical blood bags and hoses, soil.

Technical Field

The invention relates to the field of treatment of phthalate substances, in particular to a method for reducing dibutyl phthalate.

Background

Phthalate (PAEs) substances, commonly known as plasticizers, are widely used in the production and processing of plastic products to improve the flexibility and durability of the plastic. PAEs account for 70% of the global plasticizer market, with Dibutyl phthalate (DBP) being one of the most predominantly used PAEs.

PAEs are well compatible with plastics, but they do not form covalent bonds with the plastic matrix, but rather are linked by hydrogen bonds or van der Waals forces, so that when plastic articles are used, PAEs are gradually released into the environment, thereby directly or indirectly endangering the health of the organism. At present, PAEs become the most common organic pollutants in the whole world, PAEs which enter water bodies, soil and other environmental systems can be accumulated in microorganisms, animals, plants and human bodies through the biological accumulation and amplification effects of food chains due to the characteristics of persistence, high stability, biological activity, slow biological degradability, biological accumulation and the like, and further potential harm is generated to human health and ecological environment. Due to their widespread use, PAEs contaminants are detected in many environments and their concentration in surface water can be as high as 500 mg-L-1.

Research shows that DBP can interfere the endocrine system of human and animals at low concentration, and disturb reproductive capacity; the product also has carcinogenesis, teratogenesis, and mutagenesis effects at large dosage. Thus, six PAEs substances, including DBP, have been prioritized as pollutants by several national environmental protection organizations.

For the effective reduction of DBP, a high-efficiency and safe method is lacking at home and abroad so far. The existing other PAEs reduction and control methods mainly comprise non-biological pathway and biological pathway degradation, wherein the non-biological pathway comprises natural degradation including hydrolysis and photolysis and accelerated degradation or adsorption coagulation by a physical or chemical method; the situation that natural degradation is slow can be solved by adding exogenous substances to accelerate degradation, and the methods have the defects of slow process, insufficient degradation, efficient blood dripping, easiness in introducing secondary pollution, limitation of large-scale application and the like; therefore, it is very important to develop efficient, safe and green DBP abatement technology research.

Disclosure of Invention

The invention aims to select low-temperature plasma treatment as a core technology, generate low-temperature plasma by high-pressure gas discharge, develop experimental research for digesting mycotoxin, degrade Dibutyl phthalate (DBP) concentration and reduce DBP toxicity. Provides a brand new path and scientific basis for constructing an efficient, safe and green persistent pollutant reduction technology.

In order to achieve the above purpose of the present invention, the following technical solutions are adopted:

the invention relates to a method for reducing dibutyl phthalate, which utilizes a low-temperature plasma generated by a flat plate-flat plate electrode low-temperature plasma excitation source based on a dielectric barrier discharge technology to reduce dibutyl phthalate.

Optionally, in the method for reducing dibutyl phthalate, the effective area of the electrode in discharging is 18cm²～22cm²。

Optionally, in the dibutyl phthalate reduction method, when the dibutyl phthalate is reduced, the voltage amplitude of the power supply is 3 kV-8 kV, and the frequency is 10 kHz-50 kHz.

Optionally, in the method for reducing dibutyl phthalate, a glass carrier is placed on the lower electrode as a blocking medium, and the thickness of the glass carrier is 1.5mm to 2.5 mm.

Optionally, in the method for reducing dibutyl phthalate, the dibutyl phthalate sample is placed in the glass carrier for reduction, plasma is generated between the upper electrode and the sample, and the air gap is 1mm to 3 mm.

Optionally, in the dibutyl phthalate reduction method described above, the atmosphere for generating the low-temperature plasma is any one or more of air, oxygen-containing gas, nitrogen and rare gas.

Optionally, in the method for reducing dibutyl phthalate, the reduction time is more than or equal to 3 min.

Optionally, in the dibutyl phthalate reduction method, the output of the power supply used for the dielectric barrier discharge is a sinusoidal voltage.

Optionally, in the dibutyl phthalate reduction method, the upper and lower electrodes are circular aluminum flat plate electrodes.

According to a further aspect of the invention, the invention also relates to the use of a method as described above for the abatement of dibutyl phthalate in food products, food packaging materials, toys, plastic gaskets and hoses on mechanical equipment, medical blood bags and hoses, soil.

Compared with the prior art, the method provided by the invention has the advantages that various components such as ultraviolet rays, high-energy charged particles, active substances (molecules, excited state atoms, metastable state atoms and free radicals) and the like generated in the low-temperature plasma generating process can comprehensively act on DBP, so that the effect of reducing toxins is achieved. Compared with the traditional attenuation technology, the method has the advantages of good effect, no need of high temperature, environmental friendliness, high operation efficiency, no introduction of other pollutants, easiness in operation, high safety, no residue and the like.

The invention selects low-temperature plasma treatment as a core technology, utilizes high-pressure gas discharge to generate low-temperature plasma, develops experimental research for reducing DBP, degrades DBP and reduces the toxic effect of DBP. A brand new path and scientific basis are provided for constructing an efficient, safe and green DBP reduction technology.

The method has the advantages of high DBP eliminating rate up to 60%, good digestion effect and low cytotoxicity.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a graph showing the effect of DBP solution on zebrafish embryotoxicity after DBP and low temperature plasma treatment in one embodiment of the present invention.

Detailed Description

Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The invention relates to a method for reducing dibutyl phthalate, which utilizes a low-temperature plasma generated by a flat plate-flat plate electrode low-temperature plasma excitation source based on a dielectric barrier discharge technology to reduce dibutyl phthalate.

The existing state of the substance generally presents a solid, liquid and gaseous conversion process along with the rise of the temperature, and the basic forms of the three substances are called three states of the substance. In the case of a substance in a gaseous state, if the temperature rises to several thousand degrees centigrade or higher, molecules of the substance are accelerated by thermal motion, and gas molecules are ionized by the violent collision with each other, and the substance becomes a mixture of free electrons and positive ions, and this state of the substance is referred to as a fourth state of the substance, i.e., a plasma state.

According to the invention, a high-voltage power supply is adopted to connect a plasma electrode for micro-discharge, and various components such as ultraviolet rays, high-energy charged particles, active substances (molecules, excited atoms, metastable atoms and free radicals) and the like generated in the process of generating low-temperature plasma can comprehensively act on DBP, so that the effect of reducing toxins is achieved. Compared with the traditional attenuation technology, the method has the advantages of good effect, no need of high temperature, environmental friendliness, high operation efficiency, no introduction of other pollutants, easiness in operation, high safety, no residue and the like.

In conclusion, the method provided by the invention has a good application prospect.

In some embodiments, the method is performed without additional catalyst, for example, metal ion catalysts, such as ions of Fe, Cu.

In some embodiments, the effective electrode area during discharge is 18cm²～22cm²Alternatively, 19 cm²、20cm²、21cm²、20cm²。

In some embodiments, the voltage amplitude of the power supply is 3kV to 8kV, and optionally 4kV, 5kV, 6kV or 7kV during the subtraction.

In some embodiments, the frequency of the power source is 10kHz to 50kHz, alternatively 15, 20, 25, 30, 35, 40 or 45kHz, when the subtraction is performed.

In some embodiments, a glass carrier is placed as a barrier medium on the lower electrode, and the thickness of the glass carrier is 1.5mm to 2.5 mm.

In some embodiments, the glass support is a plate. The diameter is preferably 70mm to 90mm, and the depth is 1mm to 4 mm.

In some embodiments, the dibutyl phthalate sample is placed in the glass carrier for reduction, plasma is generated between the upper electrode and the sample, and the air gap is 1mm to 3mm, or 2 mm.

The atmosphere for generating the low-temperature plasma may be, for example, an oxygen-containing gas such as O₂、H₂O、NO₂Nitrogen and air, or inert gases (e.g., helium, neon, argon, krypton, xenon); or a mixture of the above gases. Preference is given to oxygen-containing gases, in particular O₂And air. The gas pressure may be atmospheric pressure or lower.

In some embodiments, the time of the subtraction is 3min or more, e.g., 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min or more.

Although the low-temperature plasma technology does not need harsh operating conditions such as high temperature, high pressure, chemical reagent addition and the like, the low-temperature plasma technology has higher power consumption because of being generated under the high-pressure discharge condition, so that the technology has higher cost for treating pollutants; the invention finds that when the DBP is reduced, when the reduction time is about 3min, the reduction effect of increasing the treatment time can not be obviously strengthened. Therefore, in order to improve the energy utilization rate, reduce the energy consumption and reduce the treatment cost, in a more preferred embodiment, the reduction time is 2min to 4min, and most preferably about 3 min.

In some embodiments, the power output used for the dielectric barrier discharge is a sinusoidal voltage.

In some embodiments, the upper and lower electrodes are circular aluminum flat plate electrodes.

In some embodiments, the electrode diameter is 60mm to 80mm and the electrode edge radius is 8mm to 12 mm.

According to a further aspect of the invention, the invention also relates to the use of a method as described above for the abatement of dibutyl phthalate in food products, food packaging materials, toys, plastic gaskets and hoses on mechanical equipment, medical blood bags and hoses, soil.

Embodiments of the present invention will be described in detail with reference to examples.

Examples

The invention provides the following experiments to verify the effect of low temperature plasma on DBP abatement.

1. The method comprises the following steps:

and (3) treating DBP by using low-temperature plasma, detecting the reduction efficiency of the treatment solution by using isotope dilution liquid chromatography-tandem mass spectrometry (LMS), and performing acute embryo experiment (FET) on the treatment solution to determine the biological effect.

2. Materials and reagents

A plasma generating device, a DBP sample, a standard product, a plate, a centrifuge tube, sterilization water, a zebra fish breeding and breeding system (Beijing Aisheng scientific and technological company), and the like.

3. The experimental steps are as follows:

(1) liquid preparation

Adding 1g/ml of DBP, dissolving to 0.5g/ml with ethanol, adding 1% BSA, performing ultrasonic emulsification to form a nano-emulsion, and diluting with ultrapure water to 0.1mg/ml for plasma treatment;

(2) plasma treatment

The power supply adopted by the method is a high-voltage high-frequency power supply (HFHV20-1 type), and the power supply consists of two parts: a control cabinet and a high-frequency transformer. The input is 220V power frequency voltage, the output is sinusoidal voltage, the amplitude is 0-20 kV adjustable, and the frequency is 10-60 kHz adjustable. In the experiment, the voltage amplitude is 3-8 kV, and the frequency is 30 kHz. The discharge electrode adopts a flat dielectric barrier discharge structure, the upper electrode and the lower electrode adopt circular aluminum flat electrodes, the diameter of the electrode is 70mm, the edge radius of the electrode is 10mm, and the effective area of the electrode is about 19.6cm2 during discharge. A glass plate serving as a barrier medium is placed on the lower electrode, and the glass plate is 80mm in diameter, 2mm in thickness and 2mm in depth. After the DBP was set up, 7ml each time was injected into the plate, plasma was generated between the upper electrode and the solution level, and the air gaps were 2 mm. The treatment time was set to 1 minute (short time), 3 minutes (medium time), and 10 minutes (long time) in order to compare the treatment effect of the low-temperature plasma.

(3) Resolution rate verification

According to the national standard GB5009.111, the concentration of DBP before and after treatment is determined by adopting a liquid chromatography-tandem mass spectrometry method, and the reduction efficiency is determined

(4) Biological effect verification

Zebrafish (Danio rerio) has the advantages of small body size, in-vitro fertilization, transparent embryo, easy observation and the like, and is an ideal model organism in toxicological research. The toxic effect of DBP on zebra fish embryos at different development stages is researched. The method comprises the following steps: zebra fish embryos 2h (2hpf) post fertilization were treated with 0, 0.1, 0.3, 1.0, 3.0, 10.0 μ g/mL of DBP and development of zebra fish embryos was recorded at 12, 24, 48, 72, 96hpf time points.

4. Results

(1) Resolution results

The result of the low-temperature plasma on the DBP is shown in the table 1, the DBP is hardly degraded after being treated by the low-temperature plasma for 1 minute, the digestion rate of 3 minutes can reach 61.3 percent, and the digestion rate of 10 minutes is not reduced more obviously; the results show that a significant degradation can be achieved by low temperature plasma treatment of DBP for three minutes.

TABLE 1 DBP abatement in Low temperature plasma treatment

At present, no effective degradation method for DBP in the environment exists domestically or internationally, and the existing research shows that the degradation progress of methyl bifhenate (PAEs) is expressed as microbial degradation, but no report about the microbial degradation of DBP is provided, so that the method is expected to fill the blank of the effective method lacking the degradation of DBP in the environment, and the comparison of the low-temperature plasma treatment of DBP with the treatment method in the prior art is shown in the following table (table 2).

TABLE 2 Low temperature plasma treatment of DBP in comparison to prior art treatment methods

(2) Biological effect verification test results

FET results show that obvious embryonic development inhibition occurs in DBP, and the abnormal development of zebra fish juvenile fish can be caused, including embryo incomplete hatching, 24hpf egg coagulation, 72hpf severe pericardial edema, developmental deformity and the like; after the DBP with the same concentration is treated by plasma, the influence on the development morphology of the zebra fish juvenile fish is small, and only a slight pericardial edema phenomenon is observed at the high concentration. The embryonic development status (FIG. 1) and the toxic effect value (BMDL) of zebrafish are shown below.

P-DBP is DBP solution after low-temperature plasma treatment

And (3) observing a dose-reaction relation between the DBP concentration and a zebra fish embryo development index (hatching rate) by using BMDS software and adopting different mathematical models such as Hill and the like, and calculating to obtain a toxic effect value (reference dose lower limit, BMDL) of the DBP on the zebra fish embryo development, wherein the BMDL of the DBP on the zebra fish embryo development toxicity is 0.47930ug/ml, and the BMDL is 1.2779ug/ml after plasma treatment, so that the toxicity on the zebra fish embryo is reduced.

TABLE 3 Effect of DBP and DBP solution after low temperature plasma treatment on zebra fish embryotoxicity

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The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.