CN110015727B - A kind of method for electrolytic air flotation to remove microplastics in water body - Google Patents
A kind of method for electrolytic air flotation to remove microplastics in water body Download PDFInfo
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- CN110015727B CN110015727B CN201910382548.XA CN201910382548A CN110015727B CN 110015727 B CN110015727 B CN 110015727B CN 201910382548 A CN201910382548 A CN 201910382548A CN 110015727 B CN110015727 B CN 110015727B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229920000426 Microplastic Polymers 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000005188 flotation Methods 0.000 title claims abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 21
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 13
- 150000001879 copper Chemical class 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 description 35
- 239000004033 plastic Substances 0.000 description 35
- 238000005070 sampling Methods 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000002352 surface water Substances 0.000 description 7
- -1 hydrogen ions Chemical class 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- OUNVHRVEZKVXQB-UHFFFAOYSA-N copper;dodecyl benzenesulfonate Chemical compound [Cu].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 OUNVHRVEZKVXQB-UHFFFAOYSA-N 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000012258 stirred mixture Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/465—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electroflotation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
本发明属于固体废弃物处理技术领域，特别涉及一种电解气浮除去水体中微塑料的方法，首先向分散有微塑料的水体中加入长链烷基胺与铜离子的络合物并混合充分，长链烷基胺与铜离子的络合物由铜盐和长链烷基胺混合加热反应得到，再对所得的混合水体进行电解处理，电解时在混合水体中产生气泡，这些气体气泡上升的同时也带动水体中的微塑料进行上浮，最后将水体上层集中的微塑料一并收集除去，实现微塑料与水体的分离。The invention belongs to the technical field of solid waste treatment, and in particular relates to a method for removing microplastics in a water body by electrolytic air flotation. First, a complex of long-chain alkylamine and copper ions is added to the water body in which the microplastics are dispersed, and the mixture is fully mixed. , the complex of long-chain alkylamine and copper ion is obtained by mixing and heating copper salt and long-chain alkylamine, and then electrolyzing the obtained mixed water body. During electrolysis, bubbles are generated in the mixed water body, and these gas bubbles rise At the same time, it also drives the microplastics in the water body to float, and finally collects and removes the microplastics concentrated in the upper layer of the water body to realize the separation of the microplastics from the water body.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, and particularly relates to a method for removing micro-plastics in a water body by electrolytic air flotation.
Background
The micro plastic is widely distributed in the environment, such as distributed in water and soil, and is easy to adsorb other pollutants in the water or soil, including organic pollutants, heavy metal pollutants and the like, so that the pollutants are enriched on the surface of the micro plastic and migrate along with the micro plastic. In addition, the micro-plastics are easily absorbed into the body by organisms, further causing the pollutants to be enriched in the organs of the organisms, and generating larger biological toxicity effect. Because the particle size of the micro plastic is very small, the micro plastic is difficult to separate from the environment.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for removing micro-plastics in a water body by electrolytic air flotation, which comprises the following steps:
(1) adding a complex of long-chain alkylamine and copper ions into the water body dispersed with the micro-plastics, fully mixing,
wherein the long-chain alkylamine is dodecylamine, the complex of the long-chain alkylamine and copper ions is obtained by mixing and heating copper salt and the long-chain alkylamine for reaction,
when the complex is added, the complex is firstly dispersed in ethanol, and then the obtained ethanol dispersion liquid of the complex is added into a water body, wherein the mass ratio of the complex to the ethanol is 1: 15-1: 30, of a nitrogen-containing gas;
(2) carrying out electrolytic treatment on the mixed water body obtained in the step (1),
during electrolytic treatment, correspondingly arranged anodes and cathodes are inserted into the mixed water body, graphite electrodes are adopted as the anodes and the cathodes, and the current density of direct current applied during electrolytic treatment is 80-200A/m2。
In the scheme, the electrolysis measures are utilized to generate bubbles in the mixed water body, specifically, hydrogen is generated on the cathode, oxygen is generated on the anode, the gas bubbles rise and simultaneously drive micro plastic in the water body to float, finally, the micro plastic concentrated on the upper layer of the water body is collected and removed together, the separation of the micro plastic and the water body is realized, meanwhile, the electrolysis gas floating method also generates electrode reaction, and the electrolysis gas floating method has the effects of electrochemical oxidation, electrochemical reduction and the like, and can simultaneously degrade organic pollutants in the water body. According to the principle that the water body is electrolyzed, the generated hydrogen has larger molar weight, and meanwhile, because the density of the hydrogen is obviously lower than that of the oxygen, the tendency that hydrogen bubbles generated by electrolysis float upwards to flush out of the water body is stronger, and the contribution to air floatation is obviously larger than that of oxygen bubbles generated on an anode;
before the electrolytic treatment, the complex of the long-chain alkylamine and the copper ion is fully dispersed in the water body containing the micro-plastic, the complex structurally has both a long-chain alkyl group and the copper ion complexed with the long-chain alkyl group, so that the complex has the property of a surfactant, the complex can be combined with the micro-plastic through the long-chain alkyl group, but the complex is different from a common ionic surfactant, the common ionic surfactant can be electrically ionized and decomposed in water, and the complex used in the scheme has stronger binding force between the copper ion and the long-chain alkyl group, and can possibly promote the copper ion to be also combined with the micro-plastic. On the basis, because copper ions in the water body can migrate to the cathode during electrolysis, in the scheme, the copper ions in the complex compound drive the micro-plastic to migrate to the cathode, and hydrogen bubbles are generated from the cathode and concentrated near the cathode, so that more micro-plastic floats upwards under the action of the hydrogen bubbles, and the removal effect on the micro-plastic in the water body is improved;
although the copper ions are inIn rank compared to H2The hydrogen ions in O preferentially obtain electrons, but in the scheme, microscopic copper ions drag a micro plastic to the cathode, so that the copper ions move forward under load and cannot easily reach the cathode, and a part of water still can be ionized to generate bubbles. In this embodiment, therefore, the sequence of electrons of the hydrogen ions and the copper ions on the cathode should not be obvious, in other words, the generation of bubbles and the migration of the micro-plastic to the cathode should be performed simultaneously.
Detailed Description
Preparation of the complex: dodecylamine and copper nitrate were mixed in a ratio of 9.5: 1, stirring and reacting fully at 110 ℃, discharging,
mixing the obtained materials according to the proportion of 1: the mass ratio of 20 was sufficiently dispersed in ethanol to obtain an ethanol dispersion of the complex.
Example 1
Weighing a plurality of circular micro plastic sheets with the diameter of 2mm, fully dispersing the circular micro plastic sheets into pure water to obtain a simulated dispersion liquid in which micro plastic pollution is stably suspended, wherein the concentration of the micro plastic sheets in the simulated dispersion liquid is 1g/L (176 pieces/L), adding the obtained ethanol dispersion liquid of the complex into the simulated dispersion liquid, and fully stirring the mixture until the mixture is in a suspended state, wherein the mass-volume ratio of the ethanol dispersion liquid of the complex to the simulated dispersion liquid is 100 g: 1L of the total weight of the mixture is obtained,
vertically inserting correspondingly arranged anodes and cathodes into the suspended mixed water body to a position close to the water bottom for electrolysis treatment, wherein the anodes and the cathodes are graphite electrode plates with the thickness of 4mm, the distance between the electrode plates is 30mm, 380V direct current voltage is applied in electrolysis, and the current density is 100A/m2The electrolysis time was 20 min. And after the electrolysis is finished, quickly pumping away and removing the liquid layer enriched with the micro-plastics on the upper layer of the water body, sampling at the middle position of the water body (on the height position) after the remaining water body is basically stable, and after the filtration is dried, finding that the average concentration of the micro-plastics in the water body at the moment is 9.3/L (sampling at three different positions on the same height respectively, calculating the average value, and the same below).
Comparative example 1
The procedure is as in example 1 except that no complex of a long chain alkylamine with copper ions is added:
ethanol was added to the simulated dispersion of example 1 and stirred well, the mass to volume ratio of ethanol to simulated dispersion was 95 g: 1L, adding sodium nitrate crystal powder, stirring fully to enable the density of a water body mixture in subsequent electrolysis to be the same as that in example 1 (avoiding the influence on the rise rate of the micro-plastic caused by different system densities), and then inserting an electrode for electrolysis treatment.
And after the electrolysis is finished, quickly pumping away and removing the liquid layer enriched with the micro-plastics on the upper layer of the water body, sampling at the middle position of the water body (in the height position) after the remaining water body is basically stable, and after the filtration is dried, finding that the average concentration of the micro-plastics in the water body at the moment is 73.3/L.
Comparative example 2
The procedure of example 1 was repeated except that the "complex of a long-chain alkylamine with copper ions" in example 1 was replaced with "copper dodecylbenzenesulfonate" containing copper ions in an equal molar amount with respect to the simulated dispersion liquid in example 1.
And sampling the purified water body, and after the purified water body is drained, finding that the average concentration of the micro-plastics in the water body is 94.7/L.
From the purification effect of the comparative example 2, the applicant believes that the copper dodecylbenzene sulfonate is basically ionized and decomposed into independent dodecylbenzene sulfonate ions and copper ions after entering the water body, so that the long-chain dodecylbenzene sulfonate ions and the micro plastic combined with the long-chain dodecylbenzene sulfonate ions cannot be simultaneously drawn close to the cathode region where the hydrogen bubbles float intensively when the copper ions migrate to the cathode, and the floating efficiency of the micro plastic along with the hydrogen bubbles cannot be improved; in contrast, the long-chain dodecylbenzene sulfonate ions have the function of emulsion stabilization, so that the micro-plastic can be more stably kept in the water body, and the purification effect is not as good as that of the blank control of the comparative example 1.
Example 2
Taking a ground surface water body which is concentrated by 100 times (sampling, filtering and weighing the ground surface water body which is concentrated by 100 times and is in a suspended state to obtain the mass concentration of the micro-plastic in the concentrated ground surface water body of 0.56g/L), adding the obtained ethanol dispersion liquid of the complex into the concentrated ground surface water body, and fully stirring the mixture until the mixture is in the suspended state, wherein the mass-volume ratio of the ethanol dispersion liquid of the complex to the concentrated ground surface water body is 56 g: 1L of the total weight of the mixture is obtained,
vertically inserting correspondingly arranged anodes and cathodes into the suspended mixed water body to a position close to the water bottom for electrolysis treatment, wherein the anodes and the cathodes are graphite electrode plates with the thickness of 4mm, the distance between the electrode plates is 30mm, 380V direct current voltage is applied in electrolysis, and the current density is 100A/m2The electrolysis time was 20 min. And after the electrolysis is finished, quickly pumping away and removing the liquid layer enriched with the micro-plastics on the upper layer of the water body, sampling at the central position of the water body (on the height position) after the remaining water body is basically stable, and after the filtration is dried, finding that the average mass concentration of the micro-plastics in the water body at the moment is 0.027g/L (sampling at three different positions on the same height respectively, calculating the average value, and the same below).
For comparison:
on the basis of example 2, the same procedure as in example 2 was followed except that no complex prepared as described above was added (likewise, the concentrated surface water was sufficiently dispersed by adding an amount of sodium nitrate crystal powder to the concentrated surface water so that the density of the water mixture at the time of subsequent electrolysis was the same as in example 2).
After the electrolyzed water body (the liquid layer with the upper layer enriched with the micro-plastics is extracted) is sampled and drained, the average mass concentration of the micro-plastics in the water body is found to be 0.263 g/L.
Example 3
Taking a soil sample polluted by micro-plastics, and mixing the soil and pure water according to a mass ratio of 1: 10 to be mixed and fully stirred to be suspended (the average concentration of the micro-plastics in the water body of the stirred mixture is 17.5/L), and the rest of the purification operation is the same as that of the example 2.
And (4) sampling, observing and detecting the electrolyzed water body (after the liquid layer with the upper layer enriched with the micro-plastics is extracted), and finding that the average concentration of the micro-plastics in the water body at the moment is 4/L.
For comparison:
on the basis of example 3, the same procedure as in example 3 was repeated except that no complex prepared as described above was added (similarly, the same amount of sodium nitrate crystal powder as that added to the water body of the mixture after stirring was sufficiently dispersed so that the density of the water body mixture at the time of subsequent electrolysis was the same as that of example 3).
Sampling, observing and detecting the electrolyzed water body (after the liquid layer with the upper layer enriched with the micro-plastics is extracted), and finding that the average concentration of the micro-plastics in the water body at the moment is 10.7/L.
Example 4
Taking sludge sediment at the bottom of the Yangtze river polluted by micro plastics, and mixing the sediment and pure water according to a mass ratio of 1: 10 mixing and fully stirring to a suspension state (the average concentration of the micro-plastics in the stirred mixture water body is 22.4/L), and the other purification operations are the same
Example 2.
Sampling, observing and detecting the electrolyzed water body (after the liquid layer with the upper layer enriched with the micro-plastics is extracted), and finding that the average concentration of the micro-plastics in the water body at the moment is 5.7/L.
For comparison:
on the basis of example 4, the same procedure as in example 4 was repeated except that no complex prepared as described above was added (similarly, the same amount of sodium nitrate crystal powder as that added to the water body of the mixture after stirring was sufficiently dispersed so that the density of the water body mixture at the time of subsequent electrolysis was the same as that of example 4).
Sampling, observing and detecting the electrolyzed water body (after the liquid layer with the upper layer enriched with the micro-plastics is extracted), and finding that the average concentration of the micro-plastics in the water body at the moment is 13/L.
Claims (5)
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| CN201910382548.XA CN110015727B (en) | 2019-05-09 | 2019-05-09 | A kind of method for electrolytic air flotation to remove microplastics in water body |
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Families Citing this family (6)
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| CN110369117B (en) * | 2019-08-14 | 2020-07-24 | 中国环境科学研究院 | A device and method for efficiently separating flotation microplastics |
| KR102121952B1 (en) * | 2019-09-26 | 2020-06-26 | 이제이콥부희 | System for creation of clean water |
| US11034592B1 (en) | 2019-12-11 | 2021-06-15 | International Business Machines Corporation | Microplastic cleaning, collection, and autonomous filtration |
| CN112830540B (en) * | 2021-01-21 | 2022-07-22 | 浙江树人学院（浙江树人大学） | A device and method for removing microplastics from polluted water bodies |
| CN115637563A (en) * | 2021-07-19 | 2023-01-24 | 青岛海尔洗涤电器有限公司 | Clothes treatment device and control method thereof |
| CN114751491B (en) * | 2022-04-29 | 2023-08-04 | 郑州大学 | Synchronous and efficient purification method and system for microplastics and heavy metal pollutants in water environment |
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| JPS5698487A (en) * | 1980-01-10 | 1981-08-07 | Asahi Glass Co Ltd | Purification method of potassium chloride brine |
| US4287052A (en) * | 1980-04-07 | 1981-09-01 | The Dow Chemical Company | Alkyl-substituted phenyl ether amine collectors in flotation |
| CN85107378A (en) * | 1984-09-13 | 1987-03-18 | 陶氏化学公司 | Frother composition and froth flotation process for recovering useful coal from raw coal |
| US4623436A (en) * | 1985-01-10 | 1986-11-18 | Showakoki Co., Ltd. | Method and apparatus for removing impurities from liquids |
| ES8706045A1 (en) * | 1985-11-29 | 1987-06-01 | Dow Chemical Co | Collector compositions for the froth flotation of mineral values |
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