CN111151570A - Development and application of rapid and efficient in-situ circulating repair system for organic pollution active oxygen of field soil and underground water - Google Patents
Development and application of rapid and efficient in-situ circulating repair system for organic pollution active oxygen of field soil and underground water Download PDFInfo
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- CN111151570A CN111151570A CN202010103776.1A CN202010103776A CN111151570A CN 111151570 A CN111151570 A CN 111151570A CN 202010103776 A CN202010103776 A CN 202010103776A CN 111151570 A CN111151570 A CN 111151570A
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- water
- active oxygen
- reaction tank
- soil
- organic
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/002—Reclamation of contaminated soil involving in-situ ground water treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Development and application of a rapid and efficient in-situ circulating repair system for organic pollution active oxygen of field soil and underground water, and belongs to the fields of ecological environment protection and ecological agriculture. The system is composed of the following parts: the system comprises a photovoltaic power generation system, a multifunctional combined storage battery, an inverter, a transformer, an air filter, a dryer, an air compressor, a cooler, an oxygen generator, a high-voltage discharge active oxygen machine, a control valve, an active oxygen reaction tank, a water-gas mixing pump, a control valve, a water well, a water pumping pipe, various electric wires, connecting pipelines and the like. The system pumps soil and underground water into the active oxygen reaction tank through a plurality of water wells, mixes with high-energy active oxygen and dissolves in water in the reaction tank, can rapidly oxidize and decompose organic pollutants in the soil and the underground water into carbon dioxide and water, and has no secondary pollution; the groundwater in 10000 soil groundwater wells of 100 + can be repaired at the same time.
Description
Technical Field
The invention belongs to the technical field of plant protection, pollution-free agriculture and ecological agriculture, and particularly relates to development and application of a rapid and efficient in-situ circulating repair system for organic pollution active oxygen of field soil and underground water.
Background
The farmland soil is a public basic resource for human production and life, and provides sufficient amount, safety and nutrition of grains for human. In the biological evolution process of billions of years, crops and pests synchronously evolve to form dynamic balance of a farmland ecosystem. However, due to the increase of the population of the earth, the demands of human beings on food and food are greatly increased, a plurality of new varieties of high-yield crops are cultivated, and meanwhile, the improvement of the multiple cropping index causes the rapid increase of crop diseases, insect pests and weeds, thereby increasing the technical requirements of people on the prevention and control of the diseases, insect pests and weeds. After world war II, with the great progress of organic chemical industry, the artificial synthesis and large-scale industrial production of various chemical pesticides brings hopes of preventing and treating crop diseases and insect pests and improving grain yield for human beings. However, in decades, chemical pesticides cause irrecoverable ecological disasters, pests and germs have strong resistance, a large amount of soil pesticides remain, soil ecosystems are polluted, underground water and surface water are polluted, atmosphere is polluted, pesticide residue of crop seeds exceeds standard, human health is seriously harmed, and three events of frequent teratogenesis, carcinogenesis and mutagenesis are more and more concerned in the world. Meanwhile, antibiotics are added into the feed in order to prevent diseases in the animal feeding process, and most of the antibiotics are discharged closely to feces to enter farmland soil as fertilizers, so that soil antibiotic pollution is caused.
Since many of the early pesticides were persistent toxic substances and difficult to degrade in a short period of time, especially organophosphorus and organochlorine pesticides have caused multiple environmental problems such as health hazards, various acute and chronic effects on the development of human and animals and nerve interference, since most of the artificially synthesized pesticides are fat-soluble and have high biostability, they seriously affect the biodiversity of plants, microorganisms and animals after bioaccumulation and bioamplification effects, and they enter human body through the transmission of food chain transmission, thus harming human health. The pesticide makes great contribution to agricultural production in China, but also causes serious environmental pollution to farmland soil and water environment in China, and seriously influences the sustainable development of agriculture in China.
Organochlorine pesticides such as hexachloro-hexa, dichlorodiphenyl trichloroethane, dieldrin, aldrin, pentachlorophenol (Chenorihong et al, 2018), heptachlor, hexachlorobenzene, chlordane (Populus. Hui, 2008), toxaphenol, benzofuran, nonachlor, endosulfan, etc., organophosphorus pesticides such as dimethoate, omethoate, parathion, methyl parathion, phorate, etc., stable in properties, is not easy to decompose in the environment, has strong fat solubility, is easy to accumulate and transfer in organisms, influences the activity of acetylcholinesterase in the organisms, thereby inhibiting the conduction of organism nerve signals, causing the disturbance of organism secretion system, the destruction of reproduction and immune system, inducing cancer and nervous diseases, being two main pesticides in the early development stage of pesticide industry, more than 600 products, wherein organophosphorus pesticide accounts for more than 80 percent of all pesticides, if the food is not treated as soon as possible, the food safety and the ecological environment safety in China are greatly harmed.
1. Common restoration method for agricultural and antibiotic pollution of farmland soil
Remediation of contaminated soil refers to the physical, chemical and biological methods used to transfer, absorb, degrade and transform pollutants in soil to reduce their concentration to acceptable levels, or to transform toxic and harmful pollutants into harmless materials. The polluted soil remediation can generally adopt three operation modes of in-situ remediation, on-site remediation and ex-situ remediation. According to different process principles, the existing remediation technologies of the polluted soil mainly comprise physical remediation, chemical remediation, physical and chemical remediation, biological remediation and a composite remediation technology combining multiple remediation methods.
1.2.1 chemical remediation
The chemical remediation is to inject solubilizing agents such as a surfactant, humic acid, cyclodextrin or an organic solvent and the like into the polluted soil or underground water, improve the solubility of adsorbed, solid or liquid organic pollutants in a water phase or increase the fluidity of non-water phase liquid, and migrate the pollutants out of an underground system through the action of water flow so as to achieve the purpose of removing the pollutants; or the formation of organoclays increases the retention and stability of the contaminants and reduces their ability to migrate into other environmental media. The common chemical remediation technologies comprise a solvent/steam extraction method, an in-situ soil leaching method, a solvent extraction technology, a chemical oxidation method, a chemical degradation method, a chemical reduction and reductive dechlorination dephosphorization technology, a soil performance improvement and remediation technology and the like, and have the advantages of low remediation cost, high organic pollutant removal rate, short remediation period and the like, and the site remediation effect on high organic pollution degree is obvious.
The advanced oxidation is to utilize ultraviolet-hydrogen peroxide and ultraviolet-ozone technology to generate free radicals or peroxy radicals with high activity to quickly oxidize organic matters in soil and decompose the free radicals or peroxy radicals into water molecules and carbon dioxide molecules, thereby eliminating the environmental hazard of organic pesticides without secondary pollution. Photocatalytic TiO2, WO3 and the like perform electron transfer to oxidize organic pollutants in soil. The adoption of the Fenton reagent can quickly and effectively oxidize the organic pesticide in the soil. The hexavalent iron oxidation technology has better effect than that of oxidizing PCB by a common oxidant, 40% of PCB can be removed by treating the polluted soil by combining hexavalent iron and persulfuric acid, the polluted soil with high carbonate content influences the oxidation effect of the hexavalent iron, and the oxidation effect of the hexavalent iron is also obviously influenced by the soil texture.
The organochlorine pesticide in the soil can be effectively removed by adopting ultrasonic heating, adding an oxidant and coating a graphite electrode. The persulfate method is more and more used for soil organic pollution remediation in recent years, and different methods are adopted to activate persulfate, wherein the remediation effect is directly influenced by heat activation, metal ion activation, ultraviolet activation and alkali activation.
Ozone, because of its strong oxidizing property, is widely used in the semiconductor industry, water treatment and air pollutant removal. The ozone catalytic oxidation organic matter has the characteristics of high efficiency and low energy consumption. The oxidation efficiency of organic matters is greatly improved by catalyzing ozone oxidation with aluminum oxide and silicon oxide, and ozone is decomposed into oxygen and singlet oxygen atom active oxygen, so that the method is mainly used for preventing and treating organic air pollution and organic sewage pollution.
1.2.2 physical repair
Physical remediation is primarily intended to mitigate the hazards of pollutants by reducing the concentration of pollutants on the surface of the soil or by enhancing the stability of the pollutants in the soil so that their water solubility, diffusivity and bioavailability are reduced. The physical remediation mainly adopts a soil turning, soil changing and soil covering method, or a steam stripping, thermal desorption, incineration and other methods to remove or solidify pollutants. The soil turning is to deeply turn the soil, so that pollutants gathered on the surface of the soil can be dispersed to the deep layer of the soil, and the purposes of dilution and self-treatment are achieved. The soil replacement is to take away the polluted soil and replace the polluted soil with fresh and clean soil. The method is suitable for treating the soil with small area and serious pollution, but the changed soil must be treated. In the operation process, operators can contact the polluted soil, and the labor cost is high, so that the method is generally only suitable for simple treatment after an accident. The soil-bearing method is to add a large amount of clean soil into the polluted soil, cover the surface layer or mix the soil uniformly to reduce the concentration of pollutants or reduce the contact of the pollutants and the plant root system. The newly added soil should be selected as soil with higher organic matter content as much as possible so as to increase the environmental capacity of the soil, increase the self-cleaning capacity of the soil and reduce the amount of the soil. Thermal desorption is to carry out direct or indirect heat exchange on soil, and organic pollutants are evaporated to be separated from a soil medium after the soil is heated to a certain temperature. The microwave heating technology is also used in recent years, and is a newer form based on thermal remediation, and the microwave heating technology has the advantages that different pollutants in soil can be repaired, the microwave heating technology can be used for different types of soil, and the removal rate of the pollutants is relatively high. The physical remediation effect is good, but the soil turning and soil dressing method does not remove pollutants from soil, and the remediation cost is high, so that the method is not suitable for remediation of polluted sites with large areas (Chengwei, 2009). The addition of a proper amount of copper can catalyze and promote the degradation of pyrethroid in the polluted soil (Liujun, 2009; Zhang Ning, 2017).
The thermal desorption technology or the thermal desorption technology with the best effect is most commonly used at present, the thermal desorption effect of the organophosphorus contaminated soil is influenced by the change of the thermal desorption temperature and the retention time, the thermal desorption temperature of the dichlorvos is preferably 200 ℃, the thermal desorption temperature of the omethoate is preferably 250 ℃, and the thermal desorption temperature of the parathion is preferably 400 ℃. Within 30min of thermal desorption, the removal rate of organic phosphorus pollutants in soil is obviously increased, the removal rate is over 90% at 30min, and the removal efficiency is over 95% at 40min of thermal desorption retention time. The removal rate of pollutants caused by thermal desorption in the low-temperature operation stage is DDVP, omethoate and parathion. Meanwhile, the particle size of the soil influences the removal effect of the organophosphorus pesticide, and the larger the particle size of the soil is, the more the organophosphorus in the soil is removed. The maximum removal rates of dichlorvos, omethoate and parathion in the organophosphorus soil respectively reach 94.3 percent, 97.8 percent and 99.5 percent. The electric heating rotary kiln thermal desorption technology can effectively repair the polluted soil containing DDTs and HCHs, wherein the thermal desorption temperature and time are key factors influencing the repair effect, and when the thermal desorption temperature reaches 340 ℃ and 370 ℃, the removal rate of the total HCH and the total DDT exceeds 99 percent.
Surface adsorption material and active carbon technology. Surfactants can enhance the bioavailability of organic pesticides in soil, since bioremediation depends on the availability and bioavailability of organic contaminants. The organic phosphorus and organochlorine pesticides with soil pollution remediation effects are prepared from clay particles, clay and surfactant combination, active carbon, zeolite, high molecular materials such as cyclodextrin, dendritic macromolecules, highly crosslinked polymers and the like. Since being discovered by James Orton in 1870, activated carbon has good surface adsorption performance and fixing performance due to high permeability, and is widely reported to be an effective substance capable of improving soil and reducing soil acidification side effects, and capable of degrading sulfamethoxazole, atrazine, polycyclic aromatic hydrocarbon and the like in soil; 2 percent of activated carbon is added into the soil polluted by the organochlorine pesticide, so that organochlorine in the soil can be well adsorbed and eliminated. Biochar has many properties, such as negative charge and large surface area, to remediate soil contamination. The biochar applied to the soil can promote nutrient utilization, increase and decrease microbial activity, improve the utilization rate of organic matters in the soil, improve the water retention of the soil, promote crop growth and can be used for soil pesticide remediation. The biochar restoration has many advantages compared with the traditional organic pesticide soil restoration, and when the biochar is applied to restore the organic phosphorus pesticide in the soil, the removal rate of the organic phosphorus pesticide can be improved by adding a proper amount of ammonium nitrate, namely the microbial activity in the soil is increased. The biological carbon is added, so that the organic phosphorus bioavailability on the polluted soil can be obviously reduced, the organic phosphorus accumulation in the vegetable body is reduced by more than 85 percent, and the life-long cancer risk of eating the vegetable by a human body is reduced by more than 87 percent.
The ultrasonic wave can generate cavitation bubbles, millions of cavitation bubbles can be generated in a short time, the cavitation bubbles are broken to generate strong oscillation, and chemical bonds of organic matters are broken, so that the organic pollution of the soil is eliminated. The zero-valent iron has strong reducibility, and the nano zero-valent iron can reduce and degrade organic pollution pesticides, particularly organic chlorine pesticides, in soil. The soil containing organic pesticides of metolachlor, alachlor, atrazine, pendimethalin, chlorpyrifos and the like is added with 5 percent by weight of nano zero-valent iron, 60 percent of the pesticides can be degraded within 90 days, and if 2 percent by weight of aluminum sulfate is added, the degradation rate of the organic pesticides reaches over 90 percent within 90 days.
1.2.3 electric repair (electrochemical repair)
The electric restoration technology is characterized in that electrodes are inserted into soil, voltage is applied between the electrodes, a series of electrodynamic processes are driven by potential gradient, including water movement (electroosmosis), ion movement (electric migration) and dotted particle movement (electrophoresis), and oxidation-reduction reaction can also occur when the electric restoration technology is adopted in polluted organic pesticide soil. The electric restoration technology has proved to be a soil pollution restoration technology with great application value and prospect, and particularly, low-voltage direct current is adopted as a cleaning reagent on polluted clay soil. From the last 80 s, electrokinetic remediation technology has been successfully used for the treatment of various contaminated soils. The technology can be used for repairing heavy metal, organic phenol, organic chlorine, organic phosphorus, petroleum, herbicide, polycyclic aromatic hydrocarbon and the like in soil.
The method adopts an electric restoration technology and a Fenton reaction coupling technology and an enhanced electric restoration-Fenton reaction technology to treat HCH and DDT polluted by soil, can greatly improve the removal rate of organochlorine pesticides in the soil, and can reach more than 71 percent at most.
1.2.4 Bioremediation
Bioremediation refers to the absorption, degradation, and transformation of pollutants in soil by various organisms-plants, soil animals, and microorganisms in soil, such that the concentration of pollutants is reduced to an acceptable level, or toxic and harmful pollutants are transformed into harmless substances. Bioremediation in the broad sense includes phytoremediation, animal remediation and microbial remediation, and bioremediation in the narrow sense refers to microbial remediation. The phytoremediation technology for the contaminated soil mainly comprises a plant fixing method, a plant volatilization method, a plant absorption and enrichment method, a plant secretion method/enzyme remediation method, a plant rhizosphere remediation method and the like. The microbial remediation of the organic contaminated soil mainly comprises in-situ remediation and ex-situ remediation, wherein the in-situ remediation comprises a bacterium feeding method, a biological culture method, a biological aeration method and the like; ex situ remediation techniques include prefabricated bed techniques, bioreactor techniques, anaerobic treatment, and conventional composting. The bioremediation technology has low remediation cost and simple operation, is not easy to generate new pollution, and is more suitable for remediation of large-area organic polluted sites compared with physical remediation. However, most pesticides in soil belong to hydrophobic organic pollutants, are low in water solubility and strongly adsorbed by soil, and microorganisms can only absorb and degrade the organic pollutants in a liquid phase in a dissolved state, so that the absorption, degradation and bioremediation efficiency of plants and microorganisms on the organic pollutants are greatly limited. Meanwhile, the concentration of organic pollutants in the organochlorine pesticide polluted site is very high, the biotoxicity is high, and the biological repair technology is difficult to popularize.
1.2.5 photochemical remediation
The photorepair is to break down chemical bonds of organic pesticides under the action of sunlight. Pesticides are sprayed on plant leaves, the soil surface or structure is very different, the stability of the pesticides is different, and when sunlight irradiates on the leaves or the soil surface, the pesticides can be subjected to photolysis to different degrees. As with other degradation processes, photolysis reduces the content of pesticides in the soil. The Dichlobenil (DCBN) can be subjected to photodegradation under the illumination condition, the dichlobenil molecules in a stable state are converted into excited dichlobenil with active chemical properties from the dichlobenil molecules in a stable state through energy transfer in the reaction process under the illumination condition, and then subsequent series of reactions occur. The water body generates hydroxyl free radicals with strong oxidizing property under the illumination condition. Under the action of system hydroxyl free radicals, chlorine atoms on benzene rings of o-chlorobenzonitrile molecules can continue to generate hydroxyl substitution reaction to generate cyanobenzene. Under the condition of illumination, the nano TiO2 and the H2O2 can generate a large amount of hydroxyl radicals, and the hydroxyl radicals have strong oxidizing property and can oxidize and decompose dichlobenil to promote the conversion of chlorine atoms on benzene rings from an organic state to an inorganic state. By adding the nano TiO2, DDT in soil can be repaired in situ, and the DDT is degraded under the irradiation of ultraviolet light, so that the efficiency is greatly improved. Photocatalytic TiO2, WO3 and the like perform electron transfer to oxidize organic pollutants in soil.
1.3 Farmland soil pesticide and antibiotic pollution existing in the existing remediation method
The research on the organochlorine pesticide contaminated site treatment technology is the most extensive in foreign research, and various mature technologies such as an in-situ heat treatment technology, a soil steam extraction/underground water aeration technology, an in-situ vitrification technology, a high-temperature incineration technology, a cement kiln co-disposal technology, a low-temperature thermal desorption technology, ex-situ bioremediation, an underground water pumping treatment system and the like have been developed. The technologies are limited by factors such as high restoration cost, long restoration period, damage to farmland soil structures and the like in actual field restoration operation, and are difficult to popularize and apply in the restoration of polluted fields on a large scale.
After being applied to polluted soil, common pesticide degrading bacteria are affected by the complex environment of the soil and the competition of main microorganisms, so that the survival state and the repairing effect of the soil are often affected. Wild bacteria with better degradation effect are often used in laboratory conditions, and when the wild bacteria are applied to ectopic polluted soil for bioremediation, the degradation effect is not ideal, so that the wild bacteria are rarely applied to actual remediation of pesticide pollution of farmland soil at present.
The biodegradation of soil organic pesticide pollution has been a great deal of research work, but the problems are also very prominent. Firstly, although a plurality of organic pesticide degrading bacteria are screened, the number of high-efficiency bacterial strains is small; secondly, the degradation spectrum of the degrading bacteria is not wide enough, and the components in the organic pesticide cannot be completely metabolized; in addition, the high-efficiency degrading bacteria obtained in many laboratories have low efficiency in practical application, have unsatisfactory repairing effect and are difficult to be applied on large scale in production.
The chemical restoration construction has high safety requirement, secondary pollution and serious damage to farmland soil structure and fertility. The plant restoration speed is slow, and the animal restoration is not suitable for large-area farmland soil pollution. Physical remediation, particularly the soil reclamation method, is not a true soil remediation but merely transfers the contamination to another environment. Electric remediation requires control of many environmental factors and causes a decrease in soil fertility. The activated carbon or the biochar repairing technology has high cost, can not be borne by the general farmland soil pollution repairing technology, and the activated carbon or the biochar still exists in the farmland, so that organic pollutants adsorbed by the biochar can be released into the soil environment again to pollute the soil again with the lapse of time or the change of environmental conditions.
1.4 Farmland soil pesticide and antibiotic remediation development trend
The green pollution remediation technology is a future development trend and meets the requirements of human sustainable development. The method has the advantages of good removal effect, high speed, no secondary pollution, no damage to farmland soil structure, change of soil physical and chemical properties, damage to soil microbial ecosystem, reduction of soil fertility, reduction of soil organic matters, and contribution to sustainable development and harmonious development of farmlands.
Ozone is a substance with strong oxidizability, can quickly oxidize and decompose various small molecular organic substances to form carbon dioxide and water, and can form oxygen by itself, so that no secondary pollution is caused. At present, a plurality of articles and patents describe the application of ozone in sewage treatment and food disinfection, but most of the patents describe how to disinfect and sterilize by using ready-made ozone water, and the application of the ozone to organic matters in soil machines and underground water, especially organic pesticides and antibiotics is not reported yet.
The rapid and efficient in-situ circulation restoration system for the organic pollution of the site soil and the underground water is designed by adopting a mechanism of generating high-concentration active oxygen and ozone through high-voltage discharge, ozone is dissolved in water and forms strong oxidizing substances containing ozone, hydroxyl radical peroxy radicals and the like with a small amount of organic substances, the strong oxidizing substances can rapidly react with organic substance molecules in the soil and the underground water to generate carbon dioxide and water, the active oxygen is converted into oxygen, no residue is generated, no secondary pollution is generated, and the system is green and environment-friendly.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical defects, the invention develops a rapid and efficient in-situ circulating repair system for organic pollution active oxygen in field soil and underground water, which can rapidly oxidize and decompose organic pollutants in the soil and the underground water into carbon dioxide and water without residue and secondary pollution, protect the ecological environment and develop ecological agriculture.
The technical scheme is as follows: the development, application, manufacture and application of a rapid and efficient in-situ circulating repair system for organic pollution active oxygen of site soil and underground water comprises the following steps: a the system is composed of three functional units: an active oxygen forming unit, a groundwater extraction unit and an active oxygen reaction unit. The active oxygen forming unit is composed of a plurality of square metal boxes with the length of 100-200cm, the width of 50-100cm and the height of 80-180 cm. One side of the square container body is provided with a photovoltaic power generation system, an inverter, a commercial power distribution cabinet, a charger, a storage battery, an alternating current-direct current converter, a frequency converter, a transformer, a timer and the like which are connected in series; an air filter, an adsorption dryer, an air compressor, a cooler, a molecular sieve oxygen generator, a high-voltage discharge active oxygen generator (ozone), a water-gas mixing pump, a control valve and the like are arranged in the middle; the underground water pumping unit comprises a plurality of water wells and two-way water pumps, wherein each water well is inserted into a water pipe and connected in series with each other, underground water is pumped into the active oxygen reaction tank through the two-way water pumps, water in the active oxygen reaction tank is continuously pumped through a water inlet pipe of the water-gas mixing pump to be mixed with active oxygen for reaction, meanwhile, water containing the active oxygen flows back into the active oxygen reaction tank through a water outlet pipe of the water-gas mixing pump to be continuously mixed with the underground water in the active oxygen reaction tank for reaction, the reaction is repeated repeatedly in a circulating way, and after organic matters in the underground water react with the active oxygen, purified water in the active oxygen reaction tank can be pumped back into the underground water through; the active oxygen reaction unit comprises a water-gas mixing pump, an active oxygen reaction tank, a water inlet pipe, a water outlet pipe and the like; the water inlet pipe and the water outlet pipe of the water-gas mixing pump are connected with the active oxygen reaction tank, all devices are connected by pipelines, the whole system is powered by a mains supply system, when power is cut off, the photovoltaic power generation system can be used for supplying power, the photovoltaic power generation system can be used for charging a storage battery at ordinary times, an alternating current-direct current converter converts direct current into alternating current, a timer can be used for timing, the water-gas mixing pump mixes active oxygen (ozone) and water to form active oxygen water, and the active oxygen water reacts with organic matters in the water to generate carbon dioxide and water; soil groundwater is extracted by a bidirectional pump and is sent into an active oxygen reaction tank, groundwater in the reaction tank is sent into a water-gas mixing pump by a water-gas mixing pump inlet pipe to be mixed with active oxygen to form various active oxygen free radicals, then the active oxygen reaction tank is returned to by a water-gas mixing pump outlet pipe to be continuously mixed and reacted with groundwater in the reaction tank, organic substances in water in the reaction tank are oxidized and decomposed, after organic pollutants in the groundwater are oxidized and decomposed into carbon dioxide and water, the purified water is sent back to the soil groundwater by the bidirectional pump and a pipeline, and the purpose of repairing organic pollution of the soil groundwater is achieved. b. After the unit devices in the a are assembled, a plurality of underground water wells are excavated, pipelines are introduced, well mouths are sealed, power is supplied to a system formed in the a, the high-voltage discharge active oxygen machine can continuously generate and discharge active oxygen, the quantity of the active oxygen entering water of the water-gas mixing pump is controlled by a control valve, the active oxygen is dissolved in sucked underground water and reacts with a small amount of organic substances in the underground water to generate a large amount of active oxygen free radicals, the active oxygen free radicals are pumped into the active oxygen reaction tank through a water outlet of the water-gas mixing pump, the large amount of free radicals and the active oxygen rapidly react with organic pesticide antibiotics and the like of soil underground water organic pollutants in the reaction tank, and the organic substances are rapidly oxidized and decomposed into carbon dioxide and water without residues and secondary pollution. c. In the process b, if the commercial power is cut off or the commercial power is not available, the photovoltaic power generation system can be used for supplying power, and when the commercial power is available, the photovoltaic power generation system can be used for generating power and charging and storing for later use. The reaction time can be set by adjusting a timer on the control panel, the groundwater inlet and the water outlet of the water-gas mixing pump are automatically controlled, and when all organic substances in pumped groundwater are oxidized and decomposed in the reaction tank, clean water with organic pollutants removed is sent back to the soil groundwater well by the bidirectional pump. d. According to the actual needs, in order to improve the treatment efficiency of the system, a plurality of active oxygen forming units can be connected in parallel to generate more active oxygen, a plurality of reaction tanks are connected in series, each reaction tank can be made into a round or square stainless steel tank, the volume is 10-100 cubic meters, a plurality of active units can be connected in parallel for use, a stirrer in each reaction tank is started simultaneously, the full contact, reaction and decomposition of the active oxygen and organic pesticides in water in the reaction tanks are enhanced, and the oxidative decomposition effect and efficiency of the active oxygen on organic matters in underground water are enhanced.
The application of any one of the rapid and efficient in-situ circulating remediation system for organic pollutants in field soil and underground water to remediation of organic pollutants in field soil and farmland soil and underground water.
Has the advantages that: the quick high-efficient normal position circulation repair system of this application place soil and groundwater organic pollution active oxygen can be fast furthest's getting rid of soil groundwater organic pollutant, protects ecological environment, develops ecological agriculture organic agriculture.
Compared with the prior art, the invention has the advantages that:
1) the method has the advantages that active oxygen generated by dissolving ozone in water is adopted, and the ozone and free radical high-oxidizing technology is utilized, so that the method is simple and convenient, quick to take effect, simple and feasible in technology, strong in operability, low in cost and high in practicability;
2) the ozone-free radical technology of the high-efficiency in-situ circulating repair system adopting two power supply modes of commercial power and photovoltaic power generation can simultaneously oxidize and decompose various organic pollutants, organic pesticides, antibiotics and the like in soil and underground water, and compared with the current common single chemical treatment, the ozone water treatment system is more efficient, quicker and free of environmental pollution because the ozone water is finally changed into water and oxygen; meanwhile, the in-situ circulating remediation is carried out, and the soil is returned to the soil groundwater in situ without the need of ex-situ remediation, so that a large amount of cost and possible secondary pollution are saved. Compared with the prior common thermal desorption, thermal desorption and perchloric acid and persulfuric acid oxidation methods, the method is safer, saves cost, is convenient to operate, has no secondary pollution and does not damage the soil structure.
Drawings
Fig. 1 is a schematic structural diagram of the appearance of the system. 1-cooler 2-air compressor 3-adsorption drier 4-filter 5-electric wire 6-solar cell and inverter 7-storage battery 8-solar generator 9-system and circuit control board 10-programmable controller and frequency converter 11-transformer 12-oxygen generator 13-active oxygen ozone generator 14-water gas mixing pump 15-active oxygen outlet pipe 16-groundwater 17-active oxygen reaction tank 18-groundwater 19-water mixing pump liquid control valve 20-water gas mixed liquid outlet pipe 21-soil 22-groundwater well 23-groundwater seeped from soil 24-groundwater extraction pipe 25-groundwater extraction reflux bidirectional pump 26-groundwater extraction reflux control valve 27-stirrer.
Detailed Description
The invention is further described below with reference to examples:
example 1: organic pesticide pollution remediation of soil and underground water in production field of certain abandoned pesticide plant
According to the technical route and the scheme, the quick and efficient in-situ circulating repair system for the organic polluted active oxygen is assembled and debugged, and after the active oxygen ozone is normally generated and the active oxygen free radicals and water can be stably mixed, the following organic pollutant repair test is carried out.
1.2018, No. 3 and No. 5 tests on the site soil and the underground water of a waste production workshop of a certain pesticide factory in Yangzhou, starting an organic pollution active oxygen rapid and efficient in-situ circulating remediation system, digging a well at 5 holes in the site soil of the workshop, starting to extract the underground water when the underground water is sufficient after digging the well for 1 day, starting the circulating remediation system at the same time, and timing for 50 minutes;
2. pumping underground water from a pumping well into a reaction tank, wherein the volume of the reaction tank is 4 cubic meters, starting a circulating repair system, generating active oxygen, mixing and dissolving the active oxygen through a water-gas mixing pump, feeding the active oxygen into the reaction tank, starting a stirrer in the reaction tank, and continuously mixing and dissolving the active oxygen with the underground water in the reaction tank to contact, react and decompose organic pesticide in the underground water;
3. and (4) finishing timing, automatically stopping the generation of active oxygen by the system, closing the water-gas mixing pump, continuing stirring for 5 minutes, starting the bidirectional water pump, and sending the repaired underground water with 96% decomposed organic pesticide back to the water well to return to the soil underground water.
Example 2: remediation of soil and underground water pollution of production site of certain waste organic dyeing synthesis plant
According to the technical route and the scheme, the quick and efficient in-situ circulating repair system for the organic polluted active oxygen is assembled and debugged, and after the active oxygen ozone is normally generated and the active oxygen free radicals and water can be stably mixed, the following organic pollutant repair test is carried out.
1.2018 No. 4 and No. 11 tests on the site soil and the underground water of a waste production workshop of a certain dye factory in Thai, starting an organic pollution active oxygen rapid and efficient in-situ circulating repair system, digging a well at 10 openings in the site soil of the workshop, wherein the well depth is 3 meters, starting to extract the underground water when the underground water is sufficient after 2 days of well digging, starting the circulating repair system and timing for 60 minutes;
2. pumping underground water from a pumping well into a reaction tank, wherein the volume of the reaction tank is 4 cubic meters, starting a circulating repair system, generating active oxygen, mixing and dissolving the active oxygen through a water-gas mixing pump, feeding the active oxygen into the reaction tank, starting a stirrer in the reaction tank, continuously mixing and dissolving the active oxygen with the underground water in the reaction tank, and contacting, reacting and decomposing the active oxygen with organic dye in the underground water;
3. and (4) finishing timing, automatically stopping the generation of active oxygen by the system, closing the water-gas mixing pump, continuing stirring for 10 minutes, starting the bidirectional water pump, and sending the repaired underground water with 94% of decomposed organic dye back to the water well to return to the soil underground water.
Example 3: pollution remediation of organic intermediate in soil and underground water of production site of certain waste cosmetic factory
According to the technical route and the scheme, the quick and efficient in-situ circulating repair system for the organic polluted active oxygen is assembled and debugged, and after the active oxygen ozone is normally generated and the active oxygen free radicals and water can be stably mixed, the following organic pollutant repair test is carried out.
1.2018 No. 6 and No. 17 tests on waste production workshop site soil and underground water of certain cosmetics factory in Nanjing, starting an organic pollution active oxygen rapid and efficient in-situ circulating remediation system, digging a well at 15 holes in the workshop site soil, wherein the well depth is 2 meters, starting to extract the underground water when the underground water is sufficient after 3 days of well digging, starting the circulating remediation system, and timing for 70 minutes;
2. pumping underground water from a pumping well, enabling the underground water to enter a reaction tank, dissolving the underground water for 2 cubic meters, starting a circulating repair system, generating active oxygen, mixing and dissolving the active oxygen through a water-gas mixing pump, enabling the active oxygen to enter the reaction tank, starting a stirrer in the reaction tank, enabling the active oxygen to be continuously mixed and dissolved with the underground water in the reaction tank, and enabling the active oxygen to be in contact with an organic intermediate in the underground water, react and decompose;
3. and (4) finishing timing, automatically stopping the generation of active oxygen by the system, closing the water-gas mixing pump, continuing stirring for 10 minutes, starting the bidirectional pump, and returning the repaired underground water with 97.4% decomposed organic intermediates to the water well and returning the repaired underground water to the soil underground water.
Application examples of the invention:
the technology of the invention is used for preventing and controlling the diseases and insect pests of seed seedlings and root tubers of watermelon, strawberry and sweet potato planted in a greenhouse.
1. Referring to example 1, after the organic pesticide is treated by the technology, compared with the contrast without the technology, the decomposition rate of organic pollutants in soil groundwater reaches 96% after the active oxygen treatment of the remediation system is adopted;
2. referring to example 2, after the organic dye is treated by the technology, compared with the contrast without the technology, the decomposition rate of organic pollutants in the soil groundwater reaches 94% after the active oxygen treatment of the remediation system is adopted;
3. referring to example 3, after the organic intermediate is treated by the technology, compared with the contrast without the technology, the decomposition rate of the organic pollutants in the soil groundwater can reach 97.4% after the active oxygen treatment by the remediation system.
Claims (6)
1. Development and application of a rapid and efficient in-situ circulating repair system for organic pollution active oxygen of site soil and underground water are characterized by comprising the following steps:
a the system is composed of three functional units: an active oxygen forming unit, a groundwater extraction unit and an active oxygen reaction unit. The active oxygen forming unit is composed of a plurality of square metal boxes with the length of 100-200cm, the width of 50-100cm and the height of 80-180 cm. One side of the square container body is provided with a photovoltaic power generation system, an inverter, a commercial power distribution cabinet, a charger, a storage battery, an alternating current-direct current converter, a frequency converter, a transformer, a timer and the like which are connected in series; an air filter, an adsorption dryer, an air compressor, a cooler, a molecular sieve oxygen generator, a high-voltage discharge active oxygen generator (ozone), a water-gas mixing pump, a control valve and the like are arranged in the middle; the underground water pumping unit comprises a plurality of water wells and a bidirectional water pump, wherein each water well is inserted into a water pipe and connected in series with each other, underground water is pumped by the bidirectional water pump and sent to the active oxygen reaction tank, water in the active oxygen reaction tank is continuously pumped by a water inlet pipe of the water-gas mixing pump to be mixed with active oxygen for reaction, meanwhile, water containing active oxygen flows back to the active oxygen reaction tank by a water outlet pipe of the water-gas mixing pump and is continuously mixed with underground water in the active oxygen reaction tank for reaction, the reaction is repeated repeatedly in a circulating way, and after organic matters in the underground water react with the active oxygen, purified water in the active oxygen reaction tank can be pumped back to the underground water by the bidirectional pump; the active oxygen reaction unit comprises a water-gas mixing pump, an active oxygen reaction tank, a stirrer, a water inlet pipe, a water outlet pipe and the like; the water inlet pipe and the water outlet pipe of the water-gas mixing pump are connected with the active oxygen reaction tank, all devices are connected by pipelines, the whole system is powered by a mains supply system, when power is cut off, the photovoltaic power generation system can be used for supplying power, the photovoltaic power generation system can be used for charging a storage battery at ordinary times, an alternating current-direct current converter converts direct current into alternating current, a timer can be used for timing, the water-gas mixing pump mixes active oxygen (ozone) and water to form active oxygen water, and the active oxygen water reacts with organic matters in the water to generate carbon dioxide and water; the method comprises the steps of extracting soil underground water through a bidirectional pump, feeding the soil underground water into an active oxygen reaction tank, feeding underground water in the reaction tank into a water-gas mixing pump through a water inlet pipe of the water-gas mixing pump to be mixed with active oxygen to form various active oxygen free radicals, then returning the active oxygen reaction tank to the active oxygen reaction tank through a water outlet pipe of the water-gas mixing pump, continuously mixing and reacting with underground water in the reaction tank, carrying out oxidative decomposition on organic substances in water in the reaction tank, and after organic pollutants in the underground water are oxidized and decomposed into carbon dioxide and water, feeding purified water back into the soil underground water through the bidirectional pump and a pipeline to achieve the purpose of.
b. After the unit devices in the a are assembled, a plurality of underground water wells are excavated, pipelines are introduced, well mouths are sealed, power is supplied to a system formed in the a, the high-voltage discharge active oxygen machine can continuously generate and discharge active oxygen, the quantity of the active oxygen entering water of the water-gas mixing pump is controlled by a control valve, the active oxygen is dissolved in sucked underground water and reacts with a small amount of organic substances in the underground water to generate a large amount of active oxygen free radicals, the active oxygen free radicals are pumped into the active oxygen reaction tank through a water outlet of the water-gas mixing pump, the large amount of free radicals and the active oxygen rapidly react with organic pollutants, such as organic pesticide antibiotics and the like in the underground water in the reaction tank, and the organic substances are rapidly oxidized and decomposed into carbon dioxide and water without residues and secondary pollution.
c. In the process b, if the commercial power is cut off or the commercial power is not available, the photovoltaic power generation system can be used for supplying power, and when the commercial power is available, the photovoltaic power generation system can be used for generating power and charging and storing for later use. The reaction time can be set by adjusting a timer on the control panel, the groundwater inlet and the water outlet of the water-gas mixing pump are automatically controlled, and when all organic substances in pumped groundwater are oxidized and decomposed in the reaction tank, clean water with organic pollutants removed is sent back to the soil groundwater well by using the bidirectional water pump.
d. According to the actual needs, in order to improve the treatment efficiency of the system, a plurality of active oxygen forming units can be connected in parallel to generate more active oxygen, a plurality of reaction tanks are connected in series, each reaction tank can be made into a round or square stainless steel tank, the volume is 10-100 cubic meters, a plurality of active units can be connected in parallel for use, a stirrer in each reaction tank is started simultaneously, the full contact, reaction and decomposition of the active oxygen and organic pesticides in water in the reaction tanks are enhanced, and the oxidative decomposition effect and efficiency of the active oxygen on organic matters in underground water are enhanced.
2. The development and application of the rapid and efficient in-situ circulation restoration system for the organic pollution of site soil and underground water by active oxygen according to claim 1 are characterized in that the method is characterized in that the system consists of three functional units: the active oxygen forming unit, the groundwater extraction unit and the active oxygen reaction unit can be combined by a plurality of (5-100) functional units in specific application. The active oxygen forming unit is composed of a plurality of (50-10000) square metal boxes with the length of 100-200cm, the width of 50-100cm and the height of 80-180cm, and in specific application, a plurality of (5-100) metal boxes can be combined for use. One side of the square container body is provided with a photovoltaic power generation system, an inverter, a commercial power distribution cabinet, a charger, a storage battery, an alternating current-direct current converter, a frequency converter, a transformer, a timer and the like which are connected in series; the middle is provided with an air filter, an adsorption dryer, an air compressor, a cooler, a molecular sieve oxygen generator, a high-voltage discharge active oxygen generator, a water-gas mixing pump, a control valve and the like; the underground water pumping unit comprises a plurality of water wells and a bidirectional water pump, wherein each water well is inserted into a water pipe and connected in series with each other, underground water is pumped by the bidirectional water pump and sent to the active oxygen reaction tank, water in the active oxygen reaction tank is continuously pumped by a water inlet pipe of the water-gas mixing pump to be mixed with active oxygen for reaction, meanwhile, water containing active oxygen flows back to the active oxygen reaction tank by a water outlet pipe of the water-gas mixing pump and is continuously mixed with underground water in the active oxygen reaction tank for reaction, the reaction is repeated repeatedly in a circulating way, and after organic matters in the underground water react with the active oxygen, purified water in the active oxygen reaction tank can be pumped back to the underground water by the bidirectional pump; the active oxygen reaction unit comprises a water-gas mixing pump, an active oxygen reaction tank, a stirrer, a water inlet pipe, a water outlet pipe and the like; the water inlet pipe and the water outlet pipe of the water-gas mixing pump are connected with the active oxygen reaction tank, all devices are connected by pipelines, the whole system is powered by a mains supply system, when power is cut off, the photovoltaic power generation system can be used for supplying power, a storage battery can be charged by the photovoltaic power generation system at ordinary times, a direct current is converted into an alternating current by an alternating current-direct current converter, a timer can be used for timing, the water-gas mixing pump mixes active oxygen (ozone) and water to form active oxygen water, and the active oxygen water reacts with organic matters in the water for 10-120 minutes to generate carbon dioxide and water; the method comprises the steps of extracting soil underground water through a bidirectional pump, feeding the soil underground water into an active oxygen reaction tank, feeding underground water in the reaction tank into a water-gas mixing pump through a water inlet pipe of the water-gas mixing pump to be mixed with active oxygen to form various active oxygen free radicals, then returning the active oxygen reaction tank to the active oxygen reaction tank through a water outlet pipe of the water-gas mixing pump, continuously mixing and reacting with underground water in the reaction tank, carrying out oxidative decomposition on organic substances in water in the reaction tank, and after organic pollutants in the underground water are oxidized and decomposed into carbon dioxide and water, feeding purified water back into the soil underground water through the bidirectional pump and a pipeline to achieve the purpose of.
3. The development and application of a rapid and efficient in-situ circulation remediation system for organic contaminated active oxygen in site soil and underground water according to claim 1, wherein the method comprises the steps of assembling the above 2 units, excavating 10000 underground water wells, introducing into a pipeline, sealing a well mouth, supplying power to the system consisting of 2, continuously generating and discharging active oxygen (ozone) by a high-voltage discharge active oxygen machine, controlling the amount of active oxygen entering the water-gas mixing pump by a control valve, dissolving active oxygen in the sucked underground water and performing radical reaction with a small amount of organic substances in the underground water to generate a large amount of active oxygen radicals, delivering the active oxygen radicals into an active oxygen reaction tank through a water outlet of the water-gas mixing pump, continuously stirring by 3-20 groups of stirrers, mixing the underground water and the active oxygen for chemical reaction, and rapidly performing chemical reaction with organic pesticide antibiotics and the like of soil underground water in the reaction tank, the organic substance is rapidly oxidized and decomposed into carbon dioxide and water, and no residue and no secondary pollution exist.
4. The development and application of the system for rapidly and efficiently restoring organic pollution by active oxygen in situ according to claim 1, wherein in the treatment process 3, if commercial power is cut off or no commercial power is available, a photovoltaic power generation system can be used for supplying power, and when commercial power is available, the photovoltaic system can be used for generating power and charging and storing the power for later use. The reaction time can be set for 10-120 minutes by adjusting a timer on a control panel, the groundwater inlet and the water outlet of the water-gas mixing pump are automatically controlled, and when all organic substances in pumped groundwater are oxidized and decomposed in the reaction tank, clean water with organic pollutants removed is sent back to the soil groundwater well by the bidirectional pump.
5. The development and application of the rapid and efficient in-situ circulation remediation system for organic pollution of site soil and underground water by active oxygen according to claim 1 are characterized in that according to actual needs, in order to improve the system treatment efficiency, a plurality of (5-100) active oxygen forming units can be connected in parallel to generate more active oxygen, a plurality of (10-100) reaction tanks are connected in series, each reaction tank can be made into a round or square stainless steel tank with the volume of 10-100 cubic meters, a plurality of active units can be connected in parallel to be used, and meanwhile, a stirrer in each reaction tank is started to enhance the full contact, reaction and decomposition of the active oxygen and organic pesticides in the water of the reaction tank, and the oxidative decomposition effect and efficiency of the active oxygen on organic matters in the underground water are enhanced.
6. The application of the active oxygen rapid and efficient in-situ circulation restoration system for organic pollution of site soil and underground water according to any one of claims 1 to 5 in the restoration of organic pollutants of site soil, farmland soil and underground water.
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