CN115636464A - Method for repairing underground water pollution by coupling circulating well with permeable reactive barrier - Google Patents
Method for repairing underground water pollution by coupling circulating well with permeable reactive barrier Download PDFInfo
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Abstract
The invention relates to a method for remedying underground water pollution by a circulating well coupled permeable reactive barrier, which comprises the following steps: s1, detecting the polluted condition and field exploration parameters of an area to be repaired; s2, preparing an active composite material; s3, filling the active composite material serving as a filler into a wall body of the permeable reactive barrier; and S4, arranging the filled permeable reactive barrier in a three-dimensional flow field of the circulating well in a horizontal/vertical mode to establish a coupling restoration system and finish restoration work, wherein the active composite material is zero-valent iron prepared by taking plant leaf extracting solution as a reducing substance and loaded on biochar, the active composite material is filled in a treatment layer of the permeable reactive barrier, and a water inlet area and a water outlet area are respectively arranged on two sides of the treatment layer, so that underground water to be restored can flow into the permeable reactive barrier from the water inlet area outside the circulating well body under the driving action of the circulating well, and flows out from the water outlet area after pollutants are removed through the treatment layer.
Description
Technical Field
The invention relates to the technical field of remediation of organic polluted underground water, in particular to a method for remediating underground water pollution by a circulating well coupled permeable reactive barrier.
Background
Chlorophenol is commonly used in modern industry and agriculture as a raw material of preservatives, insecticides, disinfectants and the like, and is a typical halogenated organic substance. Common chlorophenols are Monochlorophenol (MCP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP), which are increasingly toxic with increasing substitution sites for chlorine atoms in the molecule and are considered persistent organic pollutants due to their longer half-life in the environment. And compared with other aromatic ring compounds, the chlorophenol has the characteristics of higher solubility, difficulty in adsorbing and fixing the chlorophenol, and the like, and can cause large-area groundwater pollution because the chlorophenol is transferred along with the flow of groundwater.
The underground water circulating well technology is often applied to in-situ remediation of organic polluted soil and underground water due to the advantages of small disturbance on the stratum structure, large influence range, simple operation and maintenance and the like. The existing circulating well technology mainly drives groundwater in a water-bearing layer to flow by matching the special design of a main body well pipe with the aeration/water pumping and injecting effects, so that three-dimensional water circulation is formed in the surrounding space of the groundwater circulating well. And the three-dimensional water flow circulation is adopted to continuously disturb the underground water-bearing stratum, so that organic pollutants in the water-bearing stratum are driven to enter the well. Finally, the volatile organic pollutants and the semi-volatile organic pollutants in the underground water are blown off by means of aeration and the like in the well, so that the aim of degrading the organic pollutants in the underground water is fulfilled. However, for organic pollutants with high solubility, the single circulation well technology is difficult to achieve the ideal remediation effect, and the organic pollutants can be efficiently removed by coupling other remediation technologies.
The PRB technology is also called permeable reactive barrier technology, and has been widely applied to the remediation of organic polluted groundwater. In general, PRB technology implements removal of organic pollutants in underground water by constructing a permeable reactive wall or a reactive zone in the underground, and when the underground water flows through the reactive wall or the reactive zone, a series of interactions (precipitation, adsorption, oxidation-reduction, immobilization, biodegradation) occur between the organic pollutants and the reactive wall. At present, the report that PRB technology and circulating well technology combine together is not seen yet, and the characteristics such as vertical circulation migration are made to groundwater circulating well technology has disturbance within a certain range rivers in consideration simultaneously, and this patent plans to design a horizontal PRB, forms vertical hydraulic circulation through the reaction wall and takes place the interaction through the guide contaminated groundwater to reach the mesh of strengthening circulating well and restoreing organic contaminated groundwater ability.
CN103991942B discloses promotion of Fe by using crustacean fluorescein 3+ /H 2 O 2 Systematic degradation of waste waterA method for neutralizing chlorophenol organic pollutants. In order to solve the technical problems, the technical scheme of the invention is as follows: controlling certain pH and temperature operation conditions, adding crustacean fluorescein, fe (III) salt and H into wastewater with chlorophenol concentration of 1-200 mg/L 2 O 2 The degradation percentage of the chlorophenol pollutants in the water body can reach 93.5-98% after stirring treatment for a certain time without special illumination conditions. The method solves the problem that ultraviolet radiation is needed in the process of treating the chlorophenol-polluted wastewater by using the traditional photo-assisted advanced oxidation system, has the advantages of simple process, less equipment investment, low cost and rapid and efficient treatment, and has wide application prospect in the aspect of treating underground water polluted by chlorophenols and chlorophenol-polluted water with poor light transmittance.
The underground water circulation well (GCW) and Permeable Reactive Barrier (PRB) technology is a research hotspot in the field of in-situ groundwater remediation in recent years and is widely applied due to the advantages of small disturbance to the stratum structure, large remediation range, few surface facilities, resource cost saving and the like. For example:
CN114751472A discloses a groundwater circulating well device for in-situ remediation of a contaminated site and a remediation method. The device comprises a circulating well, wherein the circulating well is provided with a water permeable layer and a closed layer from top to bottom; the waste gas treatment device, the ozone generator and the saponin solution storage tank are communicated to the sealing layer; the closed layer is provided with a groundwater pumping pipe and a bubble water pumping pipe. An air-entrapping zone is formed between the ground and the water level line of the underground water; the circulation well is provided with a micro-nano bubble water output pipeline. The method comprises the following steps: pumping the underground water into the closed layer through an underground water pumping pipe; conveying the ozone and the saponin solution in the ozone generator and the saponin solution storage tank into the sealing layer; liquid in the closed layer is output to underground water through a bubble water pumping pipeline; and opening the micro-nano bubble water pumping and injecting pump, and conveying the liquid in the closed layer to the aeration zone area through the micro-nano bubble water output pipeline. The method has the advantages of more comprehensive repair area and good repair effect.
CN107739083A discloses a permeable reactive barrier in-situ remediation method for cyanogen-containing groundwater, the permeable reactive barrier is a two-section permeable reactive barrier specially designed for cyanogen-containing polluted groundwater, permeable reactive materials are added into the wall, the cyanogen-containing polluted groundwater is enabled to pass through the permeable reactive barrier under a certain PH condition by utilizing the oxidation effect of active chlorine in hypochlorite, the cyanide is contacted with a reaction medium to be oxidized into cyanate, and the cyanate is further oxidized into carbon dioxide and nitrogen. The invention has the advantages of capability of continuously repairing and treating pollutants in underground water in situ, good treatment effect, less disturbance to the surrounding environment, small occupied area, convenient installation and construction, low operation and maintenance cost, high cost performance and the like, and has wide application prospect.
But the traditional circulating well technology has limitations in repairing non-aqueous phase and organic pollutants with weak volatility, and the PRB technology also has the problems of filler inactivation and blockage, insufficient contact efficiency and the like. Based on the current situation that the removal effect of chlorophenols in underground water is difficult to ensure by a single repair technology, an in-situ coupling repair technology is developed in a targeted manner, and the repair efficiency of chlorophenols organic pollutants is improved urgently.
Furthermore, on the one hand, due to the differences in understanding to the person skilled in the art; on the other hand, since the applicant has studied a great deal of literature and patents when making the present invention, but the disclosure is not limited thereto and the details and contents thereof are not listed in detail, it is by no means the present invention has these prior art features, but the present invention has all the features of the prior art, and the applicant reserves the right to increase the related prior art in the background.
Disclosure of Invention
In view of the deficiencies of the prior art, the present invention provides a method for remedying groundwater pollution by using a circulating well coupled Permeable Reactive Barrier (PRB), so as to at least solve the above technical problems.
The invention discloses a method for remedying underground water pollution by a circulating well coupled permeable reactive barrier, which comprises the following steps:
s1, detecting the pollution condition and field exploration parameters of an area to be repaired;
s2, preparing an active composite material;
s3, filling the active composite material serving as a filler into a wall body of the permeable reactive barrier;
s4, arranging the filled permeable reactive barrier in a three-dimensional flow field of the circulating well in a horizontal or vertical mode to establish a repairing system and finish repairing work, wherein,
the active composite material is prepared by taking plant leaf extracting solution as a reducing substance to prepare zero-valent iron and loading the zero-valent iron on charcoal, the active composite material is filled in a treatment layer of the permeable reactive barrier, a water inlet area and a water outlet area are respectively arranged on two sides of the treatment layer, and a vertical hydraulic flow field is formed through the circulating well, so that underground water to be repaired can flow into the permeable reactive barrier from the outside of the circulating well through the water inlet area under the driving action of the circulating well, and flows out of the water outlet area after pollutants are removed through the treatment layer.
According to a preferred embodiment, the biochar is prepared by calcining carbon-rich biomass, particularly crop straws under the anoxic or anaerobic condition, cooling, carrying out acid soaking, cleaning until the pH is neutral, drying, grinding and sieving, wherein the crop straws are corn straws, and the calcining temperature of the corn straws in a muffle furnace can be set to be 350-900 ℃. Preferably, the corn stover is calcined in a muffle furnace at a calcination temperature set to at least 700 ℃.
Preferably, the straw biochar is a porous medium with a large specific surface area, can enrich a large amount of chlorophenols in the surrounding water environment, and can remove the chlorophenols in the underground water mainly in a physical adsorption mode. However, the toxicity of chlorophenol cannot be changed by single physical adsorption, and only the migration control effect is achieved, and most adsorption processes are reversible, and the enriched chlorophenol can return to the underground water to continue migration at any time. The zero-valent iron particles can quickly reduce chlorine-containing organic matters, so that the toxicity of the chlorine-containing organic matters is reduced and the biocompatibility is improved. Therefore, the invention aims to optimize and modify by utilizing the advantages of the two to prepare the corn straw loaded nano zero-valent iron composite material so as to improve the probability of capturing pollutants and improve the dispersibility of zero-valent iron and further increase the reaction rate of the pollutants and the nano iron.
According to a preferred embodiment, the plant leaf extract is obtained by adding green tea into pure water, heating in water bath, and filtering, wherein the plant leaf extract mainly contains tea polyphenols. Tea Polyphenols (Tea Polyphenols) account for 20% -35% of the weight of the dry green Tea, are the general name of Polyphenols in the Tea, and comprise four types of catechins, anthoxanthins (flavonoids), phenolic acids and anthocyanins.
According to a preferred embodiment, the prepared biochar and ferric salt are mixed with an ethanol solution in the environment of introducing nitrogen to obtain a mixed solution of the biochar and ferrous ions, wherein the ferric salt is ferrous sulfate heptahydrate.
According to a preferred embodiment, the biochar, the ferrous ion mixed solution and the plant leaf extracting solution are mixed according to a preset iron-carbon loading ratio to obtain a composite material suspension, and the composite material suspension is washed, separated and dried to obtain the active composite material, wherein the preset iron-carbon loading ratio comprises 1:2.
preferably, the invention adopts a green synthesis method to prepare zero-valent iron, and high reducing components such as polyphenol, caffeine and the like in plant leaves are extracted to replace toxic chemical reduction reagents, and the advantages of the synthesis method mainly comprise: (1) Polyphenols contained in the plant extract are used as a reducing agent and a protective agent of zero-valent iron; and (2) the environment-friendly and low-cost. Meanwhile, zero-valent iron is loaded on the charcoal, so that chlorophenols in underground water can be effectively repaired, and environmental risks caused by the zero-valent iron are reduced.
According to a preferred embodiment, the dosage of the active composite material is 2-3 g/L when the pH value of the underground water is adjusted to be less than 5.8 under the condition that the concentration of the pollutant is at a first threshold value; when the pH value of the underground water is adjusted to be more than or equal to 5.8 and less than 7, the adding amount of the active composite material is 3-4 g/L; when the pH value of the underground water is adjusted to be more than or equal to 7, the adding amount of the active composite material is more than 4g/L, wherein the first threshold value is less than or equal to 10mg/L.
According to a preferred embodiment, the dosage of the active composite material is 3-4 g/L when the pH value of the underground water is adjusted to be less than 5.8 under the condition that the concentration of the pollutant is at a second threshold value; when the pH value of the underground water is adjusted to be more than or equal to 5.8, the adding amount of the active composite material is more than 4g/L, wherein the second threshold value is more than 10mg/L and less than or equal to 20mg/L.
According to a preferred embodiment, the active composite material is dosed in an amount of more than 4g/L at a concentration of the contaminant at a third threshold value of more than 20mg/L and the groundwater is rendered acidic in such a way that the dosing amount of the acidic substance is increased.
According to a preferred embodiment, a sieve of a corresponding size, based on the thickness of the active composite material, is arranged between the active composite material-filled treatment layer and the water inlet zone and/or the water outlet zone, wherein the active composite material is filled in the treatment layer by mixing at least 2 volumes of quartz sand.
Preferably, different filler filling modes of the active composite GT-nZVI @ BC during dynamic treatment can influence the penetration effect of 2,4-DCP. For permeable reactive barriers with the same filler quality but different filling modes, 2,4-DCP is quickly removed in the initial stage, and then the permeable reactive barriers adopting the mixed filling mode show better 2,4-DCP removal performance, and the more the mixed quartz sand is, the better the relative removal effect is. The reaction process is indirectly promoted because the active filler thickness is increased while the filler is dispersed because more quartz sand is mixed.
According to a preferred embodiment, the monitoring unit configured in the restoration system formed by coupling the permeable reactive barrier and the circulating well records the occurrence of the preset water quality unit variation as a driving event when the underground water quality is monitored.
Drawings
FIG. 1 is a schematic flow chart of a method for remediating groundwater pollution by using a circulating well coupled permeable reactive barrier provided by the invention;
FIG. 2 is a scanning view of a corn stalk charcoal electro-mirror;
FIG. 3 is (a) a curve of adsorption of corn stover biochar to 2,4-DCP at different calcination temperatures (b) a curve of adsorption kinetics fit of corn stover biochar to 2,4-DCP at different calcination temperatures;
FIG. 4 is (a) a 2,4-DCP removal curve at different iron-carbon mass loading ratios (b) a 2,4-DCP two-chamber one-stage kinetic fit curve at different iron-carbon mass loading ratios;
FIG. 5 is (a) a 2,4-DCP removal curve at different material dosages (b) a 2,4-DCP two-compartment first order kinetic fit curve at different material dosages;
FIG. 6 is a bar graph of (a) removal curve of 2,4-DCP at different pH (b) 2,4-DCP two-chamber first order kinetics fit curve at different pH (c) pH change before and after reaction solution;
FIG. 7 is (a) the removal curve at different 2,4-DCP concentrations (b) the two-compartment first order kinetic fit curve at different 2,4-DCP concentrations;
FIG. 8 is a scanning electron microscope image of corn stalk charcoal loaded green tea nanometer zero-valent iron (a: GT-nZVI; b: size distribution of GT-nZVI (rough calculation); cd: GT-nZVI @ BC);
FIG. 9 is a schematic diagram of the structure of a recurring well-coupled horizontal PRB in a preferred embodiment;
FIG. 10 is a schematic diagram of the structure of a preferred embodiment of a circulating well multi-type circulation pattern coupling level PRB for remediation of contaminated groundwater.
List of reference numerals
1: pumping and injecting a water pump; 2: a water pumping pipe; 3: a water outlet screening section; 4: a packer; 5: circulating the downhole screen section; 6: an underground water flow field line; 7: the circulating well hydraulic influence radius (R); 8: non-horizontal PRB radius of action (r) 2 ) (ii) a 9: horizontal PRB radius of action (r) 1 ) (ii) a 10: a permeable reactive barrier; 11: circulating the screen section on the well; 12: a water outlet pipe; 13: an aeration zone; 14: the groundwater aquifer is saturated with water.
Detailed Description
The following detailed description is made with reference to the accompanying drawings.
The invention discloses a method for remedying underground water pollution by a circulating well (GCW) coupled Permeable Reactive Barrier (PRB), wherein the underground water pollutants at least comprise various organic matters including chlorophenols, and the chlorophenols can persistently cause soil and underground water pollution when entering the environment and can form certain threat to an underground water biological system. In addition, because the benzene ring has more chlorine atom substitution positions, the degradation difficulty is increased along with the increase of the number of chlorine atoms, and the biocompatibility is further reduced. Preferably, the method for remediating underground water organic pollution disclosed by the invention can be at least used for remediating 2,4-dichlorophenol pollution.
Preferably, the circulating well (GCW) remediation technique is a combination of an in-situ air turbulence (AS) technique and a pump-out treatment (P & T) technique. In the process of repairing groundwater, contaminated groundwater enters the well through the water inlet screen section and flows out of the water outlet screen section 3 to form a circulating flow field in the formation and the well.
Preferably, permeable Reactive Barrier (PRB) technology is a method for in-situ remediation of groundwater pollution by active reaction media filled in walls. Organic pollutants pass through the wall body and then are adsorbed or degraded by the active reaction medium, so that the concentration of the pollutants in the flowing underground water is reduced or eliminated.
Further, since the permeable reactive barrier 10 is buried underground for a long time, it has at least the following disadvantages: such as incomplete coverage in the direction of aquifer water flow, easy clogging of the active packing media, difficulty in monitoring, difficulty in adjustment, etc. For the insoluble phase organic matters, the insoluble phase organic matters are insoluble in water and have slow flow rate of underground water, and are usually blocked or adsorbed in soil and rock gaps, and are also not easy to migrate to the restoration area of the permeable reactive barrier 10 along with underground water flow. Therefore, the circulation well technology can be utilized to form vertical water flow circulation so as to make up the defect of insufficient pollutant contact efficiency of the PRB technology and improve the pollutant trailing phenomenon of the low-permeability area of the stratum, thereby changing passive repair into active repair.
Preferably, as shown in fig. 9, the hydraulic influence radius R of the circulation well is limited by the thickness of the aquifer, the anisotropy of the stratum structure, the flow rate of the groundwater and the structural design of the circulation well, and the design parameters of the circulation well can be adjusted in time according to the requirement of the actual repair radius. Preferably, the permeable reactive barrier 10 can be arranged at any position within the range of the hydraulic influence radius 7 (R) of the circulating well according to the restoration requirement of the polluted site, and the horizontal PRB action radius 9 (R1) is 0 < R 1 Within the range of less than R, the action radius 9 (R1) of the horizontal PRB is adjusted as required, thus effectively reducing the ground fault in the repair processThe disturbance of the layer can further reduce the repair cost to a certain extent. Preferably, based on the adjustment of the horizontal PRB action radius 9 (R1), there is a non-horizontal PRB action radius 8 (R2) within the range of the circulating well hydraulic influence radius 7 (R). Preferably, as shown in fig. 10, the horizontally/vertically placed PRBs are suitable for remediation in circulation well multi-type circulation pattern conditions, including but not limited to the forward circulation, reverse circulation, and multi-filter circulation of the circulation well.
According to a preferred embodiment, as shown in FIG. 1, the method for remediating organic contamination of groundwater may comprise the steps of:
s1, detecting the polluted condition and field exploration parameters of an area to be repaired;
s2, preparing an active composite material;
s3, filling the active composite material serving as a filler into the wall body of the permeable reactive barrier 10;
and S4, arranging the filled permeable reactive barrier 10 in a vertical flow field of the circulating well in a horizontal mode to establish a repairing system and finish repairing work.
Preferably, in step S2, the preparation method of the active composite material at least comprises the following sub-steps:
s2.1, preparation of biochar
Cutting clean and dry crop straws into sections, putting the sections into a container, setting a heating rate of 10 ℃/min in a muffle furnace, keeping the temperature for 2 hours after reaching a specified temperature, naturally cooling, soaking overnight with dilute hydrochloric acid, washing with pure water until the pH value is neutral, drying, and grinding through a 80-mesh screen.
Preferably, the temperatures may be designated as BC300, BC400, BC500, BC600, BC700, respectively, according to the designated temperatures.
Alternatively, the crop straw may be a mixture of one or more of corn, wheat and cotton straw mixed in any proportion. Preferably, the crop straw is corn straw.
S2.2 preparation of Green tea extract
Weighing a certain amount of green tea, adding into pure water (solid-to-liquid ratio is 1.
S2.3, preparation of crop straw biochar and ferrous ion mixed solution
Weighing biochar and ferric salt in a certain mass ratio, adding the biochar and ferric salt into a 1L three-neck flask, introducing nitrogen, adding a proper amount of oxygen-free pure water, adding 60mL of ethanol solution while stirring, and fully mixing for 20min to obtain a mixed solution of the biochar and ferrous ions.
Optionally, the iron salt is a mixture of one or more of ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, ferrous nitrate and ferric nitrate mixed in any proportion. Preferably, the iron salt is ferrous sulfate heptahydrate (FeSO) 4 ·7H 2 O)。
S2.4, preparation of green tea nano zero-valent iron loaded biochar material
Slowly dropping a certain volume of green tea extract (green tea extract and 0.1mol/L Fe) into the mixed solution in step S2.3 2+ The solution is mixed according to the volume ratio of 2:1), and the solution is continuously stirred for 30min under the nitrogen environment after the dripping is finished, so as to obtain the composite material suspension. And (3) cleaning and separating the composite material solution by adopting a high-speed centrifuge, and drying the separated solid at 80 ℃ in vacuum overnight to obtain the composite material GT-nZVI @ BC.
Preferably, the straw biochar is a porous medium with a large specific surface area, can adsorb chlorophenols in a surrounding water environment in a large amount, however, the toxicity of the chlorophenol cannot be changed by single physical adsorption, only the function of controlling the migration of the chlorophenol is achieved, most of adsorption processes are reversible, and the enriched chlorophenol can return to underground water to continue migration at any time. The nanometer zero-valent iron particles can quickly remove chlorine-containing organic matters, so that the toxicity of the chlorine-containing organic matters is reduced, and the biocompatibility is improved, therefore, the advantages of the chlorine-containing organic matters and the chlorine-containing organic matters are fully utilized and optimized and modified, the capacity of capturing pollutants can be effectively improved by preparing the zero-valent iron-loaded corn straw composite material, and meanwhile, the dispersity of the zero-valent iron is improved, so that the reaction rate of the pollutants and the nanometer zero-valent iron is increased.
Furthermore, the invention adopts a green synthesis method to prepare the nano zero-valent iron, namely, high reducing components such as polyphenol, caffeine and the like in the plant leaves are extracted to replace toxic chemical reduction reagents, so that the polyphenol substances contained in the plant extracting solution can be used as a reducing agent and a protective agent of the nano zero-valent iron, and meanwhile, the green synthesis method has the advantages of environmental friendliness and low cost.
Preferably, corresponding parameter conditions need to be controlled in the preparation and use processes of the active composite material GT-nZVI @ BC so as to improve the adsorption performance and removal rate of 2,4-DCP, wherein the parameter conditions can comprise calcination temperature, iron-carbon loading ratio, material adding amount, initial pH and the like.
Preferably, as shown in fig. 2, the corn straw biochar at different temperatures can be seen to have different morphological structures through a scanning electron microscope, and formed frameworks and pores are not seen in the biochar in a calcining temperature region of 300-400 ℃, so that the biochar is represented as a smooth and irregular sheet, which indicates that organic matters at a lower calcining temperature are not completely pyrolyzed, the requirements of a better carrier are not met, and the performance of the biochar is influenced; the temperature is continuously raised, a biochar framework in a calcination temperature region of 500-600 ℃ can be obviously observed, a formed pore channel is arranged on the side surface, fuzzy micropores can be seen at the magnification, but a plurality of impurities are arranged on the carbon sheet and possibly residual heat-resistant components; when the temperature reaches 700 ℃, the skeleton of the biochar is developed, and the surface of a formed pore channel has no impurities and is uniformly distributed with a plurality of micropores. The corn stalk biomass is continuously developed into a high-quality material with clear framework, smooth pore passage and rich pores in the calcining process from low temperature to high temperature.
Preferably, the biochar yield is only 18.53% at the lowest at a high temperature of 700 ℃, but the specific surface area is the largest (396.99 m) 2 And/g) shows that the biochar has developed skeleton pores and relatively higher adsorption effect.
And (3) fitting the corn straw biochar adsorption 2,4-DCP at different calcination temperatures by selecting a quasi-first-stage adsorption kinetic equation and a quasi-second-stage adsorption kinetic equation to obtain a linear fitting curve and fitting equation parameters shown in FIG. 3, wherein the performance of the biochar (BC 700) at the high temperature of 700 ℃ is better based on the quasi-second-stage adsorption kinetic equation with higher fitting degree.
Preferably, the iron-carbon loading ratio of GT-nZVI @ BC is changed by adjusting the adding amount of the corn stalk biochar and ferrous sulfate heptahydrate to obtain the best removal effect on 2,4-DCP, wherein GT-nZVI @ BC has relatively higher adsorptivity and reducibility at the same time when the iron-carbon loading ratio is 1:2 as shown in FIG. 4.
Preferably, according to the fitting result of the double-chamber first-order kinetic model, the removing process of the 2,4-DCP by the GT-nZVI @ BC is divided into two stages, wherein the reduction reaction occupies the main part and the adsorption effect is the second time. The reduction reaction rate is influenced most by pH, the acidic environment promotes the reduction reaction, the alkaline environment brings negative effects, and meanwhile, the reduction reaction rate is increased by increasing the dosage of GT-nZVI @ BC or reducing the concentration of 2,4-DCP. Then recovering GT-nZVI @ BC after reaction for phase identification, and the result shows that the peak intensity of the nano zero-valent iron (alpha-Fe) is reduced, and the reduction reaction generates Fe 2 O 3 、Fe 3 O 4 And (3) waiting for iron oxide.
Preferably, as shown in FIG. 5, the removal efficiency of 2,4-DCP is gradually improved as the addition amount is gradually increased, wherein the removal rate of 2,4-DCP is higher than 80% when the addition amount is more than 3 g/L. Further, when the amount added was 4g/L, the removal rate of 2,4-DCP was 89%. Therefore, in order to ensure that the method for remedying the organic pollution of the underground water has higher removal rate of 2,4-DCP, the adding amount is at least more than 3g/L, preferably not less than 4g/L, and further preferably 4g/L.
Preferably, as shown in FIG. 6, the pH of the solution significantly affected the GT-nZVI @ BC removal of 2,4-DCP, with the increase in pH from 3 to 9,2,4-DCP removal decreasing from 87% to 37%. At a solution pH of 3, the removal rate was greatest for the same reaction time, with the reaction rate increasing with decreasing pH, primarily due to the large amount of H + The oxide film generated on the surface of GT-nZVI is subjected to acidolysis, which is beneficial to the zero-valent iron component in the material to further participate in the reaction of 2,4-DCP, so that the reduction dechlorination of 2,4-DCP is more beneficial under the acidic condition. When the solution pH was 9, the same reaction time resulted in a removal of 2,4-DCP of only 37%, indicating that the alkaline environment removal efficiency decreased dramatically due to the presence of more OH in the alkaline environment - With corroded Fe (II) and Fe (III)Hydrolysis reaction and precipitation, aggravate the surface passivation of GT-nZVI, hinder the GT-nZVI surface reaction from going on, simultaneously because GT-nZVI @ BC contains carboxyl and hydroxyl and other acidic functional groups are easy to be consumed in alkaline environment, reduce the 2,4-DCP capture ability, and then influence the overall removal efficiency. Therefore, the initial pH of the solution is at least less than 5.8, preferably not more than 3, and more preferably 3.
Preferably, the optimal parameter conditions determined after optimization through orthogonal experiments are as follows: the loading ratio was 1:2, the amount added was 4g/L, and the pH was 3.
Preferably, GT-nZVI @ BC has a removal rate of more than 85% when the concentration of 2,4-DCP in groundwater is less than 20mg/L as shown in FIG. 7, further, the GT-nZVI @ BC has a removal rate of 90% to 2,4-DCP when the concentration of 2,4-DCP in groundwater is 10mg/L, therefore, the method for remedying organic pollution of groundwater is suitable for the case that the concentration of 2,4-DCP in groundwater is less than 20mg/L (especially the concentration of 2,4-DCP in groundwater is close to 10 mg/L).
Preferably, as shown in FIG. 8, the GT-nZVI particles are prepared in irregular spherical and ellipsoidal shapes with an average particle size of 60.57nm and have agglomeration phenomena, and the GT-nZVI particles are dispersed in carbon sheets and channels after loading, and the agglomeration phenomena are reduced. The GT-nZVI surface polyphenol has rich content of reduction active substances, effectively participates in the reaction of reducing ferrite, is coated on the GT-nZVI surface to serve as a sealing agent, and makes functional groups on the GT-nZVI @ BC surface richer after loading.
Preferably, GT-nZVI @ BC is filled in the wall of the permeable reactive wall 10 as an active filler to dynamically remove 2,4-DCP pollution, wherein based on the penetration process curve of 2,4-DCP in different conditions, the optimal flow rate is 0.92m/d, the optimal filler thickness is 10cm, and the optimal filler mode is mixed 2 volumes of quartz sand.
Preferably, the quartz sand with three grain sizes of coarse, medium and fine is subjected to acid impurity removal, washed to be neutral and dried, the thickness of the coarse, medium and fine quartz sand filled at the upper end and the lower end is adjusted according to the thickness of the composite material filler, and the coarse, medium and fine quartz sand is compacted once every 2cm of the filler, wherein the quartz sand with multiple grain sizes can ensure the uniformity of inlet and outlet water.
Due to the complex flowing direction of underground water in natural environment, the heterogeneity of stratum can cause pollutants to flow through a high-permeability area, so that a dominant flow can be formed, and a turbulent flow phenomenon can occur when the pollutants flow through a low-permeability area. Both phenomena result in a decrease in the effective contact rate of the active reaction area of permeable reactive barrier 10 with the target contaminant. Therefore, the invention utilizes the active water circulation of the circulating well technology to make up the contact efficiency deficiency of the permeable reactive barrier technology. Further, the permeable reactive barrier 10 may be disposed in a horizontal/vertical arrangement on one side or more sides of the circulation well body such that the permeable reactive barrier 10 is arranged in a substantially perpendicular manner to the groundwater flow direction, which is an active water flow circulation direction caused by the circulation well, the circulation direction being substantially parallel and same direction with the gravity direction outside the circulation well body, and substantially parallel and opposite direction with the gravity direction inside the circulation well body. The permeable reactive barrier 10 arranged in a horizontal direction takes in more groundwater with a maximum contact area to prevent groundwater from bypassing the permeable reactive barrier 10 and being directly sucked into by the circulation well body. The permeable reactive barrier 10 can reduce disturbance to the formation in such a manner that it is not necessary to be buried deep underground.
Preferably, as shown in fig. 9, the circulation well body may excavate a ground surface contaminated by groundwater in a vertical shaft excavation manner to a certain depth of the underground region in a direction towards the ground bottom, so that the excavated underground region and the surface of the surrounding formation can be used for accommodating and/or carrying the circulation well body, wherein the underground region provided with the circulation well body is a region where groundwater to be repaired is located, and includes an aeration zone 13 and a groundwater aquifer saturated zone 14, the aeration zone 13 is a zone above a submergence surface below the ground, and the groundwater aquifer saturated zone 14 is an aquifer zone below a submergence surface. Preferably, a packer 4 is arranged in the circulating well body to divide the internal space of the circulating well body into a circulating downhole screen section 5 and a circulating uphole screen section 11. Preferably, the circulating underground screen section 5 and the circulating aboveground screen section 11 can be communicated through the water pumping pipe 2, the pumping and injection water pump 1 and the water outlet pipe 12, so that underground water in the circulating underground screen section 5 can enter the circulating aboveground screen section 11 through the water pumping pipe 2 and the water outlet pipe 12 under the driving action of the pumping and injection water pump 1, wherein the water pumping pipe 2 is communicated with the circulating underground screen section 5, and the water outlet pipe 12 is communicated with the circulating aboveground screen section 11. Preferably, the groundwater entering the screen section 11 of the circulation well can flow out of the screen section 3 opened on the side wall of the circulation well body, and then flows through the permeable reactive barrier 10 and enters the screen section 5 of the circulation well through the screen section of the inflow, thereby forming the circulating groundwater flow field line 6.
Preferably, based on experimental data, the concentration of 2,4-DCP can be partially reduced by starting the circulating well alone, the overall distribution is relatively high, a small part of DCP may volatilize under the influence of circulating water flow, and the repairing effect is poor; in comparison, the adoption of the repairing mode of the circulating well coupled horizontal permeable reactive barrier 10 can enable the concentration of 2,4-DCP to be always kept at a lower level, the highest concentration of a monitoring point 2,4-DCP is relatively greatly reduced, and the repairing effect is greatly improved. Furthermore, for the repairing mode of the circulating well coupled horizontal permeable reactive barrier 10, the concentration of the circulating water close to two sides of the circulating well is low, the circulating water flow speed of the two sides is fastest, the water conservancy circulation is large, the permeable reactive barrier 10 is in most frequent contact with an active filler layer, and the lowest point of the concentration of 2,4-DCP is near the area. At the furthest distance from the recycle well, the highest point 2,4-DCP concentration is monitored to be higher relatively close to both sides of the recycle well due to the slower recycle flow rate. As the reaction is carried out, the nano zero-valent iron on GT-nZVI @ BC is gradually consumed, and the removal process of 2,4-DCP by the GT-nZVI @ BC is divided into two parts of reduction and adsorption, wherein the reduction dechlorination is the main part and the reaction rate is higher, and then the removal rate of 2,4-DCP is lower, but the reaction is still active, and the adsorption effect of the biochar is simultaneously accompanied, so that the concentration of 2,4-DCP in the water flow can still be reduced to a certain degree after the circulating well circularly pollutes the aquifer for many times. Therefore, the repairing method of the circulating well coupled permeable reactive barrier 10 of the present invention can have a better repairing effect.
Further, the groundwater contained in the surrounding soil layer may also flow through the permeable reactive wall 10 based on the pumping action of the pumping and injecting unit and its own gravity.
Further, the permeable reactive barrier 10 may be configured with a multi-layered structure, which may include an influent zone, a treated zone, and an effluent zone, wherein a screen may be configured between the layers. Preferably, when the permeable reactive walls 10 are arranged, the water inlet region is disposed closer to the ground surface than the water outlet region so that groundwater flowing in the direction of gravity may pass through the water inlet region, the treatment layer, and the water outlet region in this order, and the permeable reactive walls 10 arranged in the horizontal direction can prevent the overflow of the contaminants as much as possible. Preferably, the groundwater remediation can be completed through multiple cycles of the circulation well.
Preferably, the prepared GT-nZVI @ BC can be used as an active filler to be filled in the treatment layer, wherein the main body area for groundwater remediation is positioned in the permeable reactive barrier 10 to avoid the well body of the circulating well, so that the corrosion reaction which may occur in the well body of the circulating well is greatly reduced, and the service life of the circulating well is further prolonged.
Preferably, the steel reinforcement box frame can be connected with the steel reinforcement lifting hook so that permeable reactive barrier 10 can be integrated into the box that can hoist so as to hoist permeable reactive barrier 10 through external hoisting equipment at the same side that is located the district of intaking to be convenient for change and position adjustment to permeable reactive barrier 10.
According to a preferred embodiment, the restoration system may be provided with a monitoring unit for acquiring the operation state of the permeable reactive barrier 10 and the circulation well and the pollutant removal effect in the groundwater pollution plume region. Preferably, the monitoring unit can monitor the underground water quality and the water level, and also can monitor the activity and the aging degree of the permeable reactive barrier 10, wherein the activity of the permeable reactive barrier 10 generally has an opposite trend to the aging degree. Further, the permeable reactive wall 10 is replaced in time based on the data acquired by the monitoring unit, and the installation position thereof can be optimized.
Preferably, the monitoring unit records the occurrence of a preset water quality unit variation as a driving event when monitoring the underground water quality. Specifically, when the monitoring unit monitors that the time from the time when the monitoring data is recorded in the time series above the distance to the time when the change value of the underground water quality in the current time series is exactly equal to the preset water quality unit change amount, the underground water quality real-time information acquired at the time of the current time series is sent to the processing unit so as to perform circulation of the next time series, wherein the preset water quality unit change amount can be set or calibrated based on experience, limited tests, numerical simulation, big data sharing and the like. Further, for any current time sequence, the time interval between the last time sequence and the current time sequence and the time interval between the current time sequence and the next time sequence can be used as a recording time period, and recording time periods with different time spans can be formed between time sequences of different segments, that is, the recording time period can be an indeterminate value based on real-time situation change. For example, for the same predetermined water quality unit variation, factors such as permeable reactive barrier 10 with different activity or aging degree, groundwater with different water quality, and different water flow rate may all affect the recording time period.
Further, the recording time period can also be adaptively changed along with the change of the unit change of the preset water quality. Generally, decreasing the set value of the unit change amount of the preset water quality may increase the recording frequency to decrease the recording time period; conversely, increasing the set value of the unit change of the preset water quality can reduce the recording frequency to increase the recording time period. When the restoration system is in a normal underground water restoration process, the frequently recorded data with a too short recording time period has a limited effect, and meanwhile, the transmission, processing and/or storage capacity of the data is increased, the load of the system is increased, and the delay effect of the data is aggravated; and an excessively long recording time period may miss the recording of some important data and cause a corresponding time lag, thereby possibly causing low groundwater remediation efficiency of the remediation system. Therefore, it is necessary to flexibly set the appropriate unit change amount of the preset water quality to ensure efficient remediation of the organic pollution of the groundwater.
Preferably, the preset water quality unit change amount may be adjusted based on the activity state of the permeable reactive barrier 10 and/or the overall condition of the underground water quality. Generally, as the repair system continues the repair time of the corresponding polluted groundwater, the permeable reactive barrier 10 replaces the purification of groundwater at the cost of activity reduction to improve the quality of the groundwater, therefore, in a general case, as the repair time continues, the preset unit change amount of the water quality can be set in a decreasing manner to more sensitively acquire the subtle change of the quality of the groundwater, so that the active state of the permeable reactive barrier 10 can be conveniently confirmed while the overall condition of the water quality is more accurately judged, and the aged and inactivated permeable reactive barrier 10 can be replaced in time. Further, in an unusual case, the relationship between the activity state of the permeable reactive barrier 10 and the overall underground water quality condition is broken due to the intervention of specific factors, so that the preset water quality unit variation can be adjusted based on the characteristics and the influence degree of the specific factors, wherein the specific factors may include secondary pollution, the permeable reactive barrier 10 being replaced, and the like, so as to cause the mutation of the activity state of the permeable reactive barrier 10 and/or the overall underground water quality condition.
Further, the preset water quality unit change amount is set in such a manner that the recording time period is shortened as the pumping action of the pumping and injection water pump 1 is increased. Specifically, under the condition that the power of the water pumping and injecting pump 1 is increased, the circulation speed of underground water in the circulating well body is increased, the flow speed of water flowing out of the circulating well body through the permeable reactive barrier 10 is increased through circulating water flow, so that the retention time of the water flow in the permeable reactive barrier 10 is shortened, the recording time period can be shortened in a mode of reducing the preset water quality unit variation set value, and the change condition of the water quality can be acquired at a higher recording frequency.
Further, the monitoring unit can simulate the prediction data based on the numerical model to judge the current groundwater state through comparison of the prediction data and the monitoring data based on time parameters, so that the repair efficiency can be adjusted at least by adjusting the power of the water pumping and injecting pump 1 and/or replacing the permeable reactive wall 10 and/or optimizing the installation position of the permeable reactive wall 10, and meanwhile, under the condition that the difference value between the prediction data and the recorded monitoring data exceeds the threshold value, the monitoring unit can improve the monitoring precision through reducing the unit variation of the preset water quality and discover the abnormality of the repair process in time. For the condition that the groundwater quality monitoring data basically does not change within a time threshold, the data may be caused by aging and inactivation of the permeable reactive barrier 10, or may be caused by other reasons (such as sensor failure and the like), so that the staff can timely overhaul and troubleshoot the equipment to ensure normal groundwater remediation.
Preferably, the higher the rotating speed of the water pumping and injecting pump 1 is, the higher the pumping and injecting efficiency is, and the more beneficial the influence radius of the circulating well is to be enlarged.
Preferably, after the circulation well is started, the chemical indexes of water in the aquifer with the thickness of 10-25 cm around the active filler layer are influenced, the pH around the active filler is reduced, an acid area in the horizontal direction is formed, and the pH is about 5, because H is generated by the dechlorination reduction reaction under the environment + And in addition, the filler is acidic, and simultaneously, the pH value of the whole simulation tank is relatively reduced along with the circulating water flow of the circulating well. H as the reaction proceeds + The concentration decreased and the pH gradually increased. Thus, the change in pH can be considered as a water chemistry indicator for the GT-nZVI @ BC reaction. The pH changes in the aqueous layer were consistent with the total Fe, 2,4-DCP changes.
Preferably, the oxidation-reduction potential ORP value may represent a macroscopic aquifer redox environment to characterize the remediation process. After the circulation well is started, the ORP value of the aquifer near the active filler rapidly drops to about-69 mV, which macroscopically represents a reducing environment. The ORP value of this region rises back after a period of remediation due to the reduced content of reducing iron in GT-nZVI @ BC. In general, the change of the ORP value of the water chemistry index in the aquifer indirectly reflects the activity of GT-nZVI @ BC, and the change rule of the ORP value is consistent with the change rule of pH, total Fe, 2,4-DCP concentration.
Preferably, the pH value and the ORP value are available as monitoring targets of the monitoring unit.
It should be noted that the above-mentioned embodiments are exemplary, and that those skilled in the art, having benefit of the present disclosure, may devise various arrangements that are within the scope of the present disclosure and that fall within the scope of the invention. It should be understood by those skilled in the art that the present specification and figures are illustrative only and are not limiting upon the claims. The scope of the invention is defined by the claims and their equivalents. The present description contains a plurality of inventive concepts such as "preferably", "according to a preferred embodiment" or "optionally" each indicating that the respective paragraph discloses a separate concept, the applicant reserves the right to apply for divisional applications according to each inventive concept. Throughout this document, the features referred to as "preferably" are only an optional feature and should not be understood as necessarily requiring that such applicant reserves the right to disclaim or delete the associated preferred feature at any time.
Claims (10)
1. A method for repairing underground water pollution by a circulating well coupled permeable reactive barrier is characterized by comprising the following steps:
s1, detecting the polluted condition and field exploration parameters of an area to be repaired;
s2, preparing an active composite material;
s3, filling the active composite material serving as a filler into a wall body of the permeable reactive barrier (10);
s4, arranging the filled permeable reactive barrier (10) in a three-dimensional flow field of the circulating well in a horizontal or vertical mode to establish a repairing system and complete repairing work,
wherein the content of the first and second substances,
the active composite material is zero-valent iron prepared by taking plant leaf extracting solution as reducing substances and loaded on biochar, the active composite material is filled in a treatment layer of the permeable reactive barrier (10), a water inlet area and a water outlet area are respectively arranged on two sides of the treatment layer, a vertical hydraulic flow field is formed through the circulating well, so that underground water to be repaired can flow into the permeable reactive barrier (10) from the outside of the circulating well through the water inlet area under the driving action of the circulating well, and flows out from the water outlet area after pollutants are removed through the treatment layer.
2. The method as claimed in claim 1, wherein the biochar is obtained by calcining carbon-rich biomass under anoxic or anaerobic condition, cooling, acid soaking, washing to neutral pH, drying, grinding and sieving, wherein when the carbon-rich biomass is corn straw, the calcining temperature of the corn straw in a muffle furnace can be set to 350-900 ℃.
3. The method according to claim 1 or 2, wherein the extract solution of plant leaves is obtained by adding plant leaves to purified water, heating in water bath, and filtering, wherein the extract solution of plant leaves contains tea polyphenols.
4. The method according to any one of claims 1 to 3, wherein the prepared biochar and ferric salt are mixed with ethanol solution in an environment of introducing nitrogen gas to obtain a mixed solution of biochar and ferrous ions, wherein the ferric salt is ferrous sulfate heptahydrate.
5. The method as claimed in any one of claims 1 to 4, wherein the biochar and ferrous ion mixed solution and the plant leaf extracting solution are mixed according to a preset iron-carbon loading ratio to obtain a composite material suspension, and the composite material suspension is washed, separated and dried to obtain the active composite material, wherein the preset iron-carbon loading ratio comprises 1:2.
6. the method according to any one of claims 1 to 5, wherein the active composite is added in an amount of 2 to 3g/L when the groundwater pH is adjusted to be less than 5.8 under the condition that the pollutant concentration is at the first threshold value; when the pH value of underground water is adjusted to be more than or equal to 5.8 and less than 7, the adding amount of the active composite material is 3-4 g/L; when the pH value of underground water is adjusted to be more than or equal to 7, the adding amount of the active composite material is more than 4g/L, wherein the first threshold value is less than or equal to 10mg/L.
7. The method according to any one of claims 1 to 6, wherein the active composite is added in an amount of 3 to 4g/L when the groundwater pH is adjusted to be less than 5.8 with the contaminant concentration at the second threshold value; when the pH value of underground water is adjusted to be more than or equal to 5.8, the adding amount of the active composite material is more than 4g/L, wherein the second threshold value is more than 10mg/L and less than or equal to 20mg/L.
8. The method according to any one of claims 1 to 7, wherein the active composite material is added in an amount of more than 4g/L in case the contaminant concentration is at a third threshold value, and the groundwater is made acidic in such a way that the amount of acidic substance added is increased, wherein the third threshold value is more than 20mg/L.
9. The method according to any one of claims 1 to 8, wherein a sieve having a size determined based on the thickness of the active composite material is disposed between the treatment layer filled with the active composite material and the water inlet zone and/or the water outlet zone, wherein the active composite material is filled in the treatment layer by mixing at least 2 volumes of silica sand.
10. The method according to any one of claims 1 to 9, wherein the monitoring unit of the restoration system formed by coupling the permeable reactive barrier (10) with the circulating well is used for recording the occurrence of the preset water quality unit variation as the driving event when monitoring the underground water quality.
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