CN117902770A - Magnetic coagulation treatment system and method for efficiently and rapidly treating thallium-containing sewage - Google Patents
Magnetic coagulation treatment system and method for efficiently and rapidly treating thallium-containing sewage Download PDFInfo
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- 239000010865 sewage Substances 0.000 title claims abstract description 55
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Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention provides a magnetic coagulation treatment system and a treatment method for efficiently and rapidly treating thallium-containing sewage, comprising the following steps: an oxidation treatment unit for carrying out oxidation treatment on thallium-containing sewage by utilizing a magnetic material and sodium persulfate; the magnetic coagulation unit is used for carrying out magnetic coagulation treatment on thallium-containing sewage by adding a chemical coagulant; a microwave digestion unit for carrying out microwave digestion on the magnetic coagulation substance by a microwave digestion instrument; the magnetic separation unit is used for recycling magnetic materials in the coagulated material, so that the rGO-Fe 3O4@TiO2 magnetic nano material and PS are used as emergency treatment agents, the synergistic strengthening effect of the magnetic materials and coagulation can be fully exerted through a magnetic coagulation technology, the thallium pollution problem can be effectively solved, the thallium removal rate and the stability are high, the removal of soluble materials is promoted, the floccules are more compact, the chemical sludge amount is less, the recovery rate of the magnetic seeds is high, the residual metal ions are less, and the energy consumption is low.
Description
Technical Field
The invention belongs to the technical field of thallium-containing sewage treatment, and particularly relates to a magnetic coagulation treatment system and a treatment method for efficiently and rapidly treating thallium-containing sewage.
Background
In recent years, thallium pollution occurs, which poses serious threats to the ecological environment and to the health of the residents. At present, the condition that the industrial wastewater is connected into a municipal sewage pipe network, and the out-of-stock water is caused by out-of-stock water still exists generally, a sewage plant bears a plurality of 'unbearable weights', and once thallium pollutants enter a municipal sewage treatment system, serious impact can be caused on an original biological treatment unit, and even the treatment system is paralyzed. Meanwhile, the sewage has high TOC content and complex water quality, and provides new challenges for thallium pollution emergency treatment schemes. The technical scheme has better treatment effect on the high-concentration thallium-containing water body, but has limited treatment effect on the low-concentration thallium-containing water body, the quality of the treated water environment cannot meet the water quality standard, and the flocculated sludge has high yield and needs to be treated according to dangerous waste, so that the treatment difficulty and cost are improved. Therefore, there is a need to establish efficient treatment schemes to cope with the problems of thallium pollution control and magnetic material recovery under complex conditions.
The recovery of magnetic materials often adopts an external magnetic field directly, if the materials are magnetically separated from the treated water directly, the treated water is large in quantity, equipment is required to be high in cost, and the requirements of quick and convenient thallium pollution emergency accident treatment cannot be met. The magnetic coagulating sedimentation technology is used as a novel separation technology, magnetic particles are added in the common coagulating sedimentation process, and then the magnetic particles are separated in an external magnetic field or sediment is carried out, so that the aggregate of 'target pollutants' in the suspension is removed, and the technology is an effective upgrade of the traditional coagulating sedimentation technology. Compared with the traditional precipitation technology, the method has higher precipitation speed and precipitation efficiency, and can effectively remove turbidity, chromaticity, suspended particles, organic matters, heavy metals and the like of the wastewater. At present, the magnetic coagulation separation technology is widely applied to the fields of sewage emergency treatment, urban sewage treatment, industrial wastewater advanced treatment and the like. Research shows that the addition of magnetic nano particles and other particles form magnetic floccules with better sedimentation performance, which is not only beneficial to the formation of floccules, but also can effectively recover the magnetic nano particles from the floccules under the action of an external magnetic field, and compared with the separation of the magnetic particles from the treated water, the treatment capacity of the magnetic coagulation floccules can be greatly reduced.
Disclosure of Invention
The invention provides a magnetic coagulation treatment system and a treatment method for efficiently and rapidly treating thallium-containing sewage, which can effectively solve the thallium pollution problem and have the degradation efficiency of organic pollutants.
The technical scheme of the invention is realized as follows: a magnetic coagulation treatment method for efficiently and rapidly treating thallium-containing sewage comprises the following steps:
step 1, adding a magnetic material and sodium persulfate into thallium-containing sewage, and uniformly mixing to obtain a mixed solution A;
Step 2, adding a chemical coagulant into the mixed solution A for carrying out magnetic coagulation reaction to obtain a mixed solution B;
and step 3, carrying out solid-liquid separation on the mixed solution B to obtain a magnetic coagulation substance, and recovering the magnetic material.
As a preferred embodiment, the magnetic material in step 1 comprises rGO-Fe 3O4@TiO2, and the concentration of the magnetic material is 0.05-0.2g/L;
The addition amount of sodium persulfate in the step 1 is 15mM.
As a preferred embodiment, the preparation method of rGO-Fe 3O4@TiO2 comprises the following steps:
Step 10, synthesizing graphene oxide nano sheets by using a Hummers method;
Step 11, preparing a reduced graphene oxide nano sheet and ferroferric oxide composite material by a coprecipitation method, wherein the molar ratio of the graphene oxide nano sheet to the ferroferric oxide composite material is 2:1, and slowly dropwise adding ammonia under the condition of intense stirring to form an rGO-Fe 3O4 composite material;
Step 12, dispersing the rGO-Fe 3O4 composite material in absolute ethyl alcohol, adding ammonia water, uniformly stirring to prepare a rGO-Fe 3O4 dispersion solution, and dissolving TBOT in absolute ethyl alcohol under stirring to prepare a TiO 2 precursor;
And 13, slowly dropwise adding the TiO 2 precursor into the rGO-Fe 3O4 dispersion solution, taking out solid particles through magnetic separation, washing, and vacuum drying to obtain the rGO-Fe 3O4@TiO2.
As a preferred embodiment, the chemical coagulant in step 2 comprises aluminum sulfate, the concentration of aluminum sulfate being 20-80 mg/L.
In a preferred embodiment, the pH of the mixed solution B is adjusted before the solid-liquid separation of the mixed solution B in the step 3 by adding 0.01mol/L NaOH solution to adjust the pH of the mixed solution B to 10.
As a preferred embodiment, the uniform mixing in step 1 is carried out by reacting for 5 hours in a water bath shaker at a rotational speed of 160 r/min.
In the step 3, the magnetic coagulation material obtained by carrying out solid-liquid separation on the mixed solution B is subjected to ultrasonic treatment, the ultrasonic treatment temperature is 25 ℃, the ultrasonic treatment time is 15min, the ultrasonic treatment is carried out for 3-5 times by using ultrapure water, the microwave digestion is carried out after the washing, and the microwave digestion time is 30min.
In a preferred embodiment, the method for recovering the magnetic material in step 3 comprises washing the magnetic material with ultrapure water 2-3 times, freeze-drying, then placing into the ultrapure water to obtain a cleaning solution, introducing the cleaning solution into the hollow glass tube at a speed of 1ml/min by using a peristaltic pump during stirring, attaching a magnet to the outside of the hollow glass tube, collecting the magnetic material attached to the hollow glass tube, and drying.
A magnetic coagulation treatment system for efficiently and quickly treating thallium-containing sewage comprises:
An oxidation treatment unit for carrying out oxidation treatment on thallium-containing sewage by utilizing a magnetic material and sodium persulfate;
the magnetic coagulation unit is used for carrying out magnetic coagulation treatment on thallium-containing sewage by adding a chemical coagulant;
a microwave digestion unit for carrying out microwave digestion on the magnetic coagulation substance by a microwave digestion instrument;
And a magnetic separation unit for recovering the magnetic material in the coagulated material.
After the technical scheme is adopted, the invention has the beneficial effects that:
The invention takes rGO-Fe 3O4@TiO2 magnetic nano material and PS as emergency treatment agents, can fully exert the synergistic strengthening effect of the magnetic material and coagulation by a magnetic coagulation technology, can effectively solve the thallium pollution problem and has the degradation effect of organic pollutants.
The invention has the advantages of high thallium removal rate and stability, promotion of removal of soluble substances, more compact floccules, less chemical sludge, high recovery rate of magnetic seeds, large treatment capacity, less residual metal ions, low energy consumption and the like.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a schematic illustration of a process flow;
FIG. 2 is a schematic diagram of the combined process treatment effect with rGO-Fe 3O4@TiO2 as the core;
FIG. 3 is a schematic diagram of the efficiency of magnetic separation and magnetic coagulation recovery of adsorbents;
FIG. 4 is a graph showing turbidity values after treatment by a combination process with rGO-Fe 3O4@TiO2 magnetic material as core;
FIG. 5 is a comparative schematic diagram of wastewater;
FIG. 6 is a schematic diagram showing the particle size distribution of residual particles of the reaction solution after treatment by different combination processes;
FIG. 7 is a schematic diagram of the reusability of the rGO-Fe 3O4@TiO2/PS/magnetic coagulation coupling system in removing Tl and TOC in the course of treating thallium-containing wastewater;
FIG. 8 is a schematic diagram of residual iron and titanium concentrations in effluent from thallium-containing wastewater treatment with rGO-Fe 3O4@TiO2/PS/coagulation coupling system;
FIG. 9 is a schematic diagram showing analysis of element distribution on the surface of the collected particles after ultrasonic and magnetic separation of the flocs in sequence;
FIG. 10 is a schematic diagram showing morphology of rGO-Fe 3O4@TiO2 particles treated by the process 3;
FIG. 11 is a schematic diagram showing a comparison of surface topography;
FIG. 12 is a schematic diagram of an X-ray spectroscopy analysis;
FIG. 13 is a schematic view of an X-ray photoelectron spectroscopy analysis;
FIG. 14 is a schematic diagram showing experimental results of the addition amount of rGO-Fe 3O4@TiO2;
FIG. 15 is a schematic diagram showing experimental results of the addition amount of sodium persulfate;
FIG. 16 is a schematic diagram showing the experimental results of the addition amount of the chemical coagulant.
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Firstly, detecting the water quality of sewage, wherein the detection result is as follows:
TABLE 1 Water quality detection results of wastewater
| Index (I) | pH | Conductivity (ms/cm) | COD(mg/L) | TOC(mg/L) | Turbidity (NTU) |
| Measurement value | 8.22 | 1.10 | 202 | 160.1 | 87 |
TlNO 3 is added into the sewage to obtain 1mg/L thallium-containing sewage.
Comparative example
In this experimental example, an adsorption oxidation experiment, a PH adjustment treatment experiment, a magnetic separation experiment and a magnetic coagulation experiment were performed, and meanwhile, in this experimental example, comparative analysis experiment results were also performed by five conditions of an adsorption oxidation experiment, an adsorption oxidation+ph adjustment treatment experiment, an adsorption oxidation+magnetic separation experiment, an adsorption oxidation+magnetic separation+ph adjustment treatment experiment, and an adsorption oxidation+magnetic coagulation experiment.
Process 1, adsorption oxidation experiment
The thallium-containing wastewater 100 mL prepared above was placed in a 250 mL blue cap bottle, and after PS 15mM was added, the solution was sonicated in an sonicator for 10. 10 min. After 0.2 g/L of rGO-Fe 3O4@TiO2 magnetic nano material is added, the blue cap bottle is placed in an ultrasonic instrument for ultrasonic treatment of 3 min, so that the blue cap bottle is fully dispersed. Sealing the blue cap bottle, then placing the blue cap bottle into a water bath oscillator to react for 5 hours at a rotating speed of 160r/min, and regulating the pH value of the solution in the reaction process.
In the process, the added rGO-Fe 3O4@TiO2 magnetic material activates PS, and the removal rate of Tl in thallium-containing sewage is 97.6%, as shown in figure 2.
In FIG. 2, process1 is process1, process2 is process2, process3 is process3, process4 is process4, and process5 is process 5.
Process 2, adsorption oxidation+pH adjustment treatment experiment
The thallium-containing wastewater 100mL prepared above was placed in a 250 mL blue cap bottle, and after PS 15mM was added, the solution was sonicated in an sonicator for 10. 10 min. After 0.2 g/L of rGO-Fe 3O4@TiO2 magnetic nano material is added, the blue cap bottle is placed in an ultrasonic instrument for ultrasonic treatment of 3 min, so that the blue cap bottle is fully dispersed. Sealing the blue cap bottle, placing the blue cap bottle into a water bath oscillator to react for 5 hours at a rotating speed of 160r/min, adding sodium hydroxide to adjust the pH of the solution to 10, sealing, and placing the blue cap bottle into a shaking table to continue the reaction for 3 hours.
In the above process, after the thallium-containing solution is subjected to adsorption oxidation treatment, the pH of the solution is adjusted to be strong alkaline (for example, pH=10), so that the removal effect of Tl pollutants can be further improved, and the removal rate of Tl is 98.7%, as shown in fig. 2.
Process 3, adsorption oxidation+magnetic separation experiment
The thallium-containing wastewater 100 mL prepared above was placed in a 250 mL blue cap bottle, and after PS 15mM was added, the solution was sonicated in an sonicator for 10. 10min. After 0.2 g/L of rGO-Fe 3O4@TiO2 magnetic nano material is added, the blue cap bottle is placed in an ultrasonic instrument for ultrasonic treatment of 3 min, so that the blue cap bottle is fully dispersed. Sealing the blue cap bottle, placing the blue cap bottle into a water bath oscillator to react for 5 hours at a rotating speed of 160r/min, using ultrapure water to wash the magnetic material for 2-3 times, freeze-drying the blue cap bottle, placing the blue cap bottle into the ultrapure water to obtain a cleaning liquid, introducing the cleaning liquid into a hollow glass tube at a speed of 1ml/min by using a peristaltic pump in the stirring process, attaching a magnet to the outside of the hollow glass tube, collecting the magnetic material attached to the hollow glass tube, and drying the magnetic material.
The reacted rGO-Fe 3O4@TiO2 magnetic material is subjected to magnetic separation by means of an external magnet, the removal rate of Tl is 96.8%, as shown in figure 2, compared with the process 1, the removal rate is not obviously changed, under the condition of strong magnet selected in a laboratory, the time consumption of the magnetic separation process is about 60min, and the magnetic separation time is directly related to the magnetic intensity and the separation energy consumption.
Process 4, adsorption oxidation, magnetic separation and PH adjustment treatment experiment
The thallium-containing wastewater 100 mL prepared above was placed in a 250 mL blue cap bottle, and after PS 15mM was added, the solution was sonicated in an sonicator for 10. 10min. After 0.2 g/L of rGO-Fe 3O4@TiO2 magnetic nano material is added, the blue cap bottle is placed in an ultrasonic instrument for ultrasonic treatment of 3 min, so that the blue cap bottle is fully dispersed. Sealing the blue cap bottle, placing the blue cap bottle into a water bath oscillator to react for 5 hours at a rotating speed of 160r/min, using ultrapure water to wash the magnetic material for 2-3 times, freeze-drying the blue cap bottle, placing the blue cap bottle into the ultrapure water to obtain a cleaning liquid, introducing the cleaning liquid into a hollow glass tube at a speed of 1ml/min by using a peristaltic pump in the stirring process, attaching a magnet to the outside of the hollow glass tube, collecting the magnetic material attached to the hollow glass tube, and drying the magnetic material.
The pH of the separated solution is adjusted to 10 by adding sodium hydroxide, the Tl removal rate is improved to 98.0%, and as shown in figure 2, compared with the process 2, the Tl removal rate is slightly reduced, which shows that the rGO-Fe 3O4@TiO2 magnetic material can be used as a Tl precipitation carrier to promote the Tl precipitation process.
Process 5, adsorption oxidation+magnetic coagulation experiment
The thallium-containing wastewater 100mL prepared above was placed in a 250 mL blue cap bottle, and after PS 15mM was added, the solution was sonicated in an sonicator for 10. 10min. After 0.2 g/L of rGO-Fe 3O4@TiO2 magnetic nano material is added, the blue cap bottle is placed in an ultrasonic instrument for ultrasonic treatment of 3min, so that the blue cap bottle is fully dispersed. After the blue bottle is sealed and put into a water bath oscillator to react for 5 hours at the rotating speed of 160r/min, the pH of the solution is not required to be regulated, aluminum sulfate is used as a chemical coagulant, and after 50 mg/L of aluminum sulfate is added, rapid stirring and slow stirring and static precipitation are sequentially carried out, wherein the rapid stirring speed is 250r/min, the stirring time is 1min, the slow stirring speed is 60r/min, the stirring time is 10min, and the static precipitation time is 30min.
In order to compare the recovery efficiency of rGO-Fe 3O4@TiO2 magnetic particles by the magnetic separation and magnetic coagulation treatment technology, a digestion solution is added into the reaction solution after the magnetic separation (process 3) and the magnetic coagulation (process 5) for digestion.
After the treatment of the process 1, the PH of the thallium-containing sewage is about 7.8, and the condition of directly carrying out coagulation treatment (within the optimal PH range of the aluminum sulfate coagulant) is satisfied, so that the pH adjustment is not needed after the adsorption oxidation, the magnetic coagulation treatment (Magnetic Coagulation) is directly carried out, the PH of the solution after coagulation is reduced to about 7.5, and the pH range meeting the requirement of direct discharge is satisfied. The magnetic coagulation process mainly comprises three links of rapid stirring and slow stirring and precipitation, the required time for separating the magnetic material from the treated water is only 30 min, the recovery speed of the magnetic material under low energy consumption is greatly improved, the running cost and convenience of the magnetic coagulation process are superior to those of the magnetic separation, and the magnetic coagulation process has more excellent application potential in practical application. The recovery efficiency of the magnetic materials in the treatment of the process 4 and the process 5 is 92.79% and 94.09%, respectively, as shown in fig. 3, the recovery efficiency of the magnetic particles of the rGO-Fe 3O4@TiO2 by the magnetic coagulation is slightly higher than that of the magnetic separation. Therefore, the magnetic coagulation treatment is more rapid and efficient for Tl removal and magnetic material recovery.
In the above process 1-5, the preparation method of the rGO-Fe 3O4@TiO2 magnetic material is as follows:
Step A, preparing graphene oxide nanosheets: graphene oxide nanoplatelets were synthesized using Hummers method.
Preparation of rGO-Fe 3O4: 0.5 g rGO powder is weighed and dispersed into 200 mL ultrapure water by ultrasonic, and then 1.080 g FeCl 3·6H2 O and 0.560 g FeSO 4·7H2 O are added to prepare rGO-Fe 3O4.
And B, preparing an rGO-Fe 3O4 composite material: the reduced graphene oxide nano-sheet and ferroferric oxide composite material (rGO-Fe 3O4) are prepared by a coprecipitation method, the molar ratio of the graphene oxide nano-sheet to the ferroferric oxide composite material is 2:1, and the graphene oxide nano-sheet and the ferroferric oxide composite material are mechanically stirred at 80 ℃ under the atmosphere of N 2 for 4 h. Under the condition of intense stirring, slowly dropwise adding ammonia water until the pH value of the solution is about 10, naturally cooling to room temperature, separating a synthesized product from a liquid phase by using a magnet, washing the solution with deionized water until the solution is neutral, washing the solution with absolute ethyl alcohol for 3 times, drying the solution at 60 ℃, and finally obtaining the rGO-Fe 3O4 composite material after grinding.
Step C, preparing a rGO-Fe 3O4@TiO2 magnetic material: dispersing the 5 mg rGO-Fe 3O4 composite material in 50mL absolute ethyl alcohol, adding 0.3 mL ammonia water to ultrasonically treat 20 min, placing in a water bath kettle at 45 ℃, and mechanically stirring at 450 r/min; then 1.5 mL TBOT is dissolved in 20 mL absolute ethyl alcohol under magnetic stirring to prepare a pale yellow TiO 2 precursor; and finally, slowly dropwise adding a TBOT/ethanol solution containing a pale yellow TiO 2 precursor into the rGO-Fe 3O4 dispersion solution, carrying out hydrothermal reaction at 180 ℃ for 48 and h, taking out solid particles through magnetic separation, washing with pure water and absolute ethyl alcohol for 3 times respectively, and then carrying out vacuum drying at 60 ℃ for 12 hours to obtain the rGO-Fe 3O4 @TiO2 composite magnetic material.
As shown in FIG. 14, the method for determining the addition amount of rGO-Fe 3O4@TiO2 is to perform an addition amount experiment, wherein the experiment is to add 0-1g/L of rGO-Fe 3O4@TiO2 to a Tl polluted water body containing 8.9 mg/L, then add 15 mmol of sodium persulfate, and the effect of the addition amount of rGO-Fe 3O4@TiO2 on the removal effect of organic pollutants in thallium-containing sewage is basically consistent with the removal of Tl. Under the condition of no rGO-Fe 3O4@TiO2 addition, the TOC removal rate is only 10.0 percent. When the addition amount of rGO-Fe 3O4@TiO2 is increased to 0.1g/L, the TOC removal rate is improved to 88.1%. When the addition amount of rGO-Fe 3O4@TiO2 is higher than 0.2 g/L, the TOC removal rate can reach more than 98.4 percent. Therefore, the invention uses the magnetic material adding amount of 0.2 g/L.
As shown in FIG. 15, the method for determining the addition amount of sodium humate is to perform an addition amount experiment, wherein the experiment is to add 0-20mmol sodium humate into Tl polluted water containing 0.2g/LrGO-Fe 3O4@TiO2 and 8.9 mg/L, the TOC concentration of effluent after PS treatment is reduced to a certain extent with different addition amounts, and rGO has certain adsorption performance on organic pollutants without PS addition, and the TOC removal rate reaches 16.4%. With the increase of PS addition amount, TOC removal efficiency is obviously improved; when the PS addition amount is 15 mM, the TOC removal efficiency can reach 98.4%, so the addition amount is selected in the invention.
As shown in FIG. 16, the method for determining the addition amount of the chemical coagulant is to perform an addition amount experiment, wherein the experiment is to add 0.2g/L of rGO-Fe 3O4@TiO2 into Tl polluted water containing 8.9 mg/L, then add 15 mmol sodium persulfate, add 50-100 mg/L of chemical coagulant after the reaction is finished, increase the addition amount of the coagulant from 50 mg/L to 100 mg/L, reduce the Tl concentration in the effluent from 3.4 mug/L to 1.7 mug/L, and only 1.1 mug/L when the addition amount of the coagulant is increased to 150 mg/L. The increase of the coagulant addition amount can further strengthen the removal of Tl pollutants to a certain extent. The present invention therefore selects 100 mg/L of chemical coagulant.
Experimental example
As shown in FIG. 4, the turbidity of the water sample treated by the rGO-Fe 3O4@TiO2 magnetic material and the PS coupling system is improved compared with that of the water sample treated by the raw water, which is mainly caused by the addition of the nano material. The turbidity of the water sample of the raw water was 115 NTU, and the turbidity of the reaction solution after the treatment of process 2 increased from 115 NTU to 132 NTU, mainly due to Tl hydroxide precipitation generated under ph=10.
In FIG. 4, process1 is process1, process2 is process2, process3 is process3, process4 is process4, and process5 is process 5.
After the treatment of the process 3, the turbidity of the water sample can be reduced to 74 NTU which is lower than that of raw water, which shows that the rGO-Fe 3O4@TiO2 magnetic material has good magnetic separation performance, and can reduce the turbidity while removing Tl and organic matters, as shown in fig. 5, (a) is raw sewage and (b) is sewage after the magnetic separation treatment.
After the treatment of the process 4, the turbidity of the solution rises. The turbidity of the water sample after the treatment is greatly reduced, and the turbidity value of the water sample after the treatment is only 22 NTU, which indicates that the magnetic coagulation treatment process can effectively separate and remove substances such as particles, colloids and the like inherent in the added magnetic material and raw water. Therefore, after Tl ion pollutants and organic pollutants in water are removed by high-efficiency adsorption and oxidation of rGO-Fe 3O4@TiO2/PS, the magnetic coagulation technology is directly applied, and the turbidity treatment effect on sewage is optimal.
And measuring the particle size distribution of the solution residual particles treated by different combination processes by using a laser particle sizer. As shown in fig. 6 (in fig. 6, process1 is process1, process2 is process2, process3 is process3, process4 is process4, process5 is process 5), the main particles in the solution after the process1 treatment are the original sewage particle pollutants and the added rGO-Fe 3O4@TiO2 magnetic particles, the particle size distribution shows a broad peak state, and the particle size is mainly between 1nm and 50 nm. After the treatment of process2, the particle size distribution in the solution was substantially identical to that of process1, but the peak intensity of the particle size around 1nm was increased due to the presence of Tl hydroxide.
The residual particles in the solution treated by the process 3 show normal distribution characteristics, the particle size dimension of main particles is distributed between 0.4 and 10 nm, and the magnetic particle dimension of rGO-Fe 3O4@TiO2 is mainly concentrated between 10 and 50 nm, which indicates that the residual particles are mainly original particle pollutants in sewage.
The residual particles in the solution after the treatment of the process 4 have slightly increased proportion in the low particle size range. After the treatment of the process 5, the residual particles in the supernatant are normally distributed between 1-20 nm, and a small amount of particles in the range of 20-100 nm exist in the solution, so that the flocculant can be agglomerated with the particle pollutants in the raw sewage and the added rGO-Fe 3O4@TiO2 magnetic particles through the actions of electric neutralization, adsorption bridging, rolling and net capturing and the like in the magnetic coagulation process, and the rGO-Fe 3O4@TiO2 magnetic particles can be efficiently recovered and the particle pollutants in the raw sewage can be removed.
The reacted magnetic coagulation floc is treated by ultrasound, an external magnet is added to recycle rGO-Fe 3O4@TiO2 magnetic particles, DI cleaning, 0.1M HNO 3 solution soaking and oscillating treatment is carried out for 3 h, and the treated floc is dried and then is used for thallium-containing sewage treatment process again, wherein PS with the same molar concentration is added in each cycle test. As can be seen from fig. 7, compared with the rGO-Fe 3O4@TiO2/PS/magnetic coagulation coupling system (control group/cycle 0) directly used for the initial rGO-Fe 3O4@TiO2 magnetic particles, both the Tl and TOC removal efficiency of the rGO-Fe 3O4@TiO2/PS/magnetic coagulation coupling system in the thallium-containing wastewater treatment process was slightly reduced with the increase of the number of recycling.
After the tertiary cycle test, the removal rate of Tl is still 89.2%, which shows that rGO-Fe 3O4@TiO2 magnetic particles can be repeatedly applied to activated PS, and then Tl in thallium-containing sewage is removed by adsorption and oxidation. The rGO-Fe 3O4@TiO2/PS/magnetic coagulation coupling system also has stable application performance in the aspect of removing organic pollutants in sewage, and the TOC removal rate is kept above 94.3% after three cycles. As the number of cycles increases, the Fe and Ti concentrations in the aqueous solution gradually increase, as shown in fig. 8. After tertiary circulation, the concentration of Fe and Ti in the treated water is 25.9 and 6.25 mug/L respectively, which is far lower than the concentration limit value (Fe: 0.3 mg/L and Ti: 0.1 mg/L) in the surface water source of the centralized drinking water, and the subsequent utilization of the treated water is not affected.
And (3) carrying out ultrasonic crushing and magnetic separation recovery on the collected flocs treated by the rGO-Fe 3O4 @TiO2/PS/magnetic coagulation coupling system, and analyzing the distribution of the elements on the surface of the particles by using EDS. As shown in fig. 9, the particle surface mainly contains oxygen, titanium, iron and thallium elements, and no characteristic elements of the coagulant such as aluminum and sulfur. This shows that ultrasonic treatment can effectively separate rGO-Fe 3O4@TiO2 magnetic particles from the flocs, and the magnetic material can be recycled after the magnetic coagulation process.
And (3) performing morphology analysis on the rGO-Fe 3O4@TiO2 magnetic particles treated by the process 3 by using a field emission scanning electron microscope after magnetic separation, DI cleaning and drying. Compared with the initial rGO-Fe3O4@TiO2 magnetic particles, the material surface is smoother after thallium-containing sewage is treated, as shown in figure 10, a small amount of pollutants exist on the surface, but obvious nano particle morphology features can still be observed on the surface of the rGO-Fe 3O4@TiO2 magnetic particles, and the obvious nano particle morphology features are mainly caused by TiO 2 nano particles loaded on the surface.
And (3) collecting solid particles in the process 3, performing coagulation treatment on the supernatant to form flocs serving as a reference, and collecting the surface morphology and chemical composition of the flocs by adopting an electronic scanning electron microscope, an X-ray energy spectrum and an X-ray photoelectron energy spectrum for comparison analysis, wherein the flocs are treated in the process 3 and the process 5. The surface morphology of the rGO-Fe 3O4@TiO2 particles recovered by the magnetic separation after the treatment of the process 3 shows a flaky structure, as shown in (a) of fig. 11, and is mainly the morphology characteristics of the rGO carrier. After the added magnet effectively recovers rGO-Fe 3O4@TiO2 magnetic particles, the residual solution is subjected to coagulation treatment, and the formed floccules are in a compact structure, as shown in (b) of fig. 11, which shows that the sewage still contains a large amount of particles, colloid and organic matters after magnetic separation, so that the floccules generated by coagulation are compact.
In fig. 11, (a) is a surface topography of the rGO-Fe 3O4@TiO2 particles recovered by magnetic separation after the treatment of the process 3, (b) is a surface topography of the flocs formed by coagulation of the supernatant after the recovery of the magnetic particles, and (c) is a surface topography of the flocs formed after the treatment of the process 5.
In contrast, the floccule structure formed after the fifth treatment is uniform and loose, and the flaky structure of the rGO-Fe 3O4@TiO2 magnetic particles can be observed, as shown in (c) of FIG. 11. The magnetic coagulation directly treats sewage containing rGO-Fe 3O4@TiO2 magnetic particles, can effectively separate the reacted rGO-Fe 3O4@TiO2 magnetic material from the water, and is also beneficial to further separation and recovery of the rGO-Fe 3O4@TiO2 magnetic material from the flocs due to a uniform and loose structure.
As shown in FIG. 12 (a), since aluminum sulfate is used as a coagulant, the flocs formed by directly treating raw sewage by coagulation are mainly composed of O, na, al and S elements. After the treatment of the process 3, that is, the rGO-Fe 3O4@TiO2 magnetic material is separated by using an external magnet, the residual solution is subjected to coagulation treatment, and the surface element composition of the formed floc contains a small amount of Tl elements (the relative atomic proportion is 7.21%) except the characteristic elements, which indicates that the coagulation treatment has a certain Tl pollutant removal efficiency, as shown in fig. 12 (b). As can be seen from fig. 12 (c), the sewage is treated by the process 5, the relative atomic proportions of Ti element and Fe element on the surface of the formed floc are 4.32% and 1.38%, respectively, and it is proved that the magnetic coagulation treatment can effectively recover the rGO-Fe 3O4@TiO2 magnetic material.
In fig. 12, (a) is a floc formed by directly adopting coagulation treatment raw sewage in X-ray energy spectrum analysis, (b) is a floc formed by coagulating supernatant fluid after treatment in the X-ray energy spectrum analysis process 3, and (c) is a floc formed after treatment in the X-ray energy spectrum analysis process 5.
The X-ray photoelectron spectroscopy is adopted to analyze the flocs formed by directly adopting the raw sewage after coagulation treatment and the flocs formed by adopting the process five treatment respectively, the result is shown in figure 13, the flocs formed by directly adopting the raw sewage after coagulation treatment show characteristic peaks of Al and S elements, and the flocs formed by adopting the process 5 after treatment have obvious characteristic peaks of Tl 2 p. The rGO-Fe 3O4@TiO2 magnetic material activated PS can be used for effectively adsorbing and oxidizing Tl pollutants. The technology 5 can synchronously remove Tl pollutants, organic matters and suspended particulate pollutants in sewage, and has application potential as thallium pollution emergency treatment.
Fig. 13 shows flocs (Coagulation) formed by directly adopting coagulation treatment of raw sewage and flocs (Magentic coagulation) formed by five treatments of the process in an X-ray photoelectron spectroscopy analysis.
Examples
According to the comparative example and the experimental example, a magnetic coagulation treatment system and a treatment method for efficiently and rapidly treating thallium-containing wastewater in this example are shown in fig. 1.
Step 1, adding a rGO-Fe 3O4@TiO2 magnetic material with the concentration of 0.05-0.2g/L and sodium persulfate (PS 0-20 mM) into a 50ml thallium-containing sewage solvent bottle, and placing the solvent bottle into a water bath oscillator to react at the rotating speed of 160 r/min for 5 h;
Step 2, performing magnetic coagulation reaction on chemical coagulant with the concentration of 20-80 mg/L, and fully mixing the chemical coagulant with the thallium-containing wastewater after the reaction to obtain a mixed solution containing magnetic materials, thallium-containing wastewater and coagulation substances;
Step 3, carrying out PH adjustment treatment on the mixed solution containing the magnetic material, thallium-containing sewage and the coagulation substance, wherein the treatment method comprises the steps of adding 0.01mol/L NaOH solution to adjust the PH value of the solution to 10;
Step 4, carrying out solid-liquid separation on the mixed solution containing the magnetic material, thallium-containing sewage and the coagulation substance, collecting the coagulation solid at the bottom, carrying out ultrasonic treatment at 25 ℃ for 15min, then washing 3-5 times by using ultrapure water, and adding the washed magnetic coagulation substance into a microwave digestion instrument for 30min for microwave digestion;
And 5, washing the material with ultrapure water for 2-3 times, freeze-drying, then placing the material into 500ml of ultrapure water, introducing the liquid into a hollow glass tube with a diameter of 2.5cm and a magnet outside at a speed of 1ml/min by using a peristaltic pump in the stirring process, collecting the magnetic material attached to the hollow glass tube after a period of time, and drying to complete the recovery of the magnetic material.
The invention takes rGO-Fe 3O4@TiO2 magnetic nano material and PS as emergency treatment agents, can effectively solve the thallium pollution problem and has the degradation efficiency of organic pollutants. Meanwhile, the magnetic coagulation technology can fully exert the synergistic strengthening effect of magnetic materials and coagulation, so that the coagulation efficiency and the pollutant removal efficiency are improved, the rGO-Fe 3O4@TiO2/PS/magnetic coagulation coupling technology mainly comprises the steps of adding rGO-Fe 3O4@TiO2 and PS for adsorption and oxidation treatment, then directly carrying out magnetic coagulation treatment, and then, the generated floccules are subjected to magnetic separation devices to recover rGO-Fe 3O4@TiO2 magnetic materials from the floccules, and the volume of the floccules is far smaller than the water treatment amount, so that the requirements on magnetic separation equipment are greatly reduced.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. A magnetic coagulation treatment method for efficiently and rapidly treating thallium-containing sewage is characterized by comprising the following steps:
step 1, adding a magnetic material and sodium persulfate into thallium-containing sewage, and uniformly mixing to obtain a mixed solution A;
Step 2, adding a chemical coagulant into the mixed solution A for carrying out magnetic coagulation reaction to obtain a mixed solution B;
and step 3, carrying out solid-liquid separation on the mixed solution B to obtain a magnetic coagulation substance, and recovering the magnetic material.
2. The magnetic coagulation treatment method for efficiently and quickly treating thallium-containing sewage according to claim 1, wherein the magnetic material in the step 1 comprises rGO-Fe 3O4@TiO2, and the concentration of the magnetic material is 0.05-0.2g/L;
The addition amount of sodium persulfate in the step 1 is 15mM.
3. The magnetic coagulation treatment method for efficiently and quickly treating thallium-containing sewage according to claim 1, wherein the preparation method of rGO-Fe 3O4@TiO2 comprises the following steps:
Step 10, synthesizing graphene oxide nano sheets by using a Hummers method;
Step 11, preparing a reduced graphene oxide nano sheet and ferroferric oxide composite material by a coprecipitation method, wherein the molar ratio of the graphene oxide nano sheet to the ferroferric oxide composite material is 2:1, and slowly dropwise adding ammonia under the condition of intense stirring to form an rGO-Fe 3O4 composite material;
Step 12, dispersing the rGO-Fe 3O4 composite material in absolute ethyl alcohol, adding ammonia water, uniformly stirring to prepare a rGO-Fe 3O4 dispersion solution, and dissolving TBOT in absolute ethyl alcohol under stirring to prepare a TiO 2 precursor;
And 13, slowly dropwise adding the TiO 2 precursor into the rGO-Fe 3O4 dispersion solution, taking out solid particles through magnetic separation, washing, and vacuum drying to obtain the rGO-Fe 3O4@TiO2.
4. The magnetic coagulation treatment method for efficiently and quickly treating thallium-containing sewage according to claim 1, wherein the chemical coagulant in the step 2 comprises aluminum sulfate, and the concentration of the aluminum sulfate is 20-80 mg/L.
5. The method for efficiently and rapidly treating thallium-containing wastewater by magnetic coagulation according to claim 1, wherein the PH of the mixed solution B is adjusted before the mixed solution B is subjected to solid-liquid separation in the step 3 by adding 0.01mol/L NaOH solution to adjust the PH of the mixed solution B to 10.
6. The method for magnetic coagulation treatment of thallium-containing wastewater with high efficiency and high speed according to claim 1, wherein the method for uniformly mixing in step 1 is characterized in that the reaction is performed in a water bath oscillator at a rotation speed of 160r/min for 5 hours.
7. The method for efficiently and rapidly treating thallium-containing wastewater according to claim 6, wherein in the step 3, the magnetic coagulation material obtained by solid-liquid separation of the mixed solution B is subjected to ultrasonic treatment at 25 ℃ for 15min, and after ultrasonic treatment, the wastewater is washed 3-5 times with ultrapure water, and after washing, microwave digestion is performed for 30min.
8. The method for efficiently and rapidly treating thallium-containing wastewater by magnetic coagulation according to claim 7, wherein the method for recovering the magnetic material in the step 3 comprises washing the magnetic material with ultrapure water 2 to 3 times, freeze-drying the magnetic material, then placing the washed magnetic material into the ultrapure water to obtain a cleaning solution, introducing the cleaning solution into a hollow glass tube at a speed of 1ml/min by using a peristaltic pump during stirring, attaching a magnet to the outside of the hollow glass tube, collecting the magnetic material attached to the hollow glass tube, and drying the magnetic material.
9. A magnetic coagulation treatment system for efficiently and rapidly treating thallium-containing wastewater, which adopts the magnetic coagulation treatment method for efficiently and rapidly treating thallium-containing wastewater according to claim 8, comprising the steps of:
An oxidation treatment unit for carrying out oxidation treatment on thallium-containing sewage by utilizing a magnetic material and sodium persulfate;
the magnetic coagulation unit is used for carrying out magnetic coagulation treatment on thallium-containing sewage by adding a chemical coagulant;
a microwave digestion unit for carrying out microwave digestion on the magnetic coagulation substance by a microwave digestion instrument;
And a magnetic separation unit for recovering the magnetic material in the coagulated material.
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