CN110872138A - Method for treating farmland drainage by applying engineering waste as PRB filler - Google Patents
Method for treating farmland drainage by applying engineering waste as PRB filler Download PDFInfo
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- CN110872138A CN110872138A CN201811019252.3A CN201811019252A CN110872138A CN 110872138 A CN110872138 A CN 110872138A CN 201811019252 A CN201811019252 A CN 201811019252A CN 110872138 A CN110872138 A CN 110872138A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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Abstract
The invention discloses a method for treating farmland drainage by using engineering waste as PRB filler, which comprises the following steps: the method comprises the steps of selecting proper engineering waste through a static test, filling the engineering waste into a PRB reaction device as an active material, pouring simulated farmland drainage into the PRB reaction device according to a certain flow rate, sampling at an outlet of the PRB reaction device at intervals, and analyzing and testing nitrogen, phosphorus and pesticides in a sample. The invention relates to a method for restoring farmland backwater polluted by nitrogen, phosphorus and pesticides in situ by utilizing engineering waste as PRB active filler, which enables nitrogen, phosphorus and pesticide polluted water flowing through PRB to be fully contacted with active materials, thereby achieving the purpose of stably and effectively restoring farmland backwater polluted by nitrogen, phosphorus and pesticides. In addition, the engineering waste comprises industrial waste and natural slag, so that the cost of the active filler of the PRB technology is reduced, and the resource recycling is realized.
Description
Technical Field
The invention relates to the field of environmental pollution remediation, in particular to a method for treating pollutants such as nitrogen, phosphorus, pesticides (tricyclazole, malathion and isoprothiolane) and the like in farmland effluent by applying engineering wastes as PRB (plant resource blocks) fillers.
Background
The water pollution problem is one of the hottest environmental problems facing the world, and non-point source pollution becomes a main pollution source of water environment of countries in the world. The non-point source pollution of farmland mainly comes from unreasonable application of chemical fertilizers and pesticides in farming, sewage irrigation and the like, and a large amount of nitrogen, phosphorus and pesticide residues enter water environments such as rivers, lakes and the like along with farmland drainage or rainwater. The eutrophication of water body caused by nutritive salts such as nitrogen and phosphorus is not only the most common phenomenon of water body pollution, but also a difficult problem of water body pollution control at home and abroad.
Since the 80 s of the 20 th century, researches on ecological control measures of agricultural non-point source pollutants are gradually paid attention at home and abroad, and common restoration methods mainly comprise ecological ditches, artificial wetlands, ecological floating beds and the like. The ecological ditch is composed of a farmland drainage ditch and plants planted in the farmland drainage ditch, runoff and silt are intercepted by the ditch fence, and the plants retain and absorb nitrogen and phosphorus, so that the function of intercepting the ecological fence is realized; the artificial wetland technology utilizes the triple coordination of physics, chemistry and biology of a plant-microorganism-substrate composite ecosystem, realizes the high-efficiency purification of the wastewater through plant absorption, microorganism decomposition, filtration, adsorption, precipitation and ion exchange, and simultaneously promotes the growth of green plants and increases the yield through the biogeochemical circulation of nutrient substances and water, thereby realizing the reclamation and harmlessness of the wastewater; the ecological floating bed plant technology, i.e. biological floating island technology or artificial floating island technology, is a water surface plant technology which comprehensively integrates modern agricultural and ecological engineering measures by using the principle of soilless culture technology and taking high polymer materials as carriers and substrates. Although the traditional methods for purifying eutrophic water bodies by using aquatic plants have good effects, the traditional methods still have a plurality of problems and disadvantages: the filler of the artificial wetland is expensive; the purification effect of wetland plants at different growth stages is unpredictable, and the overwintering problem of the plants needs to be solved; the death of the plant can cause secondary pollution of nitrogen and phosphorus. The traditional treatment method for farmland water-return is limited by factors such as plants, seasons, treatment speed, price and the like, so that people begin to seek other efficient and economic repair technologies.
The Permeable Reactive Barrier (PRB) technology started in the 90's of the 20 th century, which means that a reactive barrier is installed in an area through which a polluted water flows, a reactive medium is filled in the barrier, and when a polluted water body flows through the barrier, a pollutant and the reactive medium are adsorbed, precipitated or degraded under physical, chemical and biological actions, so that the pollutant concentration reaches the water environment quality standard of related groundwater. The PRB technology is only applied to the prevention and the remediation of groundwater pollution at first, but along with the expansion of the demand, the PRB technology is also combined with other remediation technologies and applied to the fields of surface water pollution remediation, soil pollution remediation and the like. Because the PRB technology has the advantages of wide treatment range of pollutants, low cost, flexible selection of reaction fillers and the like, the PRB technology has great potential when being applied to interception of the polluted farmland drainage and reduction of the pollution of surface water. Through the reports of the prior literatures, the following 6 materials are screened from the mature water pollutant removal materials at home and abroad as research objects: respectively iron ore slag (main component of zero-valent iron filings), engineering waste (main component of limestone), corn straw biochar (mainly from biofuel production), magnesite ore slag (main component of magnesium carbonate), calcined magnesite ore slag (main component of magnesium oxide) and aluminum ore slag (main component of aluminum oxide). The material is used as PRB active filler to remove nitrogen, phosphorus and pesticide pollutants in farmland returned water, so that the purpose of treating wastes with wastes is achieved, and the resource utilization of wastes is realized. At present, the method for removing nitrogen, phosphorus and pesticides in farmland returned water by using engineering wastes as PRB active fillers is not reported in documents and disclosed in patents.
Disclosure of Invention
Aiming at the current situation that nitrogen, phosphorus and pesticide pollute the water body in farmland returned water, the invention aims to overcome the problems of high cost, low treatment speed and the like of the traditional treatment method, and provides a method for treating farmland returned water by applying engineering waste as PRB (plant resource Block) filler, so that the farmland returned water flowing through PRB is fully contacted with an active material, and the purpose of stably and effectively removing the nitrogen, phosphorus and pesticide pollutants in the farmland returned water is achieved.
In order to achieve the aim, the invention provides a method for treating farmland drainage by using engineering waste as PRB filler, which comprises the following steps:
(1) determining main pollutants in farmland returned water, and preparing a pollution solution;
(2) selecting engineering waste with good adsorption performance by adopting a static adsorption test;
(3) filling the selected engineering waste serving as an active filler and quartz sand into a leaching column of a simulated PRB device according to a certain volume ratio, introducing a polluted solution into the PRB device by using a peristaltic pump according to a certain flow rate, collecting effluent at an outlet of the PRB device, taking samples at intervals, and measuring residual nitrogen, phosphorus and pesticide in the samples by using an ultraviolet visible spectrophotometer and a high performance liquid chromatograph respectively.
The engineering waste is one or a mixture of more of iron ore slag, magnesite slag, calcined magnesite slag, limestone, aluminum slag and biochar.
30mg/L of nitrogen and 5mg/L of phosphorus in the polluted solution in the step (1), 1mg/L of each of pesticides tricyclazole, isoprothiolane and malathion, pH 6.5-7 and total ionic strength 10 mMol/L.
The particle size of the iron slag, the calcined magnesite slag and the aluminum slag is 0.42-0.84mm, the particle size of the limestone is 0.31-1.00mm, and the particle size of the biochar is 0-2 mm.
The volume ratio of the engineering waste to the quartz sand in the step (3) is 1: 2.
and (4) filling the engineering waste in the step (3) in the middle position of the leaching column.
The conditions of the step (2) are as follows: the temperature of the water bath constant temperature oscillator is 293K, the oscillation frequency is 150r/min, and the adsorption time is 24 h.
In the step (3), the flow rate is 0.93-1.12cm/h, and the contact time of the filler and the polluted solution is 5 h.
The particle size of the quartz sand is 0.18-0.45mM, the quartz sand is soaked in 10mM NaOH and 10mM HCl respectively for 6 hours before filling to remove impurities, the quartz sand is washed to be neutral by ultrapure water, and then the quartz sand is placed in an oven at 105 ℃ for drying.
Compared with the prior art, the invention has the following advantages:
(1) the iron ore slag, the calcined magnesite ore slag and the biochar are used as PRB fillers, so that nitrogen, phosphorus and pesticides in farmland drainage can be effectively removed, and the environmental risk is low.
(2) The iron ore slag and the calcined magnesite slag are mining waste slag, the biochar is produced from biofuel, the used filler is cheap and easy to obtain, the cost is low, and the resource recycling of waste materials can be realized.
(3) The device required by the reaction is simple, the operation is convenient, and no additional reagent is needed.
Drawings
FIG. 1 is a schematic diagram of a PRB apparatus;
wherein, the polluted solution bottle 1, the pipeline 2, the peristaltic pump 3, the PRB device 4 and the effluent liquid collecting bottle 5;
FIG. 2 is a graph showing the effect of iron ore slag on nitrogen, phosphorus and pesticides removal;
FIG. 3 is a graph showing the effect of calcining magnesite slag on removing nitrogen, phosphorus and pesticides;
FIG. 4 shows the effect of biochar on nitrogen, phosphorus and pesticide removal.
Detailed Description
The present invention is further described with reference to the following specific examples, but the scope of the present invention is not limited by the examples, and those skilled in the art who have the above-mentioned disclosure will still be able to make some insubstantial modifications and adaptations to the present invention.
Example 1
6 materials, namely iron ore slag, limestone, corn straw biochar, magnesite slag, calcined magnesite slag and aluminum slag, are researched by adopting a static adsorption method, and the removal capability of the materials on nitrate nitrogen and total phosphorus is researched. KH with pH 7, total ionic strength Ic 10mMol/L, Cp 50mg/L and CN 50mg/L is prepared2PO4-Na2HPO4And KNO3The contaminated aqueous solution was mixed and the ionic strength was adjusted with NaCl. Weighing 0.1g of each material, placing the weighed materials into a glass centrifuge tube with the volume of 50mL and added with 20mL of nitrogen-phosphorus polluted water solution, placing the glass centrifuge tube into a water bath constant-temperature oscillator for shaking, controlling the temperature to be 293K, controlling the shaking frequency to be 150r/min, and after 24 hours of adsorption, taking supernate and measuring the supernate through a 0.45-micron filter membrane. The results show the removal of phosphate from calcined magnesite and iron slagsThe capacity is strongest, and is 688mg/kg and 384mg/kg respectively; the iron slag has the strongest capacity of removing nitrate, and is 139 mg/kg.
Example 2
6 materials, namely iron ore slag, limestone, corn straw biochar, magnesite slag, calcined magnesite slag and aluminum slag, are researched by adopting a static adsorption method, and the removal capability of the materials on pesticides tricyclazole, isoprothiolane and malathion is researched. Preparing a mixed polluted water solution containing 1mg/L of each of tricyclazole, isoprothiolane and malathion, wherein the total ionic strength Ic is 10mMol/L, and adjusting the ionic strength by using NaCl. Weighing 0.1g of each material, placing the materials into a glass centrifuge tube with the volume of 50mL and added with 20mL of pesticide polluted water solution, placing the glass centrifuge tube into a water bath constant-temperature oscillator for shaking, controlling the temperature to be 293K, controlling the shaking frequency to be 150r/min, and after 24 hours of adsorption, taking supernate and measuring the supernate through a 0.22 mu m filter membrane. The removal capacity of the straw biochar and the iron slag to tricyclazole is the strongest, and the removal capacity is 213mg/kg and 117mg/kg respectively; the removal capacity of the straw biochar, the iron slag and the calcined magnesite slag to malathion and isoprothiolane is high, and is respectively 136mg/kg and 89-172 mg/kg.
Calcined magnesite slag, iron slag and straw biochar were selected as active fillers for PRB plants in combination with examples 1 and 2.
Example 3
In the embodiment, the iron ore slag which is engineering waste, namely zero-valent iron filings are used as PRB filler to treat wastewater containing nitrogen, phosphorus and pesticides (30mg-N/L,5mg-P/L, 1mg/L of each of tricyclazole, isoprothiolane and malathion, pH is 6.5-7, and total ionic strength is about 10mMol/L), and the method comprises the following steps: quartz sand (purity 99.4%) with a particle size of 0.18-0.45mm is filled at the inlet and outlet of the PRB device as an inactive filler to ensure that the polluted solution uniformly passes through the PRB device. Before filling, the mixture is soaked by 10mM NaOH and 10mM HCl respectively for 6h to remove impurities, and then is washed by ultrapure water to be neutral, and then is placed in an oven for drying at 105 ℃. Iron ore slag with a grain size of 0.42 to 0.84mm is screened. Weighing a certain amount of iron ore slag to be filled in the 1/3 position in the middle of the PRB device, weighing a certain amount of quartz sand to be filled in the upper and lower 1/3 positions, wherein the volume ratio of the quartz sand to the iron ore slag is 2: 1. the contaminated solution containing nitrogen, phosphorus and pesticides was introduced into the PRB unit using a peristaltic pump, allowing the solution to contact the iron ore slag for 5 hours (pore water flow rate of 1 cm/h). Collecting effluent at the outlet of the PRB device, sampling at intervals, filtering with a 0.22 μm filter membrane, and measuring residual nitrogen, phosphorus and pesticide in the sample by an ultraviolet-visible spectrophotometer and a high performance liquid chromatograph.
As shown in fig. 2, in 14d of the operation of the PRB plant, iron slag as PRB active filler can effectively remove pesticides and phosphates in polluted wastewater, the removal rates of malathion, isoprothiolane and tricyclazole are maintained at 100%, 95% and 85%, respectively, and the removal rate of phosphates is greater than 70%; the nitrate removal capacity is relatively small, falling to 20% within 4 d. Therefore, the iron ore slag is used as an active filler of PRB, and can effectively remove pesticide and phosphate at the same time.
Example 4
In the embodiment, magnesite slag calcined by a calcined product of natural ore is used as PRB filler to treat wastewater containing nitrogen, phosphorus and pesticides (30mg-N/L,5mg-P/L, 1mg/L of tricyclazole, isoprothiolane and malathion respectively, pH is 6.5-7, and total ionic strength is about 10mMol/L), and the method comprises the following steps: quartz sand (purity 99.4%) with a particle size of 0.18-0.45mm is filled at the inlet and outlet of the PRB device as an inactive filler to ensure that the polluted solution uniformly passes through the PRB device. Before filling, the mixture is soaked by 10mM NaOH and 10mM HCl respectively for 6h to remove impurities, and then is washed by ultrapure water to be neutral, and then is placed in an oven for drying at 105 ℃. The calcined magnesite slag with the grain size of 0.42-0.84mm is screened. Weighing a certain amount of calcined magnesite slag to be filled in the 1/3 position in the middle of a PRB device, weighing a certain amount of quartz sand to be filled in the upper and lower 1/3 positions, wherein the volume ratio of the quartz sand to the iron ore slag is 2: 1. and (3) introducing a polluted solution containing nitrogen, phosphorus and pesticide into the PRB device by using a peristaltic pump, so that the contact time of the solution and the calcined magnesite slag is 5h (the flow rate of pore water is 1 cm/h). Collecting effluent at the outlet of the PRB device at intervals, sampling at intervals, filtering with a 0.22 μm filter membrane, and measuring residual nitrogen, phosphorus and pesticide in the sample by an ultraviolet-visible spectrophotometer and a high performance liquid chromatograph.
As shown in fig. 3, in the run 12d of the PRB plant, the calcined magnesite slag as PRB active filler can effectively remove malathion and phosphate in polluted wastewater, with removal rates of 100% respectively. Nitrate can be effectively removed within 4d, the removal rate is 100%, and then the removal rate is slowly reduced. The removal rate of the isoprothiolane is more than 75 percent. The removal rate of tricyclazole was slowly decreased to 23%. Therefore, the calcined magnesite slag is used as an active filler of PRB, and can effectively and simultaneously remove nitrogen, phosphorus, malathion and isoprothiolane.
Example 5
In the embodiment, the straw biochar is used as PRB filler to treat wastewater containing nitrogen, phosphorus and pesticides (30mg-N/L,5mg-P/L, 5mg/L of tricyclazole, isoprothiolane and malathion, respectively, pH is 6.5-7, and total ionic strength is about 10mMol/L), and the method is carried out according to the following steps: quartz sand (purity 99.4%) with a particle size of 0.18-0.45mm is filled at the inlet and outlet of the PRB device as an inactive filler to ensure that the polluted solution uniformly passes through the PRB device. Before filling, the mixture is soaked by 10mM NaOH and 10mM HCl respectively for 6h to remove impurities, and then is washed by ultrapure water to be neutral, and then is placed in an oven for drying at 105 ℃. Screening the straw biochar with the particle size of less than 2 mm. Weighing a certain amount of straw biochar to be filled in the 1/3 position in the middle of the PRB device, weighing a certain amount of quartz sand to be filled in the upper 1/3 position and the lower 1/3 position, wherein the volume ratio of the quartz sand to the iron ore slag is 2: 1. and (3) introducing a polluted solution containing nitrogen, phosphorus and pesticide into the PRB device by using a peristaltic pump, so that the contact time of the solution and the straw biochar is 5h (the flow rate of pore water is 1 cm/h). Collecting effluent at the outlet of the PRB device at intervals, sampling at intervals, filtering with a 0.22 μm filter membrane, and measuring residual nitrogen, phosphorus and pesticide in the sample by an ultraviolet-visible spectrophotometer and a high performance liquid chromatograph.
As shown in fig. 4, within PRB device operation 33 d: the straw biochar serving as the PRB active filler can effectively remove three pesticides in the polluted wastewater, and the removal rate is more than 98%; the nitrate removal capacity decreased rapidly to 30% in 5d and increased rapidly to 100% from 5 d; the removal rate of phosphate gradually decreased to 10%. Therefore, the straw biochar is used as an active filler of PRB, and can effectively and simultaneously remove nitrate nitrogen and three pesticides.
Claims (9)
1. A method for treating farmland drainage by using engineering waste as PRB filler is characterized by comprising the following steps: the method comprises the following steps:
(1) determining main pollutants in farmland returned water, and preparing a pollution solution;
(2) selecting engineering waste with good adsorption performance by adopting a static adsorption test;
(3) filling the selected engineering waste serving as an active filler and quartz sand into a leaching column of a simulated PRB device according to a certain volume ratio, introducing a polluted solution into the PRB device by using a peristaltic pump according to a certain flow rate, collecting effluent at an outlet of the PRB device, taking samples at intervals, and measuring residual nitrogen, phosphorus and pesticide in the samples by using an ultraviolet visible spectrophotometer and a high performance liquid chromatograph respectively.
2. The method for treating farmland drainage by applying engineering waste as PRB filler according to claim 1, characterized in that: the engineering waste is one or a mixture of more of iron ore slag, magnesite slag, calcined magnesite slag, limestone, aluminum slag and biochar.
3. The method for treating farmland drainage by applying engineering waste as PRB filler according to claim 1, characterized in that: 30mg/L of nitrogen and 5mg/L of phosphorus in the polluted solution in the step (1), 1mg/L of each of pesticides tricyclazole, isoprothiolane and malathion, pH 6.5-7 and total ionic strength 10 mMol/L.
4. The method for treating farmland drainage by applying engineering waste as PRB filler according to claim 2, characterized in that: the particle size of the iron slag, the calcined magnesite slag and the aluminum slag is 0.42-0.84mm, the particle size of the limestone is 0.31-1.00mm, and the particle size of the biochar is 0-2 mm.
5. The method for treating farmland drainage by applying engineering waste as PRB filler according to claim 1, characterized in that: the volume ratio of the engineering waste to the quartz sand in the step (3) is 1: 2.
6. the method for treating farmland drainage by applying engineering waste as PRB filler according to claim 1, characterized in that: and (4) filling the engineering waste in the step (3) in the middle position of the leaching column.
7. The method for treating farmland drainage by applying engineering waste as PRB filler according to claim 1, characterized in that: the conditions of the step (2) are as follows: the temperature of the water bath constant temperature oscillator is 293K, the oscillation frequency is 150r/min, and the adsorption time is 24 h.
8. The method for treating farmland drainage by applying engineering waste as PRB filler according to claim 1, characterized in that: in the step (3), the flow rate is 0.93-1.12cm/h, and the contact time of the filler and the polluted solution is 5 h.
9. The method for treating farmland drainage by applying engineering waste as PRB filler according to claim 1, characterized in that: the particle size of the quartz sand is 0.18-0.45mM, the quartz sand is soaked in 10mM NaOH and 10mM HCl respectively for 6 hours before filling to remove impurities, the quartz sand is washed to be neutral by ultrapure water, and then the quartz sand is placed in an oven at 105 ℃ for drying.
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| CN112960724A (en) * | 2021-02-04 | 2021-06-15 | 中国科学院沈阳应用生态研究所 | Method for removing veterinary antibiotics by active materials |
| CN114229944A (en) * | 2021-12-15 | 2022-03-25 | 上海市政工程设计研究总院（集团）有限公司 | Device for controlling phosphorus diffusion of farmland irrigation channel |
| CN114524504A (en) * | 2021-12-27 | 2022-05-24 | 山东坊能新动能科学研究院有限公司 | Biomass-loaded permeable reactive barrier material for underground water treatment and preparation method thereof |
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