CN113121035A - Treatment device and treatment method for recycling phosphogypsum leachate - Google Patents

Treatment device and treatment method for recycling phosphogypsum leachate Download PDF

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Publication number
CN113121035A
CN113121035A CN202011466434.2A CN202011466434A CN113121035A CN 113121035 A CN113121035 A CN 113121035A CN 202011466434 A CN202011466434 A CN 202011466434A CN 113121035 A CN113121035 A CN 113121035A
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tank
reaction tank
inclined plate
leachate
reaction
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周正
陆亚超
占伟
杜冬云
祝国亮
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Hubei Meichen Environmental Protection Co ltd
South Central Minzu University
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Hubei Meichen Environmental Protection Co ltd
South Central University for Nationalities
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • 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
    • 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
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention belongs to the technical field of industrial sewage treatment, and relates to a treatment device and a treatment method for recycling phosphogypsum leachate, wherein the treatment device for recycling phosphogypsum leachate comprises a water collecting tank, an automatic control dosing system, a mixed sedimentation system, a clean water tank and a product discharge system; the water collecting tank is provided with a water inlet communicated with the water collecting tank; the water collecting tank is communicated with the clean water tank through a mixed sedimentation system; the clean water tank is connected to the mixed sedimentation system; a water outlet communicated with the clean water tank is arranged on the clean water tank; the automatic control medicine adding system and the product discharge system are communicated with the mixing and settling system respectively. The invention provides a treatment device and a treatment method for recycling phosphogypsum leachate, wherein N, P, F elements are separated and precipitated, no solid waste is generated, and the purpose of recycling is achieved.

Description

Treatment device and treatment method for recycling phosphogypsum leachate
Technical Field
The invention belongs to the technical field of industrial sewage treatment, relates to a treatment device and a treatment method for recycling phosphogypsum leachate, and particularly relates to a treatment device and a treatment method for recycling phosphogypsum leachate, which are suitable for treating wastewater with high content of ammonia nitrogen, total phosphorus and fluoride and high acidity.
Background
The phosphoric acid obtained by decomposing phosphorus ore with sulfuric acid, nitric acid or hydrochloric acid in industry is collectively called wet phosphoric acid, and the decomposition of phosphorus ore with sulfuric acid is the most commonly used process for preparing phosphoric acid. The phosphate rock is decomposed by sulfuric acid to generate a phosphoric acid solution and insoluble calcium sulfate crystals, and the reaction formula (1) is shown as follows:
Ca5F(PO4)3+5H2SO4+5nH2O＝3H3PO4+5CaSO4·nH2O↓+HF (1)
although the wet-process phosphoric acid is economical and effective, a second type of industrial solid waste, namely phosphogypsum, is generated, and serious environmental pollution is caused. Per 1 ton of phosphoric acid product produced (in P)2O5Standard), about 5 tons of phosphogypsum waste residue is produced. The main component of phosphogypsum is calcium sulfate dihydrate (CaSO)4·2H2O), small amount of CaO, trace heavy metal ions and radioactive elements, and undecomposed ground phosphate rock and P2O5And free acids and the like. The global cumulative emission of phosphogypsum is statistically about 60 hundred million t and increases at a rate of 1.5 hundred million t/year. The phosphogypsum piled by the wet process not only occupies a large amount of land, but also generates leachate with the characteristics of low pH value, strong corrosivity, high total phosphorus concentration and the like through the washing and leaching of rainwater. Soluble impurities such as phosphorus, ammonia nitrogen, fluorine, heavy metals and the like in the leachate are easy to migrate to the surrounding soil, water body and atmospheric environmentEnvironmental pollution can be caused.
Scholars at home and abroad carry out systematic research on the treatment of the phosphogypsum and the harmful substance in the leachate of the phosphogypsum heap. Battistoni and the like adopt a membrane filtration process to pretreat phosphogypsum leachate, and the removal rate of fluoride and phosphate radical is 96 percent and 80 percent respectively when the pH value is 6.7. Orescain and the like utilize plant ash to treat harmful substances such as fluoride, phosphate radical, heavy metal and the like in phosphogypsum percolate, and when the pH is adjusted to be 7 by the plant ash, the removal rate of the fluoride and the heavy metal can reach 98 percent; the phosphate removal rate can reach 96% when the pH value is 9. Ammar and the like control the release of heavy metal ions in the phosphogypsum in the water environment through organic ligands (such as citrate) to achieve the aim of reducing the pollution of percolate. Ricardo et al by Ca (OH)2The solution increases the pH value of the acidic phosphogypsum leachate, so that the removal rates of phosphate, heavy metal and fluoride respectively reach 100%, 100% and 90%. The treatment method has good removal effect on phosphate, sulfate, fluoride and heavy metal ions, but has the defects of high cost, large amount of generated sludge, low ammonia nitrogen removal rate and the like, and limits the application of the treatment method in the industrial-scale treatment of the phosphogypsum leachate.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention provides a treatment device and a treatment method for recycling phosphogypsum leachate, wherein N, P, F elements are separated, precipitated and separated, no solid waste is generated, and the purpose of recycling is achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a processing apparatus of resource recovery ardealite leachate which characterized in that: the treatment device for recycling the phosphogypsum leachate comprises a water collecting tank, an automatic control dosing system, a mixed settling system, a clean water tank and a product discharge system; a water inlet communicated with the water collecting tank is formed in the water collecting tank; the water collecting tank is communicated with the clean water tank through a mixed sedimentation system; the clean water tank is connected to a mixed sedimentation system; a water outlet communicated with the clean water tank is formed in the clean water tank; the automatic control medicine adding system and the product discharge system are communicated with the mixing and settling system respectively.
Preferably, the mixed settling system adopted by the invention comprises a first pH meter, a second pH meter, a third pH meter, a fourth pH meter, a fifth pH meter, a first reaction tank, a first vertical flow inclined plate sedimentation tank, a second reaction tank, a second vertical flow inclined plate sedimentation tank, a third reaction tank, a first flocculation tank, a third vertical flow inclined plate sedimentation tank, a fourth reaction tank, a fourth vertical flow inclined plate sedimentation tank, a sixth reaction tank and a seventh reaction tank; the water collecting tank is communicated with the first vertical flow inclined plate sedimentation tank through the first reaction tank; the top of the first vertical flow inclined plate sedimentation tank is communicated with a second vertical flow inclined plate sedimentation tank through a second reaction tank; the top of the second vertical flow inclined plate sedimentation tank is communicated with a third vertical flow inclined plate sedimentation tank through a third reaction tank and the first flocculation tank; the top of the third vertical flow inclined plate sedimentation tank is communicated with a fourth vertical flow inclined plate sedimentation tank through a fourth reaction tank; the top of the fourth vertical flow inclined plate sedimentation tank is communicated with the clean water tank through a sixth reaction tank and a seventh reaction tank; the clean water tank is connected to a third reaction tank; the bottom of the first vertical flow inclined plate sedimentation tank, the bottom of the second vertical flow inclined plate sedimentation tank, the bottom of the third vertical flow inclined plate sedimentation tank and the bottom of the fourth vertical flow inclined plate sedimentation tank are respectively connected with a product discharge system; the automatic control dosing system is respectively connected into a first reaction tank, a second reaction tank, a third reaction tank, a first flocculation tank, a fourth reaction tank, a sixth reaction tank and a seventh reaction tank; the first pH meter extends into the first reaction tank; the second pH meter extends into the second reaction tank; the third pH meter extends into a third reaction tank; the fourth pH meter extends into the fourth reaction tank; and the fifth pH meter extends into the sixth reaction tank.
Preferably, the automatic control dosing system adopted by the invention comprises a lime dosing tank, a sodium hydroxide dosing tank, a PAM dosing tank, a sulfuric acid dosing tank and a sodium hypochlorite dosing tank; the lime dosing tank is respectively connected into the first reaction tank, the second reaction tank and the fourth reaction tank; the sodium hydroxide dosing tank is connected into a third reaction tank; the PAM dosing tank is connected into a first flocculation tank; the sulfuric acid dosing tank is connected into a sixth reaction tank; and the sodium hypochlorite dosing tank is connected into a seventh reaction tank.
Preferably, the product discharge system adopted by the invention comprises a first sludge tank, a second sludge tank, a third sludge tank and a fourth sludge tank; the first sludge tank is communicated with the bottom of the first vertical flow inclined plate sedimentation tank; the second sludge tank is communicated with the bottom of the second vertical flow inclined plate sedimentation tank; the third sludge tank is communicated with the bottom of the third vertical flow inclined plate sedimentation tank; the fourth sludge tank is communicated with the bottom of the fourth vertical flow inclined plate sedimentation tank.
Preferably, the treatment device for recycling the phosphogypsum leachate also comprises a water quality analyzer arranged inside the clean water tank.
A treatment method of phosphogypsum leachate based on the treatment device for recycling the phosphogypsum leachate is characterized by comprising the following steps: the method comprises the following steps:
1) conveying the acid phosphogypsum yard leachate to a water collecting tank;
2) conveying the leachate in the water collecting tank to a first reaction tank, simultaneously monitoring the pH value in the first reaction tank in real time by using a first pH meter, controlling a lime dosing tank to dose lime into the first reaction tank (13) according to the pH value obtained by monitoring the first pH meter in real time until the pH value of the leachate is 3.0-3.5, and obtaining the leachate containing solid precipitates;
3) conveying the leachate containing the solid precipitate obtained in the step 2) to a first vertical flow inclined plate sedimentation tank to obtain a precipitate and a supernatant; collecting the sediment in a first sludge tank through a vertical centrifugal pump, and enabling the supernatant to enter the step 4);
4) conveying the supernatant obtained in the step 3) to a second reaction tank, monitoring the pH value in the second reaction tank in real time through a second pH meter, and controlling a lime adding tank to add lime into the second reaction tank according to the pH value obtained by the real-time monitoring of the second pH meter until the pH value of the solution is 6-6.5, so as to obtain a leachate containing solid precipitates;
5) conveying the leachate containing the solid precipitate obtained in the step 4) to a second vertical flow inclined plate sedimentation tank to obtain a precipitate and a supernatant, collecting the precipitate in a second sludge tank through a vertical centrifugal pump, and allowing the supernatant to enter the step 6);
6) conveying the supernatant obtained in the step 5) to a third reaction tank, monitoring the pH value in the third reaction tank in real time by using a third pH meter, and controlling a sodium hydroxide dosing tank to dose sodium hydroxide into the third reaction tank according to the pH value obtained by the real-time monitoring of the third pH meter until the pH value of the solution is 8.5-9.5, so as to obtain leachate containing solid precipitates;
7) conveying the leachate containing the solid precipitate obtained in the step 6) to a first flocculation tank, and adding a PAM medicament into the first flocculation tank through a PAM medicament adding tank to agglomerate the solid precipitate to obtain the leachate containing the solid precipitate;
8) conveying the leachate containing the solid precipitate obtained in the step 7) to a third vertical flow inclined plate sedimentation tank to obtain a precipitate and a supernatant, collecting the precipitate in the third sludge tank through a vertical centrifugal pump, and allowing the supernatant to enter the step 9);
9) conveying the supernatant obtained in the step 8) to a fourth reaction tank, monitoring the pH value in the fourth reaction tank in real time by using a fourth pH meter, and controlling a lime adding tank to add lime into the fourth reaction tank according to the pH value obtained by monitoring the fourth pH meter in real time until the pH value of the solution is 11.5-12.5, so as to obtain a leachate containing solid precipitates;
10) conveying the leachate containing the solid precipitate in the step 9) to a fourth vertical flow inclined plate sedimentation tank to obtain a precipitate and a supernatant, collecting the precipitate in the fourth sludge tank through a vertical centrifugal pump, and allowing the supernatant to enter the step 11);
11) conveying the supernatant obtained in the step 10) to a sixth reaction tank, monitoring the pH value in the sixth reaction tank in real time by adopting a fifth pH meter, and controlling a sulfuric acid adding tank to add sulfuric acid into the sixth reaction tank according to the pH value obtained by monitoring the fifth pH meter in real time until the pH value of the solution is 6-9;
12) conveying the supernatant in the step 11) to a seventh reaction tank, judging whether the ammonia nitrogen of the supernatant in the seventh reaction tank exceeds a discharge standard, if so, adding sodium hypochlorite into the seventh reaction tank through a sodium hypochlorite adding tank until the ammonia nitrogen of the supernatant in the seventh reaction tank reaches the discharge standard, and then discharging the supernatant through a water outlet; if not, performing step 13);
13) conveying the solution in the step 12) to a clean water tank, and monitoring whether phosphate in the solution in the clean water tank reaches an efflux standard in real time through a water quality analyzer; if the phosphate exceeds the standard, conveying the solution to a third reaction tank, and repeating the steps 6) to 12) until the phosphate reaches an emission standard and then discharging the phosphate through a water outlet; if the phosphate reaches the discharge standard, the phosphate is directly discharged out through the water outlet.
Preferably, in the step 1) adopted by the invention, the ammonia nitrogen content in the leaching solution of the acid phosphogypsum yard is 100-500mg/L, the phosphate content is 4000-10000mg/L, the fluorine ion content is 100-2000mg/L, and the magnesium ion content is 500-1500 mg/L.
Preferably, the reaction time for conveying the leachate in the collecting tank to the first reaction tank in the step 2) adopted by the invention is 15-30 min; the reaction time for conveying the supernatant obtained in the step 3) to the second reaction tank in the step 4) is 15-30 min; the reaction time for conveying the supernatant obtained in the step 5) to the third reaction tank in the step 6) is 10-15 min; and in the step 9), the supernatant in the step 8) is conveyed to a fourth reaction tank, and the fixed reaction time is 10-15 min.
Preferably, the surface load of the first vertical flow inclined plate sedimentation tank in the step 3) adopted by the invention is 0.5-0.8m3/m2H; the surface load of the second vertical flow inclined plate sedimentation tank in the step 5) is 0.5-0.8m3/m2H; the surface load of the third vertical flow inclined plate sedimentation tank in the step 8) is 0.7-1.0m3/m2H; the surface load of the fourth vertical flow inclined plate sedimentation tank in the step 10) is 0.6-0.9m3/m2·h。
Preferably, the amount of PAM used in step 7) of the present invention is 100m3Adding 2.4kg of PAM into the leachate; the mass fraction of sulfuric acid in the step 11) is 98 percent; the molar ratio of the sodium hypochlorite adding amount in the step 12) to the ammonia nitrogen of the supernatant in the step 11) is nClO-：nNH4+＝2.5：1。
Compared with the prior art, the method has the advantages that:
the invention provides a treatment device for recycling phosphogypsum leachate, which comprises a water collecting tank, an automatic control dosing system, a mixed settling system, a clean water tank and a product discharge system, wherein the automatic control dosing system is connected with the water collecting tank; the water collecting tank is provided with a water inlet communicated with the water collecting tank; the water collecting tank is communicated with the clean water tank through a mixed sedimentation system; the clean water tank is connected to the mixed sedimentation system; a water outlet communicated with the clean water tank is arranged on the clean water tank; the automatic control medicine adding system and the product discharge system are communicated with the mixing and settling system respectively. The invention provides a device and a method for recycling phosphogypsum heap leachate generated by separating N, P, F elements to precipitate and separate out and no solid waste, aiming at the phenomena of large sludge amount, low ammonia nitrogen removal rate and coprecipitation of various substances in the existing phosphogypsum heap leachate treatment process. The invention can not only make the concentration of each ion remained in the leachate reach the first-class standard of the Integrated wastewater discharge Standard (GB8978-1996) (wherein NH4-N<5mg/L、TP<0.5mg/L、F-<5mg/L) and can classify and precipitate the precipitate without increasing the medicament cost, thereby effectively recycling the precipitate. Compared with the traditional coprecipitation process, the mixed waste precipitate is formed, so that the precipitate cannot be separated and subsequent resource utilization cannot be carried out, the treatment device and the treatment method do not change the addition amount of the medicament and the dosing form of the medicament, and N, P, F elements in the leachate can be classified and precipitated in the forms of magnesium ammonium phosphate, calcium hydrophosphate and calcium fluoride under the condition of not increasing the cost of the treatment medicament, so that the aim of resource recycling is fulfilled. The invention has the following advantages:
1) after the wastewater is treated, NH in the wastewater4-N<5mg/L、TP<0.5mg/L、F-<5mg/L reaches the first-grade discharge standard of Integrated wastewater discharge Standard GB 8978-1996;
2) regulating and controlling the phosphogypsum heap-dump leachate to a specific pH value through CaO and NaOH, and facilitating ammonia nitrogen, total phosphorus and F in the leachate-、Mg2+Recovery of plasma, per tonThe phosphoric acid percolate can recover 21.9kg of II-type feed grade calcium hydrophosphate, 11kg of magnesium ammonium phosphate with the purity of 46 percent and 8.6kg of fluorite with the purity of 31 percent, and has important economic value;
3) the process method is green and environment-friendly, does not generate substances harmful to the environment, and does not discharge waste residues;
4) the device of the invention has simple structure and is convenient for later amplification.
Drawings
FIG. 1 is a schematic structural diagram of a treatment device for recycling phosphogypsum leachate provided by the invention;
FIG. 2 is a graph showing the change in ionic concentration in leachate when the leachate is adjusted to a pH of 3.0 by CaO;
FIG. 3 is a graph showing the change in ionic concentration in leachate when the leachate was adjusted to pH 6.2 by CaO;
FIG. 4 is the change in ionic concentration in the leachate when the leachate was adjusted to pH 8.5 with NaOH;
FIG. 5 is a graph showing the change in ionic concentration in leachate when the leachate was adjusted to a pH of 12.5 by CaO;
wherein:
1-lime dosing tank; 2-sodium hydroxide dosing tank; 3-PAM dosing tank; 4-sulfuric acid dosing tank; 5-sodium hypochlorite dosing tank; 6-a first pH meter; 7-a second pH meter; 8-a third pH meter; 9-a fourth pH meter; 10-a fifth pH meter; 11-a water quality analyzer; 12-a water collecting tank; 13-a first reaction tank; 14-a first vertical flow inclined plate sedimentation tank; 15-a second reaction tank; 16-a second vertical flow inclined plate sedimentation tank; 17-a third reaction tank; 18-a first flocculation tank; 19-a third vertical flow inclined plate sedimentation tank; 20-a fourth reaction tank; 21-a fourth vertical flow inclined plate sedimentation tank; 22-a sixth reaction tank; 23-a seventh reaction tank; 24-a clean water tank; 25-a first sludge basin; 26-a second sludge tank; 27-a third sludge basin; 28-fourth sludge pond.
Detailed Description
As shown in fig. 1, the invention provides a treatment device for recycling phosphogypsum leachate, which comprises: a water inlet and outlet and automatic control dosing system, a mixing and settling system and a product discharge system; the water inlet and outlet and automatic control dosing system is connected with the mixed sedimentation system and is used for adding leachate, medicament and drained leachate into the mixed sedimentation system; the product discharge system is connected with the mixed settling system and is used for collecting solid precipitates generated by the mixed settling system; the water inlet and outlet and automatic control dosing system comprises a lime dosing tank 1, a sodium hydroxide dosing tank 2, a PAM dosing tank 3, a sulfuric acid dosing tank 4, a sodium hypochlorite dosing tank 5, a first pH meter 6, a second pH meter 7, a third pH meter 8, a fourth pH meter 9, a fifth pH meter 10, a water quality analyzer 11, a water collecting tank 12, a sixth reaction tank 22, a seventh reaction tank 23 and a clean water tank 24; the water collecting tank 12 is used for collecting leachate and conveying the leachate to a subsequent reaction tank; one ends of a first pH meter 6, a second pH meter 7 and a fourth pH meter 9 are respectively connected with a first reaction tank 13, a second reaction tank 15 and a fourth reaction tank 20 to measure the pH value of the leachate in real time, and the other ends are connected with a lime dosing tank 1 to control the lime dosing amount and adjust the pH value of the leachate; one end of a third pH meter 8 is connected with a third reaction tank 17 to measure the pH value of the leachate in real time, and the other end is connected with a sodium hydroxide dosing tank 2 to control the dosage of sodium hydroxide and adjust the pH value of the leachate; one end of a fifth pH meter 10 is connected with a sixth reaction tank 22 to measure the pH value of the leachate in real time, and the other end is connected with a sulfuric acid dosing tank 4 to control the dosage of sulfuric acid and adjust the pH value of the leachate so that the pH value of the leachate reaches the discharge level; the PAM dosing tank 3 is connected with the first flocculation tank 18, and PAM (polyacrylamide) agent is dosed to enable the generated precipitate to be rapidly settled so as to facilitate the collection of the precipitate; the sodium hypochlorite dosing tank 5 is connected with the seventh reaction tank 23, and sodium hypochlorite is dosed to avoid the ammonia nitrogen in the effluent from exceeding the standard due to sudden conditions; the water quality analyzer 11 is connected with the clean water tank 24 and is used for monitoring whether the treated leachate ammonia nitrogen and total phosphorus reach the emission standard on line; the clean water tank 24 is connected to the fourth reaction tank 20, on one hand, to circulate the leachate that exceeds the phosphorus level for further reaction, and on the other hand, to collect the leachate that reaches the discharge standard and discharge the leachate that reaches the discharge standard.
The mixed sedimentation system comprises a first reaction tank 13, a first vertical flow inclined plate sedimentation tank 14, a second reaction tank 15, a second vertical flow inclined plate sedimentation tank 16, a third reaction tank 17, a first flocculation tank 18, a third vertical flow inclined plate sedimentation tank 19, a fourth reaction tank 20 and a fourth vertical flow inclined plate sedimentation tank 21; the first reaction tank 13 is used as a reaction site of lime and leachate to generate solid precipitate, and the leachate containing the precipitate is conveyed to the first vertical flow inclined plate sedimentation tank 14; the first vertical flow inclined plate sedimentation tank 14 serves as a solid sedimentation place on one hand, and conveys clarified leachate to the second reaction tank 15 on the other hand; the second reaction tank 15 is used as a reaction site for lime and leachate to generate solid precipitates, and the leachate containing the precipitates is conveyed to a second vertical flow inclined plate sedimentation tank 16; the second vertical flow inclined plate sedimentation tank 16 serves as a solid sedimentation place on one hand, and conveys clarified leachate to a third reaction tank 17 on the other hand; the third reaction tank 17 is used as a reaction site of the sodium hydroxide and the leachate to generate solid precipitates, and the leachate containing the precipitates is conveyed to the first flocculation tank 18; the first flocculation tank 18, on the one hand, allows the solids to settle quickly and, on the other hand, delivers the clarified leachate to a third vertical inclined-plate sedimentation tank 19; the third vertical flow inclined plate sedimentation tank 19 serves as a solid sedimentation place on one hand, and conveys the clarified leachate to the fourth reaction tank 20 on the other hand; the fourth reaction tank 20 is used as a reaction site for lime and leachate to generate solid precipitates, and the leachate containing the precipitates is conveyed to the fourth vertical flow inclined plate sedimentation tank 21; the fourth vertical flow inclined plate sedimentation tank 21 serves as a solid sedimentation place on one hand, and conveys the clarified leachate to a next stage for reaction on the other hand, so that the leachate meets the discharge standard.
The product discharge system comprises a first sludge tank 25, a second sludge tank 26, a third sludge tank 27 and a fourth sludge tank 28; the first sludge tank 25 is connected with the first vertical flow inclined plate sedimentation tank 14 through a vertical centrifugal pump, and collects solid sediment settled in the first vertical flow inclined plate sedimentation tank 14; the second sludge tank 26 is connected with the second vertical flow inclined plate sedimentation tank 16 through a vertical centrifugal pump and collects solid sediment settled in the second vertical flow inclined plate sedimentation tank 16; the third sludge tank 27 is connected with the third vertical flow inclined plate sedimentation tank 19 through a vertical centrifugal pump, and collects solid sediment settled in the third vertical flow inclined plate sedimentation tank 19; the fourth sludge tank 28 is connected with the fourth vertical flow inclined plate sedimentation tank 21 through a vertical centrifugal pump, and collects the solid sediment settled in the fourth vertical flow inclined plate sedimentation tank 21.
On the other hand, the invention also provides a process for recycling the phosphogypsum yard leachate based on the processing device for recycling the phosphogypsum leachate, and the method comprises the following steps:
1) conveying the acid phosphogypsum yard leachate containing phosphate radicals, ammonia nitrogen, fluoride ions and magnesium ions with certain concentration to a water collecting tank 12;
2) conveying the leachate obtained in the step 1) to a first reaction tank 13, simultaneously monitoring the pH value in the first reaction tank 13 in real time by using a first pH meter 6, controlling a lime adding tank 1 to add lime into the first reaction tank 13 according to the pH value obtained by the real-time monitoring of the first pH meter 6 until the pH value of the leachate is 3.0-3.5, and obtaining the leachate containing solid precipitates;
3) conveying the leachate containing the solid precipitate in the step 2) to a first vertical flow inclined plate sedimentation tank 14, collecting the precipitated substances in a first sludge tank 25 through a vertical centrifugal pump, and allowing the supernatant to enter the next step;
4) conveying the supernatant obtained in the step 3) to a second reaction tank 15, monitoring the pH value in the second reaction tank 15 in real time through a second pH meter 7, and controlling a lime adding tank 1 to add lime into the second reaction tank 15 according to the pH value obtained by the real-time monitoring of the second pH meter 7 until the pH value of the solution is 6-6.5 to obtain a leachate containing solid precipitates;
5) conveying the leachate containing the solid precipitate in the step 4) to a second vertical flow inclined plate sedimentation tank 16, collecting the precipitate in a second sludge tank 26 through a vertical centrifugal pump, and allowing the supernatant to enter the next step;
6) conveying the supernatant obtained in the step 5) to a third reaction tank 17, monitoring the pH value in the third reaction tank 17 by using a third pH meter 8 in real time, and controlling a sodium hydroxide dosing tank 2 to dose sodium hydroxide into the third reaction tank 17 according to the pH value obtained by the real-time monitoring of the third pH meter 8 until the pH value of the solution is 8.5-9.5, so as to obtain a leachate containing solid precipitates;
7) conveying the leachate containing the solid precipitate in the step 6) to a first flocculation tank 18, and adding a PAM medicament into a PAM medicament adding tank 3 to agglomerate the solid precipitate to obtain the leachate containing the solid precipitate;
8) conveying the leachate containing the solid precipitate in the step 7) to a third vertical flow inclined plate sedimentation tank 19, collecting the precipitated substances in a third sludge tank 27 through a vertical centrifugal pump, and allowing the supernatant to enter the next step;
9) conveying the supernatant obtained in the step 8) to a fourth reaction tank 20, monitoring the pH value in the fourth reaction tank 20 in real time by using a fourth pH meter 9, and controlling a lime adding tank 1 to add lime into the fourth reaction tank 20 according to the pH value obtained by monitoring the fourth pH meter 9 in real time until the pH value of the solution is 11.5-12.5, so as to obtain a leachate containing solid precipitates;
10) conveying the leachate containing the solid precipitate in the step 9) to a fourth vertical flow inclined plate sedimentation tank 21, collecting the precipitated substances in a fourth sludge tank 28 through a vertical centrifugal pump, and allowing the supernatant to enter the next step;
11) monitoring the pH value of the supernatant in the step 10) in the sixth reaction tank 22 by adopting a fifth pH meter 10 in real time, and controlling a sulfuric acid adding tank 4 to add sulfuric acid into the sixth reaction tank 22 according to the pH value obtained by monitoring the fifth pH meter 10 in real time until the pH value of the solution is 6-9;
12) conveying the supernatant obtained in the step 11) to a seventh reaction tank 23, judging whether the ammonia nitrogen of the supernatant in the seventh reaction tank 23 exceeds a discharge standard, if so, adding sodium hypochlorite into the seventh reaction tank 23 through a sodium hypochlorite adding tank 5 until the ammonia nitrogen of the supernatant in the seventh reaction tank 23 reaches the discharge standard, and then discharging the supernatant through a water outlet; if not, performing step 13);
13) conveying the solution in the step 12) to a clean water tank 24, and monitoring whether phosphate in the solution in the clean water tank 24 reaches an efflux standard in real time through a water quality analyzer 11; if the phosphate exceeds the standard, the solution is conveyed to a third reaction tank 17, and the steps 6) to 12) are repeated until the phosphate reaches the discharge standard and then is discharged through a water outlet; if the phosphate reaches the discharge standard, the phosphate is directly discharged out through the water outlet.
Wherein:
step 1), the ammonia nitrogen content of the phosphogypsum yard leachate is 500mg/L, the phosphate content is 4000 + 10000mg/L, the fluorine ion content is 100 + 2000mg/L, and the magnesium ion content is 500 + 1500 mg/L.
And 2) leaching solution reaction time is 15-30 min. H3PO4Is a tribasic acid, the conjugated acid-base pair of which is H in sequence3PO4And H2PO4 -、H2PO4 -With HPO4 2-、HPO4 2-And PO4 3-Thus, H3PO4、H2PO4 -、HPO4 2-And PO4 3-Has a distribution coefficient of delta3、δ2、δ1、δ0. Taking leachate of 1 LpH-2.3 ammonia nitrogen 0.03mol/L (423mg/L), phosphate 0.176mol/L (5450mg/L), magnesium ion 0.053mol/L (1270mg/L) and fluorine ion 0.1mol/L (1910mg/L) as an example, delta is between pH 3.0 and 3.53＝0.09891，δ2＝0.90099，δ1＝0.00011，δ00; cH in water3PO4＝0.0174mol/L，nH2PO4 -＝0.1584mol/L，nCa2+＝0.0108mol/L，nF-＝0.1mol/L；K[CaH2PO42]＝nH2PO4 -2*nCa2+＝2.71*10-4＜KSP[CaH2PO42]＝4.59*10-3，K[CaHPO4]＝nHPO4 2-*nCa2+＝2.08*10-7＞KSP[CaHPO4]＝1.0*10-7，K[CaF2]＝n(F-)2*nCa2+＝1.08*10-4＞Ksp[CaF2]＝2.7×10-11Due to Ksp[CaF2]<<KSP[CaHPO4]So that the solid precipitate formed in step 2) is predominantly CaF2The concentration of the precipitate was varied as shown in fig. 2, and when the pH was 3.0, the concentration of the precipitate was 402mg/L, 5120mg/L, 1160mg/L, and 593mg/L, and the composition of the precipitate was as shown in table 1, and fluorite having a purity of 31% was obtained.
TABLE 1
Figure BDA0002832863640000081
The surface load of the first vertical flow inclined plate sedimentation tank 14 in the step 3) is0.5-0.8m3/m2H, the water content of the sediment in the first sludge tank 25 is 54 percent after pressure filtration.
And 4) leaching solution reaction time of 15-30 min. Delta at pH 6.0-6.53＝0，δ2＝0.82426，δ1＝0.17569，δ 00 in water nH2PO4 -＝0.1449mol/L，nHPO4 2-0.0309mol/L, taking cCa2+＝4*10-5mol/L；K[CaHPO4]＝nHPO4 2-*nCa2+＝1.24*10-5＞KSP[CaHPO4]＝1.0*10-7(ii) a The solid precipitate formed in step 4 is therefore predominantly CaHPO4The concentration of the precipitate is shown in figure 3, when the pH is 6.2, the ammonia nitrogen is 345mg/L, the phosphate is 1320mg/L, the magnesium ion is 844mg/L, the fluorine ion is 29.1mg/L, and the composition of the precipitate is shown in table 2, wherein the CaHPO is shown in figure 24·2H2The highest O content reaches 16.9g, the purity is 78 percent, and P2O5The content and the fluorine content meet the production standard of feed grade calcium hydrophosphate (GB/T22549-2017).
TABLE 2
Figure BDA0002832863640000091
The surface load of the second vertical flow inclined plate sedimentation tank 16 in the step 5) is 0.5-0.8m3/m2H, the water content of the second sludge tank 26 after filter pressing is 52%.
And 6) leaching solution reaction time is 10-15 min. Adding caustic soda flakes to ensure that the percolation pH is 8.5-9.5, wherein Ca is not added externally2+So that the stage phosphate is not Ca-protected at pH 6.0-6.5 to pH 8.5-9.52+Consumption of K [ MgNH ]4PO4]＝nPO4 3-*nMg2+*nNH4 +＝2.68*10-5＞Ksp，MgNH4PO4＝2.5×10-13So PO in the solution at this stage4 3-、NH4 +、Mg2+Will mainly generate MgNH4PO4Precipitated MAP, varying in concentration, e.gFIG. 4 shows that when pH is 8.5, ammonia nitrogen is 8.24mg/L, phosphate is 309mg/L, magnesium ion is 70.1mg/L, and fluorine ion is 27mg/L, and the composition of the precipitate is shown in Table 3, wherein MgNH is present4PO4·6H2The highest O content reaches 5.05g, and the purity is 46 percent.
TABLE 3
Figure BDA0002832863640000092
The amount of PAM in step 7) is 100m32.4kg of PAM was added to the/h leachate.
The surface load of the third vertical flow inclined plate sedimentation tank 19 in the step 8) is 0.7-1.0m3/m2H, the water content of the sediment in the third sludge tank 27 is 48 percent after pressure filtration.
And 9) leaching solution reaction time is 10-15 min. Delta at pH 11.5-12.53＝0，δ2＝0，δ1＝0.13503，δ00.86497; in water, nHPO4 -＝0.0237mol/L，nPO4 3-＝0.1521mol/L，cCa2+＝0.0369mol/L；K[CaHPO4]＝nHPO4 2-*nCa2+＝8.7*10-4＞KSP[CaHPO4]＝1.0*10-7，K[Ca3(PO4)2]＝n(PO4 3-)2*n(Ca2+)3＝1.16*10-6＞KSP[Ca3(PO4)2]＝2.0*10-29(ii) a I.e. the phosphate in the system is mainly Ca3(PO4)2The concentration of the precipitate was varied as shown in fig. 5, and when the pH was 12.5, the concentration of ammonia nitrogen was 3.92mg/L, the concentration of phosphate was 0.41mg/L, the concentration of magnesium ion was 0.028mg/L, and the concentration of fluoride was 2.84mg/L, and the composition of the precipitate was as shown in table 4.
TABLE 4
Figure BDA0002832863640000101
The fourth vertical flow inclined plate in the step 10) sinksThe surface load of the sedimentation tank 21 is 0.6-0.9m3/m2H, the water content of the sediment in the fourth sludge tank 28 is 53 percent after pressure filtration.
The mass fraction of sulfuric acid in the step 11) is 98%.
The mol ratio of the sodium hypochlorite NaClO adding amount to the overproof ammonia nitrogen in the step 12) is nClO-：nNH4+＝2.5：1。
And step 14), the water quality analyzer 11 can rapidly react the ammonia nitrogen and total phosphorus concentration of the water without digesting the water quality.
Example 1
1) The pH value of the leaching liquid wastewater of a certain phosphogypsum yard is 2.4, the ammonia nitrogen content is 367mg/L, the total phosphorus content is 5103mg/L, the magnesium ion content is 1085mg/L, the fluorine ion content is 1760mg/L, the sulfate ion content is 5980mg/L, the calcium ion content is 189mg/L, and the wastewater is collected in a water collecting tank. Flow rate of 100m3H, regulating the pH value of the leachate to 3.3 through a lime dosing tank 1, reacting for 20min, and then allowing the supernatant to enter a next-stage reaction tank, wherein ammonia nitrogen, total phosphorus and Mg are contained at the moment2+、F-、SO4 2-、Ca2+The concentration of (b) is 342mg/L, 4896mg/L, 964mg/L, 429mg/L, 3762mg/L and 368mg/L in sequence.
2) Adjusting the pH of the supernatant to 6.4 by a lime dosing tank 1, continuously reacting for 20min, and allowing the supernatant to enter a next-stage reaction tank, wherein ammonia nitrogen, total phosphorus and Mg are contained2+、F-、SO4 2-、Ca2+The concentration of (A) is 316mg/L, 986mg/L, 844mg/L, 28.6mg/L, 3573mg/L and 2.6mg/L in sequence.
3) Adjusting the pH of the supernatant to 8.7 by a sodium hydroxide dosing tank 2, continuing for 10min, flocculating in a flocculation tank, and allowing the supernatant to enter a next-stage reaction tank, wherein ammonia nitrogen, total phosphorus and Mg are contained in the supernatant2+、F-、SO4 2-、Ca2+The concentrations of (a) were 7.8mg/L, 275mg/L, 106mg/L, 27.3mg/L, 3426mg/L, and 0.63mg/L in this order.
4) Adjusting the pH of the supernatant to 12.1 by a lime dosing tank 1, continuously reacting for 15min, and adjusting the pH of the supernatant in a reaction tank at the next stage to adjust the ammonia nitrogen, total phosphorus and Mg2+、F-、SO4 2-、Ca2+The concentration of (a) is sequentially 2.9mg/L, 0.37mg/L, 0.04mg/L, 2.17mg/L, 3296mg/L and 196 mg/L.
5) 98 wt% of sulfuric acid is added into a sulfuric acid adding tank 4 to adjust the pH value of the leachate back, the pH value is adjusted to 8, the treated wastewater reaches the first-class discharge standard of Integrated wastewater discharge Standard GB8978-1996 and can be directly discharged, and at the moment, suspended solids SS and SO in the solution are directly discharged4 2-、Ca2+The concentration of (a) is 11mg/L, 4320mg/L and 209mg/L in sequence.
The method has stable operation effect, the operation cost is now stabilized to be 6-8 yuan/ton of the concentration content of substances such as total phosphorus in sewage and sewage, the absolute operation cost is determined, the relative operation cost is determined by the treatment method, and the relative operation cost can be minimized on the basis of the absolute operation cost.

Claims (10)

1. The utility model provides a processing apparatus of resource recovery ardealite leachate which characterized in that: the treatment device for recycling the phosphogypsum leachate comprises a water collecting tank (12), an automatic control dosing system, a mixed settling system, a clean water tank (24) and a product discharge system; a water inlet communicated with the water collecting tank (12) is formed in the water collecting tank (12); the water collecting tank (12) is communicated with the clean water tank (24) through a mixed sedimentation system; the clean water tank (24) is connected to a mixed sedimentation system; a water outlet communicated with the clean water tank (24) is formed in the clean water tank (24); the automatic control medicine adding system and the product discharge system are communicated with the mixing and settling system respectively.
2. The treatment device for recycling the phosphogypsum leachate according to claim 1, characterized in that: the mixed sedimentation system comprises a first pH meter (6), a second pH meter (7), a third pH meter (8), a fourth pH meter (9), a fifth pH meter (10), a first reaction tank (13), a first vertical flow inclined plate sedimentation tank (14), a second reaction tank (15), a second vertical flow inclined plate sedimentation tank (16), a third reaction tank (17), a first flocculation tank (18), a third vertical flow inclined plate sedimentation tank (19), a fourth reaction tank (20), a fourth vertical flow inclined plate sedimentation tank (21), a sixth reaction tank (22) and a seventh reaction tank (23); the water collecting tank (12) is communicated with a first vertical flow inclined plate sedimentation tank (14) through a first reaction tank (13); the top of the first vertical flow inclined plate sedimentation tank (14) is communicated with a second vertical flow inclined plate sedimentation tank (16) through a second reaction tank (15); the top of the second vertical flow inclined plate sedimentation tank (16) is communicated with a third vertical flow inclined plate sedimentation tank (19) through a third reaction tank (17) and a first flocculation tank (18); the top of the third vertical flow inclined plate sedimentation tank (19) is communicated with a fourth vertical flow inclined plate sedimentation tank (21) through a fourth reaction tank (20); the top of the fourth vertical flow inclined plate sedimentation tank (21) is communicated with a clean water tank (24) through a sixth reaction tank (22) and a seventh reaction tank (23); the clean water tank (24) is connected to the third reaction tank (17); the bottom of the first vertical flow inclined plate sedimentation tank (14), the bottom of the second vertical flow inclined plate sedimentation tank (16), the bottom of the third vertical flow inclined plate sedimentation tank (19) and the bottom of the fourth vertical flow inclined plate sedimentation tank (21) are respectively connected with a product discharge system; the automatic control medicine adding system is respectively connected into a first reaction tank (13), a second reaction tank (15), a third reaction tank (17), a first flocculation tank (18), a fourth reaction tank (20), a sixth reaction tank (22) and a seventh reaction tank (23); the first pH meter (6) extends into the first reaction tank (13); the second pH meter (7) extends into the second reaction tank (15); the third pH meter (8) extends into the third reaction tank (17); the fourth pH meter (9) extends into the fourth reaction tank (20); the fifth pH meter (10) extends into the sixth reaction tank (22).
3. The treatment device for recycling the phosphogypsum leachate according to claim 2, characterized in that: the automatic control dosing system comprises a lime dosing tank (1), a sodium hydroxide dosing tank (2), a PAM dosing tank (3), a sulfuric acid dosing tank (4) and a sodium hypochlorite dosing tank (5); the lime dosing tank (1) is respectively connected into the first reaction tank (13), the second reaction tank (15) and the fourth reaction tank (20); the sodium hydroxide dosing tank (2) is connected into a third reaction tank (17); the PAM dosing tank (3) is connected into a first flocculation tank (18); the sulfuric acid dosing tank (4) is connected into a sixth reaction tank (22); and the sodium hypochlorite dosing tank (5) is connected into a seventh reaction tank (23).
4. The treatment device for recycling the phosphogypsum leachate according to claim 3, characterized in that: the product discharge system comprises a first sludge tank (25), a second sludge tank (26), a third sludge tank (27) and a fourth sludge tank (28); the first sludge tank (25) is communicated with the bottom of the first vertical flow inclined plate sedimentation tank (14); the second sludge tank (26) is communicated with the bottom of the second vertical flow inclined plate sedimentation tank (16); the third sludge tank (27) is communicated with the bottom of the third vertical flow inclined plate sedimentation tank (19); the fourth sludge tank (28) is communicated with the bottom of the fourth vertical flow inclined plate sedimentation tank (21).
5. The treatment device for recycling the phosphogypsum leachate according to the claim 1 or 2 or 3 or 4, characterized in that: the treatment device for recycling the phosphogypsum leachate also comprises a water quality analyzer (11) arranged inside the clean water tank (24).
6. The treatment method of the phosphogypsum leachate based on the treatment device for recycling the phosphogypsum leachate according to claim 5 is characterized by comprising the following steps: the method comprises the following steps:
1) conveying the acid phosphogypsum yard leachate to a water collecting tank (12);
2) conveying the leachate in the water collecting tank (12) into a first reaction tank (13), simultaneously monitoring the pH value in the first reaction tank (13) in real time by using a first pH meter (6), controlling a lime adding tank (1) to add lime into the first reaction tank (13) according to the pH value obtained by the real-time monitoring of the first pH meter (6) until the pH =3.0-3.5 of the leachate, and obtaining the leachate containing solid precipitates;
3) conveying the leachate containing the solid precipitate obtained in the step 2) to a first vertical flow inclined plate sedimentation tank (14) to obtain a precipitate and a supernatant; collecting the sediment in a first sludge tank (25) through a vertical centrifugal pump, and enabling the supernatant to enter the step 4);
4) conveying the supernatant obtained in the step 3) to a second reaction tank (15), monitoring the pH value in the second reaction tank (15) in real time through a second pH meter (7), and controlling a lime adding tank (1) to add lime to the second reaction tank (15) according to the pH value obtained by the real-time monitoring of the second pH meter (7) until the pH =6-6.5 of the solution, so as to obtain a leachate containing solid precipitates;
5) conveying the leachate containing the solid precipitate obtained in the step 4) to a second vertical flow inclined plate sedimentation tank (16) to obtain a precipitate and a supernatant, collecting the precipitate in a second sludge tank (26) through a vertical centrifugal pump, and allowing the supernatant to enter the step 6);
6) conveying the supernatant obtained in the step 5) to a third reaction tank (17), monitoring the pH value in the third reaction tank (17) in real time by using a third pH meter (8), and controlling a sodium hydroxide adding tank (2) to add sodium hydroxide to the third reaction tank (17) according to the pH value obtained by real-time monitoring of the third pH meter (8) until the pH =8.5-9.5 of the solution, so as to obtain a leachate containing solid precipitates;
7) conveying the leachate containing the solid precipitate obtained in the step 6) to a first flocculation tank (18), and adding a PAM medicament into the first flocculation tank (18) through a PAM medicament adding tank (3) to agglomerate the solid precipitate to obtain the leachate containing the solid precipitate;
8) conveying the leachate containing the solid precipitate obtained in the step 7) to a third vertical flow inclined plate sedimentation tank (19) to obtain a precipitate and a supernatant, collecting the precipitate in a third sludge tank (27) through a vertical centrifugal pump, and allowing the supernatant to enter the step 9);
9) conveying the supernatant obtained in the step 8) to a fourth reaction tank (20), monitoring the pH value in the fourth reaction tank (20) in real time by using a fourth pH meter (9), and controlling a lime adding tank (1) to add lime to the fourth reaction tank (20) according to the pH value obtained by monitoring the fourth pH meter (9) in real time until the pH of the solution is =11.5-12.5, so as to obtain a leachate containing solid precipitates;
10) conveying the leachate containing the solid precipitate in the step 9) to a fourth vertical flow inclined plate sedimentation tank (21) to obtain a precipitate and a supernatant, collecting the precipitate in a fourth sludge tank (28) through a vertical centrifugal pump, and allowing the supernatant to enter the step 11);
11) conveying the supernatant obtained in the step 10) to a sixth reaction tank (22), monitoring the pH value in the sixth reaction tank (22) in real time by using a fifth pH meter (10), and controlling a sulfuric acid adding tank (4) to add sulfuric acid into the sixth reaction tank (22) according to the pH value obtained by monitoring the fifth pH meter (10) in real time until the pH of the solution is = 6-9;
12) conveying the supernatant in the step 11) to a seventh reaction tank (23), judging whether the ammonia nitrogen of the supernatant in the seventh reaction tank (23) exceeds a discharge standard, if so, adding sodium hypochlorite into the seventh reaction tank (23) through a sodium hypochlorite adding tank (5) until the ammonia nitrogen of the supernatant in the seventh reaction tank (23) reaches the discharge standard, and then discharging the ammonia nitrogen through a water outlet; if not, performing step 13);
13) conveying the solution in the step 12) to a clean water tank (24), and monitoring whether phosphate in the solution in the clean water tank (24) reaches an efflux standard in real time through a water quality analyzer (11); if the phosphate exceeds the standard, the solution is conveyed to a third reaction tank (17) to repeat the steps 6) to 12) until the phosphate reaches the discharge standard and then is discharged through a water outlet; if the phosphate reaches the discharge standard, the phosphate is directly discharged out through the water outlet.
7. The method of claim 6, wherein: in the step 1), the ammonia nitrogen content in the acid phosphogypsum yard leachate is 100-10000 mg/L, the phosphate content is 4000-2000 mg/L, the fluorine ion content is 100-2000mg/L, and the magnesium ion content is 500-1500 mg/L.
8. The method of claim 7, wherein: the reaction time for conveying the leachate in the water collecting tank (12) to the first reaction tank (13) in the step 2) is 15-30 min; the reaction time for conveying the supernatant obtained in the step 3) to the second reaction tank (15) in the step 4) is 15-30 min; the reaction time for conveying the supernatant obtained in the step 5) to the third reaction tank (17) in the step 6) is 10-15 min; and in the step 9), the supernatant in the step 8) is conveyed to a fourth reaction tank (20) for a fixed reaction time of 10-15 min.
9. The method of claim 8, wherein: the surface load of the first vertical flow inclined plate sedimentation tank (14) in the step 3) is 0.5-0.8m3/m2H; the surface load of the second vertical flow inclined plate sedimentation tank (16) in the step 5) is 0.5-0.8m3/m2H; the surface load of the third vertical flow inclined plate sedimentation tank (19) in the step 8) is 0.7-1.0m3/m2H; the surface load of the fourth vertical flow inclined plate sedimentation tank (21) in the step 10) is 0.6-0.9m3/m2·h。
10. The method of claim 9, wherein: the dosage of PAM in the step 7) is 100m3Adding 2.4kg of PAM into the leachate; the mass fraction of sulfuric acid in the step 11) is 98 percent; the molar ratio of the sodium hypochlorite adding amount in the step 12) to the ammonia nitrogen of the supernatant in the step 11) is nClO-：nNH4+=2.5：1。
CN202011466434.2A 2020-12-13 2020-12-13 Treatment device and treatment method for recycling phosphogypsum leachate Pending CN113121035A (en)

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Application publication date: 20210716