CN114920417A - Equipment and method for deep purification treatment of phosphogypsum slag warehouse leachate - Google Patents
Equipment and method for deep purification treatment of phosphogypsum slag warehouse leachate Download PDFInfo
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- CN114920417A CN114920417A CN202210742022.XA CN202210742022A CN114920417A CN 114920417 A CN114920417 A CN 114920417A CN 202210742022 A CN202210742022 A CN 202210742022A CN 114920417 A CN114920417 A CN 114920417A
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- leachate
- phosphogypsum slag
- crystallization
- solid
- fluidized bed
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- 238000000034 method Methods 0.000 title claims abstract description 67
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 65
- 239000002893 slag Substances 0.000 title claims abstract description 58
- 238000000746 purification Methods 0.000 title claims abstract description 30
- 238000002425 crystallisation Methods 0.000 claims abstract description 75
- 230000008025 crystallization Effects 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000005345 coagulation Methods 0.000 claims abstract description 39
- 230000015271 coagulation Effects 0.000 claims abstract description 39
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 34
- 239000001205 polyphosphate Substances 0.000 claims abstract description 34
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 34
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 14
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 14
- 239000004571 lime Substances 0.000 claims abstract description 14
- 238000003860 storage Methods 0.000 claims abstract description 14
- 239000008267 milk Substances 0.000 claims abstract description 11
- 210000004080 milk Anatomy 0.000 claims abstract description 11
- 235000013336 milk Nutrition 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims description 61
- 239000007788 liquid Substances 0.000 claims description 55
- 239000007791 liquid phase Substances 0.000 claims description 37
- 238000005188 flotation Methods 0.000 claims description 31
- 239000006247 magnetic powder Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000007790 solid phase Substances 0.000 claims description 18
- 229940037003 alum Drugs 0.000 claims description 17
- 238000004062 sedimentation Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 13
- 230000003179 granulation Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 12
- 239000012629 purifying agent Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 238000012856 packing Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000009434 installation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005189 flocculation Methods 0.000 claims description 3
- 230000016615 flocculation Effects 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 68
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 34
- 238000004519 manufacturing process Methods 0.000 abstract description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 20
- 239000011574 phosphorus Substances 0.000 abstract description 20
- 238000006386 neutralization reaction Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 10
- 239000002352 surface water Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- 239000003814 drug Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000009388 chemical precipitation Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000012071 phase Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- 239000006148 magnetic separator Substances 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 8
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 239000002367 phosphate rock Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004132 Calcium polyphosphate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 235000019827 calcium polyphosphate Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
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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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- 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
- C02F2001/5218—Crystallization
-
- 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
- C02F2101/30—Organic compounds
-
- 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
Abstract
The invention discloses equipment and a method for deep purification treatment of phosphogypsum slag storage leachate, which couple the traditional two-stage lime milk neutralization chemical precipitation treatment method, a crystallization fluidized bed, magnetic coagulation and other technologies on the basis of analyzing and summarizing the components and the characteristics of the phosphogypsum slag storage leachate, and realize the deep purification of the phosphogypsum slag storage leachate through brand new medicament combination. The related treatment process is independent of a phosphoric acid production system, and provides a percolate deep purification treatment path with low investment and low operating cost for phosphorus chemical enterprises which can not recycle the percolate in the phosphogypsum slag warehouse to the production system. The water phase purified by the method meets the requirements of III types of surface water in the environmental quality standard of surface water (GB 3838-2002), and simultaneously, the consumption of phosphoric acid in the production process of calcium magnesium polyphosphate is effectively reduced, thereby bringing ideal social, economic and environmental benefits for enterprises.
Description
Technical Field
The invention relates to the technical field of chemical wastewater treatment, in particular to equipment and a method for deep purification treatment of phosphogypsum slag warehouse leachate.
Background
Phosphogypsum is a by-product in the process of producing phosphoric acid by using sulfuric acid to extract and decompose phosphorite, and each time 1 ton of phosphoric acid (100 percent P) is produced 2 O 5 Calculated) about 5 tons of dry-base phosphogypsum as by-product.
Since phosphogypsum contains about 10% of harmful impurities such as phosphorus, fluorine compounds, organic matters and the like, and the application approach is severely limited, the general treatment mode of the phosphogypsum is to adopt a slag warehouse for stockpiling.
In the process of stockpiling, because the phosphogypsum contains moisture and the phosphogypsum creeps to extrude the moisture, the phosphogypsum slag warehouse can generate leachate which mainly comprises compounds containing phosphorus, fluorine and magnesium, organic matters and the like, has pH of 2-3 and is acidic. The general treatment method is that leachate is collected by a turbid water pipe and drained to a liquid collecting tank and then recycled to working sections of ore grinding, flotation and the like, for example, Chinese documents 'application of phosphogypsum slag yard backwater in wet ore grinding' and 'treatment method of phosphogypsum slag yard water in the production and recycling process of wet phosphoric acid', but the leachate contains more impurities and is acidic, so that series problems of equipment corrosion aggravation, impurity accumulation in phosphoric acid and the like are caused, and the quality of subsequent products is influenced. Other treatment methods such as natural evaporation or spray evaporation depending on a liquid collecting tank have the defects that the water balance is difficult to realize due to limited evaporation amount, and a large amount of acid leachate is stored in the liquid collecting tank for a long time, so that the environmental protection risk of leakage exists.
The Chinese patent 'a tailing wastewater recycling system' (application number: 201810128375.4) is that tailing wastewater is subjected to primary impurity removal through a reactor, and then is clarified through a thickener, and clear liquid is returned to partial workshop section for water supplement. The method adopts a flocculating agent and precipitation method to treat the tailing wastewater, the wastewater cannot be deeply purified, and the treated reuse water is used in a production section with low requirements on water hardness. The water phase treated by the method still contains impurities such as magnesium, fluorine, organic matters and the like, and the quality of phosphoric acid and downstream products can be reduced in the recycling process.
Chinese patent ' treatment method and system for purifying phosphogypsum stock yard penetrating fluid ' (application number: 201811214534.9) ' utilizes two-stage pH adjustment of alkaline matters and is supplemented with two units of membrane treatment and biochemical treatment to remove phosphorus, fluorine and ammonia nitrogen in the penetrating fluid, so that the treated phosphogypsum stock yard penetrating fluid meets the relevant requirements of ' comprehensive sewage discharge standard ' (GB 201811214534.9-1996). However, in the method, lime is adopted to adjust pH in sections to treat phosphorus in the leachate, polyacrylamide is added to ensure the SS value of suspended matters, and then membrane filtration is adopted to treat ammonia nitrogen, at first, the phosphorus in the leachate is completely precipitated by the lime, so that a large amount of lime is undoubtedly consumed, the production cost is overhigh, the cost of raw materials is increased by adding the polyacrylamide, and the membrane filtration treatment process has the disadvantages of easy blockage and high operation and maintenance costs. The indexes of phosphorus and fluorine of the directly discharged water treated by the method are still as high as 0.5mg/L and 5mg/L, and the deep purification treatment in the true sense is difficult to realize.
The calcium magnesium polyphosphate is rich in medium and trace elements such as calcium, magnesium, sulfur and the like, has slow release property, slowly releases orthophosphate along with the passage of time so as to meet the requirements of crops, and is a novel phosphate fertilizer product with a relatively promising prospect at present. Chinese patent' A calcium magnesium polyphosphate prepared by taking phosphoric acid and phosphate tailings as raw materialsThe fertilizer and its preparation process (application No. 201810281139.6) includes calcining phosphoric acid and floating tailings at 200-600 deg.c to produce calcium magnesium polyphosphate, in which the phosphorus source for reaction with the floating tailings is P 2 O 5 The content of the wet-process phosphoric acid is more than or equal to 15 percent, the phosphoric acid with the specification can be directly used for preparing industrial-grade phosphate products by a two-stage neutralization method or a concentration method, and the method disclosed by the invention also reduces the phosphoric acid and the phosphate productivity of a downstream working section in a phase-changing manner.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides equipment and a method for deep purification treatment of phosphogypsum slag warehouse leachate.
The purpose of the invention is realized by the following technical scheme:
the equipment for deep purification treatment of the phosphogypsum slag warehouse leachate comprises a repulping tank, a solid-liquid separator, a crystallization fluidized bed and a magnetic coagulation device which are sequentially connected, wherein the magnetic coagulation device comprises an alum blossom reaction area, an acid-base regulation area and a sedimentation separation area which are sequentially communicated, the alum blossom reaction area is connected with a liquid phase outlet of the crystallization fluidized bed, a clear water outlet is arranged on the sedimentation separation area, and a flocculation precipitation outlet is arranged at the bottom of the sedimentation separation area.
Preferably, the crystallization fluidized bed is sequentially provided with a clarification zone, a separation zone and a granulation zone from top to bottom, a liquid phase outlet of the solid-liquid separator is connected to the bottom of the crystallization fluidized bed, the bottom of the granulation zone is also provided with a crystallization promoter adding port, the granulation zone is connected with a granular crystal storage tank, and a liquid phase outlet is arranged on the clarification zone.
Preferably, the sedimentation separation area is internally provided with an inclined tube filler, the installation angle of the inclined tube filler is 45-55 degrees, the ratio of the arrangement area of the inclined tube filler to the cross-sectional area of the sedimentation separation area is 0.4-0.6:1, and the tube diameter phi of the inclined tube filler is 50-80 mm.
A method for deeply purifying leachate of a phosphogypsum slag warehouse comprises the following steps:
step A, placing the phosphogypsum slag reservoir leachate, calcium magnesium polyphosphate raw material flotation tailings and hydrogen peroxide into a repulping tank, and performing solid-liquid separation on the mixture after repulping;
step B, transferring the liquid phase obtained in the step A to a crystallization fluidized bed, and transferring the liquid phase from which the crystal is removed to magnetic coagulation equipment;
and step C, adding the deep purifying agent and the magnetic powder into magnetic coagulation equipment, adjusting the pH to 6.5-9.0, and then allowing the mixture to enter a settling separation zone with inclined tube packing to realize solid-liquid separation so as to obtain clarified water.
Preferably, in the step A, the liquid-solid mass ratio is 2-6:1, the repulping time is 0.5-4H, the repulping temperature is 20-80 ℃, the pH of the repulped liquid is 4-5.5, and the leachate and H are 2 O 2 The volume ratio is 950-1200: 1.
Preferably, in step B, a crystallization promoter is added to the liquid phase and the pH is adjusted to 5.5-6.5 with lime milk.
Preferably, the crystallization promoter is loess, ceramsite or diatomite, and the mass ratio of the amount of the liquid phase entering the crystallization fluidized bed to the addition of the crystallization promoter is 1400-1700: 1.
Preferably, the deep purifying agent is polyaluminium chloride, polyferric sulfate or aluminum sulfate, and in the magnetic coagulation equipment, the ratio of Al: (P + F) molar ratio of 1-9:1 or Fe: the molar ratio of (P + F) is 4.5-7.5:1, the reaction time is 20-80 min, and the stirring speed is 25-40 r/min.
Preferably, the mass ratio of the magnetic powder to the deep purifying agent is 1:4-1: 7.
Preferably, the solid phase obtained in step B and/or step C is transferred to a reslurry tank to repeat step A.
How to effectively utilize the phosphogypsum slag warehouse leachate is a common problem faced by phosphorus chemical enterprises all the time, because P in the phosphogypsum slag warehouse leachate 2 O 5 Generally, the concentration is below 0.5 percent, the traditional dilute acid two-stage neutralization method is difficult to directly utilize, and recycling to an extraction tank or a phosphoric acid concentration working section can reduce acid concentration and increase the consumption of concentrated steam, so most enterprises directly use the phosphogypsum slag library percolate for grinding and flotation working sections or add the treated solid phase to enter a low-end phosphate fertilizer product, directly discharge the water phase, and slightly analyze the method to find that the methods are all dependent on the existing phosphoric acid production system, but actually, many phosphorus chemical enterprises are in factThe phosphogypsum slag yard is far away from a phosphoric acid production system, is difficult to recycle, and when the service life of the phosphogypsum slag yard is due, a new slag yard is put into use, and the phosphoric acid production system is difficult to digest the percolate of the old slag yard, so more and more enterprises turn to purify the percolate of the phosphogypsum slag yard for discharge or use the percolate as surface supplementary water to realize water balance, and the deep purification of the percolate to reach the surface supplementary water standard is undoubtedly the effect which is most expected to be reached by phosphorus chemical enterprises. Therefore, many phosphorus chemical enterprises have sought for a method for treating the leachate of the phosphogypsum slag warehouse, which is more economical and environment-friendly and independent of a phosphoric acid production system, and the patent technology is provided for effectively solving the problem.
Flotation tailings are a by-product of the phosphorite flotation process due to its P 2 O 5 The percentage content is generally between 5 percent and 12 percent, the existing process has larger direct utilization difficulty, and most phosphorus chemical enterprises adopt a stockpiling mode similar to that of the phosphogypsum for treatment. In recent years, enterprises propose that flotation tailings are used as raw materials to be mixed with phosphoric acid for reaction and then calcined to generate calcium magnesium polyphosphate, but the method consumes a large amount of phosphoric acid and produces other phosphorus chemical products using phosphoric acid as raw materials through phase change subtraction. The flotation tailings are adopted to be subjected to repulping reaction with the leachate of the phosphogypsum slag reservoir in advance, and the CaMg (CO) in the tailings is obtained by adjusting the liquid-solid ratio, the pH value, the reaction time and the reaction temperature 3 ) 2 、CaCO 3 、MgCO 3 When alkaline matters react with phosphoric acid and fluosilicic acid in the leachate to generate precipitates such as phosphate, calcium fluoride and the like, most of phosphorus and fluorine in the leachate of the phosphogypsum slag warehouse are purified and removed, and meanwhile, the consumption of a purifying agent for treating the leachate can be effectively reduced, and the consumption of phosphoric acid in the production process of calcium magnesium polyphosphate can also be reduced. The invention discloses a method for reducing the phosphoric acid consumption in the process of producing calcium magnesium polyphosphate by using phosphogypsum slag-house leachate, but the method is also applicable to enterprises which do not have a matched calcium magnesium polyphosphate production line and only can pile up flotation tailings, and can also greatly reduce the consumption cost of the subsequent purification treatment of the leachate by directly permeating the phosphogypsum slag-house leachate through a flotation tailing bed layer or piling up the flotation tailings after repulping and washing and solid-liquid separation.
Magnesium hydrogen phosphate and calcium hydrogen phosphate both belong to phosphate with small solubility product, the optimal sedimentation pH is 5.5-6.2, the precipitation method can be adopted for production by utilizing the characteristics, but only the traditional precipitation method is used, the indexes of phosphorus and magnesium of a water phase after solid-liquid separation can not meet the requirements of III-class surface water in the quality standard of surface water environment (GB 3838-2002). The invention adopts the crystallization fluidized bed as equipment integrating crystallization, granulation and solid-liquid separation, has the advantages of small occupied area and less equipment and labor investment compared with the traditional solid-liquid separation equipment such as a plate-frame filter press and a centrifugal separator, and can prevent impurity magnesium from entering a phosphoric acid production system again after the granular magnesium hydrogen phosphate and the calcium hydrophosphate discharged from the bottom of the crystallization fluidized bed are dried and can be used as raw materials for producing the calcium magnesium polyphosphate.
The magnetic coagulation technology is a water treatment technology which is concerned in recent years, is mainly applied to a sewage treatment plant, and related reports which are directly used for treating phosphorus-containing leachate in a phosphogypsum slag warehouse are not available at present, the patent aims to deeply purify the leachate in the phosphogypsum slag warehouse until the leachate meets the III-class surface water in the environmental quality standard of surface water (GB 3838-2002) as a result, integrates all functional areas of magnetic coagulation into a whole set of equipment, has the advantages of attractive appearance, small occupied area, convenient inspection and maintenance and the like, the set of equipment combines the dual advantages of chemical precipitation and magnetic coagulation, preferentially selects polymeric ferric sulfate as a deep purification medicament to ensure that P in a water phase is less than 0.2mg/L and F is less than 1mg/L, combines the magnetic coagulation technology, not only can remove various heavy metals in the water phase, but also can increase the specific gravity of flocs to achieve rapid sedimentation and strengthen the solid-liquid separation effect, and does not need to add membrane filtration equipment or traditional solid-liquid separation equipment such as a plate filter press or a centrifuge, thereby effectively practice thrift equipment investment and place usable floor area, simultaneously, the crystal nucleus is regarded as to tiny magnetic, changes to form alum blossom to practice thrift the medicament use amount by a wide margin.
On the basis of analyzing and summarizing the existing water treatment technology, the invention combines the index characteristics of the phosphogypsum slag reservoir leachate, integrates the crystallization fluidized bed and the magnetic coagulation sedimentation technology, and can effectively reduce the cost for treating the leachate and simultaneously reduce the phosphoric acid consumption of calcium magnesium polyphosphate compared with the prior art while the deeply purified phosphogypsum slag reservoir leachate meets the III-class surface water in the quality standard of surface water environment (GB 3838-2002), thereby bringing ideal social, economic and environmental benefits for enterprises.
The invention has the following advantages:
1. the leachate of the phosphoric acid paste residue library is pretreated by flotation tailings, most of phosphorus and fluorine in the leachate can be purified and removed, the treatment cost by adopting the traditional chemical precipitation method is greatly reduced, the consumption of phosphoric acid for producing calcium magnesium polyphosphate products is effectively reduced, and the method has the characteristic of 'treating waste with waste'.
2. The invention uses the crystallization fluidized bed as a carrier to forcibly crystallize magnesium hydrogen phosphate and magnesium hydrogen phosphate, further reduces phosphorus, magnesium and calcium impurity elements in the leachate, and also provides useful elements for the production of calcium magnesium polyphosphate, the crystallization fluidized bed is equipment integrating crystallization, granulation and solid-liquid separation, and the traditional solid-liquid separation equipment and granulator are not needed to be added, so that the invention has the advantages of small occupied area and less equipment and labor investment.
3. The method adopts the magnetic coagulation sedimentation technology to deeply purify the phosphogypsum slag warehouse leachate, preferentially selects polyferric sulfate as a deep purification medicament, combines the magnetic coagulation technology to increase the specific gravity of flocs, achieves quick sedimentation and strengthens the alum floc reaction and solid-liquid separation effect, simultaneously uses micro magnetic powder as crystal nucleus to be easier to form alum floc, thereby greatly saving the medicament using amount, finally ensuring that P in a water phase after the magnetic coagulation treatment is less than 0.2mg/L and F is less than 1mg/L, simultaneously adopting the magnetic coagulation technology to avoid newly adding solid-liquid separation equipment, and effectively saving the production cost. The phosphogypsum slag warehouse leachate after the deep purification treatment meets the index requirement of class III surface water in the quality standard of surface water environment (GB 3838-2002).
4. According to the method, the proper deep purifying agent is selected, the magnetic powder is added into the deep purifying agent, the particle size of a flocculation product is controlled by adjusting the using amounts of the deep purifying agent and the magnetic powder, and blockage of the inclined tube filler is avoided.
5. In order to purify the liquid phase, a crystallization promoter, a deep purifying agent and magnetic powder are sequentially added into a reaction system, and all or part of the components are finally transferred to a calcium magnesium polyphosphate production line, so that calcium magnesium polyphosphate with higher average polymerization rate can be obtained with relatively lower energy consumption during the production of the calcium magnesium polyphosphate, and the slow release performance of the calcium magnesium polyphosphate used in the fertilizer is better.
6. The treatment process is independent of a phosphoric acid production system, avoids the phenomenon that organic matters, magnesium, fluorine and other impurities in the phosphogypsum slag warehouse leachate are reintroduced into phosphoric acid or a downstream product system, reduces the quality of the phosphogypsum slag warehouse leachate, is more suitable for the conditions that the phosphogypsum slag warehouse is far away from an enterprise production field or the service life of the slag warehouse is due, the enterprise can not digest the phosphogypsum slag warehouse leachate, and the leachate needs to be treated separately, and has important reference significance for the treatment of the phosphogypsum slag warehouse leachate of phosphorus chemical enterprises.
Drawings
FIG. 1 is a flow chart of the deep purification treatment method of the leachate of the phosphogypsum slag warehouse.
FIG. 2 is a schematic diagram of the aqueous phase procedure of crystallization fluid bed process step A.
FIG. 3 is a schematic view of the water phase process of the treatment step B of the magnetic coagulation complete equipment.
Wherein, 1-repulping tank; 2-a solid-liquid separator; 3-a crystallization fluidized bed; 4-magnetic coagulation equipment; 5-calcium magnesium polyphosphate production line; 31-a granulation zone; 32-a separation zone; 33-a clarification zone; 6-wastewater adjusting tank; 7-transferring the storage tank; 8-granular crystalline storage tank; 41-alum blossom reaction zone; a 42-acid base regulation zone; 43-a settling separation zone; 44-a recovery pump; 9-magnetic separator; 10-a screw pump; 11-regulating pool.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without inventive efforts based on the embodiments of the present invention, are within the scope of protection of the present invention.
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
The phosphogypsum slag storehouse filtration liquid advanced purification treatment in this application includes:
A. the leachate in the phosphogypsum slag reservoir overflows or is pumped into a flotation tailing pretreatment working section of calcium magnesium polyphosphate raw material, the leachate and the flotation tailings are respectively metered and then enter a repulping tank, and H is simultaneously added 2 O 2 And removing organic matters. The liquid-solid ratio in the repulping process is 2-6:1, the repulping time is 0.5-4H, the repulping temperature is 20-80 ℃, the pH of the repulping liquid is 4-5.5, and the leachate treatment capacity and H are 2 O 2 Adding the calcium polyphosphate into the slurry according to the weight ratio of 950-1200:1, performing solid-liquid separation by using a plate-and-frame filter press or a centrifugal machine after slurry washing, feeding a solid phase S into a calcium magnesium polyphosphate production section III, calcining the solid phase S with phosphoric acid to generate a calcium magnesium polyphosphate product, and feeding a liquid phase L into a magnesium removal process;
B. and B, the liquid phase L in the step A enters a crystallization fluidized bed from the bottom through a percolate adjusting tank, a crystallization promoter enters the bottom of the crystallization fluidized bed together, and lime milk is added according to the pH value of the water phase. And B, the water phase passes through a granulation area and a separation area of the crystallization fluidized bed to realize solid-liquid separation, the solid phase is a mixture of granular magnesium hydrogen phosphate and calcium hydrophosphate and is discharged from the bottom of the crystallization fluidized bed, and the solid phase is directly recycled to the flotation tailing neutralization section in the step A to be used for producing calcium magnesium polyphosphate. The liquid phase L overflows through the top of the crystallization fluidized bed to the deep purification process. The pH value of the liquid phase in the step B after being regulated by the lime milk is 5.5-6.5, the crystallization accelerator adopts loess or ceramsite or diatomite, and the ratio of the amount of water entering the crystallization fluidized bed to the amount of the crystallization accelerator is 1400-1700: 1;
c: and (C) the liquid phase L in the step (B) enters a magnetic coagulation deep purification process, which is realized by magnetic coagulation complete equipment, wherein the complete equipment consists of an alum blossom reaction and magnetic powder coagulation aiding area, a sodium hydroxide pH adjusting area, a sedimentation solid-liquid separation area and a magnetic separator. Respectively adding the liquid phase and deep purifying agent polyaluminium chloride or polyferric sulfate or aluminum sulfate and magnetic powder into an alum blossom reaction and magnetic powder coagulation assisting area, wherein the ratio of Al: the (P + F) molar ratio is controlled to be 1-9:1 or Fe: the (P + F) molar ratio is controlled to be 1-8.5:1, the reaction time is 5-90min, the stirring speed is 20-80r/min, magnetic powder is added, the reaction effect of the alum floc can be enhanced, meanwhile, the generated floc is adsorbed and settled at the bottom by the magnetic powder, the SS value of suspended matters is effectively reduced, the ratio of the addition amount of the magnetic powder to the addition amount of polyaluminium chloride, polyferric sulfate or aluminum sulfate is 1:2.5-1:10, the pH of a solid-liquid mixture after reaction is adjusted to 6.5-9 by a sodium hydroxide solution, and then the solid-liquid mixture enters a settling separation zone with an inclined tube filler to realize solid-liquid separation, wherein the installation angle of the inclined tube filler is 40-85 degrees, the material is PP or PE or PVC, the ratio of the arrangement area to the cross-sectional area of the settling separation zone is 0.3-0.8:1, and the tube diameter phi of the inclined tube filler is 50-80. And the liquid phase 10 overflows into a finished product water tank area to be used as surface supplementary water or process water for recycling to a production process, the solid phase at the bottom layer is thick slurry C, the thick slurry C is sent into a magnetic separator by a screw pump, the recovered magnetic powder is added into a magnetic powder coagulation aiding area again, and a small amount of thick slurry C is sent back to a calcium magnesium polyphosphate raw material flotation tailing neutralization section.
Example 1:
taking the phosphogypsum slag warehouse leachate, wherein the relevant detection indexes are as follows:
pumping the phosphogypsum slag library percolate into a flotation tailing repulping tank by a pump, simultaneously adding flotation tailing and hydrogen peroxide, controlling the liquid-solid ratio in the repulping process to be 2:1, repulping for 1H, repulping temperature to be 25 ℃, repulping pH4, and treating amount and H of the percolate 2 O 2 The addition ratio is 990:1, solid-liquid separation is carried out by adopting a plate-and-frame filter press after repulping and washing, a calcium magnesium polyphosphate product is generated by calcining a solid phase and phosphoric acid, and a liquid phase enters a fluidized bed crystallization process.
Repulping the washed liquid phase with flotation tailings with Ca (OH) 2 Lime milk with the mass concentration of 4% enters a percolate adjusting tank, the pH value of a liquid phase is 5.9, the lime milk enters a crystallization fluidized bed from the bottom by a water inlet pump, loess serving as a crystallization accelerator enters the bottom of the crystallization fluidized bed, and the ratio of the amount of water entering the crystallization fluidized bed to the amount of the crystallization accelerator is 1400: 1. The water phase added with the crystallization accelerator passes through a granulation area and a separation area of a crystallization fluidized bed to realize solid-liquid separation, solid-phase granular crystals (magnesium hydrogen phosphate and calcium hydrophosphate) are discharged from the bottom of the crystallization fluidized bed, pass through a storage tank and then enter a tailing neutralization section of calcium magnesium polyphosphate raw material flotation, and the liquid phase overflows from the top of the crystallization fluidized bed and passes through a transfer storage tank to be subjected to a deep purification process.
The water phase from the crystallization process enters an adjusting tank to ensure the index stability of the water phase, and then is sent to a magnetic coagulation complete equipment by a water inlet pump, wherein the complete equipment consists of an alum blossom reaction and magnetic powder coagulation assisting area, a sodium hydroxide pH adjusting area, a sedimentation solid-liquid separation area and a magnetic separator. Adding polymeric ferric sulfate into the alum blossom reaction reagent, wherein the ratio of Fe: the (P + F) molar ratio is controlled to be 4.8:1, the reaction time is 20min, the stirring speed is 28r/min, the ratio of the addition amount of magnetic powder to the addition amount of polymeric ferric sulfate is 1:4, the pH value of a solid-liquid mixture after reaction is adjusted to 7.4 by sodium hydroxide, and then the solid-liquid mixture enters a settling separation zone with inclined tube packing to realize solid-liquid separation, wherein the installation angle of the inclined tube packing is 45 degrees, the material is PP, the ratio of the arrangement area to the sectional area of the settling separation zone is 0.4:1, and the pipe diameter phi of the inclined tube packing is 50 mm. The liquid phase of the deep purification treatment overflows into a finished product water tank area to be used as surface supplementing water, thick slurry at the bottom layer is sent into a magnetic separator by a screw pump, recovered magnetic powder is added into a magnetic powder coagulation aiding area again, and a small amount of thick slurry is sent back to a tailing neutralization section of calcium magnesium polyphosphate raw material flotation. The water phase is deeply purified by the magnetic coagulation complete equipment, and relevant detection core indexes are as follows:
example 2:
taking the phosphogypsum slag reservoir leachate, wherein the relevant detection indexes are as follows:
the phosphogypsum slag storage leachate is pumped into a flotation tailing repulping tank by a pump, meanwhile, the flotation tailing and hydrogen peroxide are added, the liquid-solid ratio in the repulping process is controlled to be 4:1, the repulping time is 0.8H, the repulping temperature is 40 ℃, the pH value of the repulping liquid is 5, the treatment capacity of the leachate and the H 2 O 2 The adding amount ratio is 1000:1, a plate-and-frame filter press is adopted for solid-liquid separation after pulp washing, a calcium magnesium polyphosphate product is generated by calcining a solid phase and phosphoric acid, and a liquid phase enters a fluidized bed crystallization process.
Repulping the washed liquid phase with flotation tailings with Ca (OH) 2 Lime milk with the concentration of 5.5 percent enters a percolate adjusting tank, the pH value of a liquid phase is 6.1, the lime milk enters a crystallization fluidized bed from the bottom by a water inlet pump, loess serving as a crystallization accelerator enters the bottom of the crystallization fluidized bed, and the ratio of the amount of the water entering the crystallization fluidized bed to the addition amount of the crystallization accelerator is 1620: 1. The water phase added with the crystallization accelerator passes through a granulation area and a separation area of a crystallization fluidized bed to realize solid-liquid separation, the solid phase is granular crystals (magnesium hydrogen phosphate and calcium hydrophosphate) and is discharged from the bottom of the crystallization fluidized bed, the granular crystals pass through a storage tank and enter a tailing flotation neutralization section of calcium magnesium polyphosphate raw materials, and the liquid phase overflows from the top of the crystallization fluidized bed and passes through a transfer storage tank to be subjected to a deep purification process.
The water phase from the crystallization process enters an adjusting tank to ensure the index stability of the water phase, and then is sent to a magnetic coagulation complete equipment by a water inlet pump, wherein the complete equipment consists of an alum blossom reaction and magnetic powder coagulation assisting area, a sodium hydroxide pH adjusting area, a sedimentation solid-liquid separation area and a magnetic separator. Adding polymeric ferric sulfate into the alum blossom reaction reagent, wherein the ratio of Fe: the molar ratio of (P + F) is controlled to be 6:1, the reaction time is 40min, the stirring speed is 26r/min, the ratio of the addition amount of magnetic powder to the addition amount of polymeric ferric sulfate is 1:5, the pH value of a solid-liquid mixture after reaction is adjusted to 7.0 by sodium hydroxide, and then the mixture enters a settling separation zone with inclined tube packing to realize solid-liquid separation, wherein the installation angle of the inclined tube packing is 48 degrees, the material is PP, the ratio of the arrangement area to the sectional area of the settling separation zone is 0.5:1, and the pipe diameter phi of the inclined tube packing is 60 mm. The liquid phase of the deep purification treatment overflows into a finished product water tank area to be used as surface supplementing water, thick slurry at the bottom layer is sent into a magnetic separator by a screw pump, recovered magnetic powder is added into a magnetic powder coagulation aiding area again, and a small amount of thick slurry is sent back to a flotation tailing neutralization section of a calcium magnesium polyphosphate raw material. The water phase is subjected to deep purification treatment by magnetic coagulation complete equipment, and relevant detection core indexes are as follows:
example 3:
taking the phosphogypsum slag reservoir leachate, wherein the relevant detection indexes are as follows:
pumping the phosphogypsum slag library percolate into a flotation tailing repulping tank by a pump, simultaneously adding flotation tailing and hydrogen peroxide, controlling the liquid-solid ratio in the repulping process to be 6:1, repulping for 4 hours, repulping temperature to be 80 ℃, repulping liquid pH5.3, and treating capacity and H of the percolate 2 O 2 The adding amount ratio is 1200:1, the solid-liquid separation is carried out by adopting a plate-and-frame filter press after repulping and washing, the solid phase and phosphoric acid (w (P2O5) are mixed and reacted for 1h according to the mass ratio of 1:3.5, the solid-liquid separation is carried out to obtain the solid phase, then the solid phase is calcined for 3h at 260 ℃ to obtain the calcium magnesium polyphosphate product with the polymerization rate of 81.3%, and the liquid phase enters the fluidized bed crystallization process.
Repulping the washed liquid phase with flotation tailings with Ca (OH) 2 Lime milk with concentration of 8% enters a percolate adjusting tank, the pH of a liquid phase is 6.3, the lime milk enters a crystallization fluidized bed from the bottom by a water inlet pump, and crystallization accelerator loess enters the bottom of the crystallization fluidized bed and enters a crystallization flowThe ratio of the amount of water in the fluidized bed to the amount of the crystallization promoter added is 1700: 1. The water phase added with the crystallization accelerator passes through a granulation area and a separation area of a crystallization fluidized bed to realize solid-liquid separation, the solid phase is granular crystals (magnesium hydrogen phosphate and calcium hydrophosphate) and is discharged from the bottom of the crystallization fluidized bed, the granular crystals pass through a storage tank and enter a tailing flotation neutralization section of calcium magnesium polyphosphate raw materials, and the liquid phase overflows from the top of the crystallization fluidized bed and passes through a transfer storage tank to be subjected to a deep purification process.
The water phase from the crystallization process enters an adjusting tank to ensure the index stability of the water phase, and then is sent to a magnetic coagulation complete equipment by a water inlet pump, wherein the complete equipment consists of an alum blossom reaction and magnetic powder coagulation assisting area, a sodium hydroxide pH adjusting area, a sedimentation solid-liquid separation area and a magnetic separator. Adding polymeric ferric sulfate into the alum blossom reaction reagent, wherein the ratio of Fe: the molar ratio of (P + F) is controlled to be 7.3:1, the reaction time is 80min, the stirring speed is 40r/min, the ratio of the addition amount of magnetic powder to the addition amount of polymeric ferric sulfate is 1:7, the pH value of a solid-liquid mixture after reaction is regulated to be 7.2 by sodium hydroxide, and then the solid-liquid mixture enters a settling separation zone with inclined tube packing to realize solid-liquid separation, wherein the installation angle of the inclined tube packing is 55 degrees, the material is PP, the ratio of the arrangement area to the sectional area of the settling separation zone is 0.6:1, and the pipe diameter phi of the inclined tube packing is 80 mm. The liquid phase of the deep purification treatment overflows into a finished product water tank area to be used as surface supplementing water, thick slurry at the bottom layer is sent into a magnetic separator by a screw pump, recovered magnetic powder is added into a magnetic powder coagulation aiding area again, and a small amount of thick slurry is sent back to a flotation tailing neutralization section of a calcium magnesium polyphosphate raw material. The water phase is deeply purified by the magnetic coagulation complete equipment, and relevant detection core indexes are as follows:
comparative example:
the only difference from example 3 is that the solid phase separated by the plate and frame filter press in step A and phosphoric acid (w (P) are separated without adding a crystallization promoter into the crystallization fluidized bed, performing solid-liquid separation by the plate and frame filter press without using a magnetic separation device, and without adding magnetic powder in step C 2 O 5 ) 20-25%) according to the mass ratio of 1:3.5, carrying out mixed reaction for 1h, carrying out solid-liquid separation to obtain a solid phase, and calcining at 260 ℃ for 3h to obtain polyThe synthetic rate of the calcium magnesium polyphosphate product is 76.7 percent.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for elements thereof.
Claims (10)
1. The device for deep purification treatment of the phosphogypsum slag warehouse leachate is characterized in that: including repulping tank, solid-liquid separator, crystallization fluidized bed and the magnetic coagulation equipment that connects gradually, the magnetic coagulation equipment is including alum blossom reaction zone, acid-base regulation district and the sedimentation separation district that communicates in proper order, and wherein alum blossom reaction zone and crystallization fluidized bed's liquid phase exit linkage are provided with the clarified water export on the sedimentation separation district, and sedimentation separation district bottom is provided with the flocculation and precipitation export.
2. The phosphogypsum slag warehouse leachate deep purification treatment equipment according to claim 1 is characterized in that: the crystallization fluidized bed is provided with a clarification zone, a separation zone and a granulation zone from top to bottom in sequence, a liquid phase outlet of the solid-liquid separator is connected to the bottom of the crystallization fluidized bed, a crystallization accelerator feeding port is further arranged at the bottom of the granulation zone, the granulation zone is connected with a granular crystal storage tank, and a liquid phase outlet is arranged on the clarification zone.
3. The phosphogypsum slag warehouse leachate deep purification treatment equipment according to claim 1 is characterized in that: the settling separation area is internally provided with an inclined tube filler, the installation angle of the inclined tube filler is 45-55 degrees, the ratio of the arrangement area of the inclined tube filler to the cross-sectional area of the settling separation area is 0.4-0.6:1, and the pipe diameter phi of the inclined tube filler is 50-80 mm.
4. The method for deeply purifying the leachate of the phosphogypsum slag warehouse is characterized by comprising the following steps of:
step A, placing phosphogypsum slag warehouse leachate, calcium magnesium polyphosphate raw material flotation tailings and hydrogen peroxide into a repulping tank, and performing solid-liquid separation on the mixture after repulping;
b, transferring the liquid phase obtained in the step A to a crystallization fluidized bed, and transferring the liquid phase from which the crystals are removed to magnetic coagulation equipment;
and step C, adding a deep purifying agent and magnetic powder into the magnetic coagulation equipment, adjusting the pH to 6.5-9.0, and then, allowing the mixture to enter a settling separation zone with inclined tube packing to realize solid-liquid separation, thereby obtaining clarified water.
5. The method for deeply purifying the leachate of the phosphogypsum slag warehouse according to claim 4, which is characterized by comprising the following steps: in the step A, the liquid-solid mass ratio is 2-6:1, the repulping time is 0.5-4H, the repulping temperature is 20-80 ℃, the pH of the repulping liquid is 4-5.5, and the leachate and H 2 O 2 The volume ratio is 950-.
6. The device and the method for deep purification treatment of leachate of the phosphogypsum slag warehouse according to claim 4 are characterized in that: and step B, adding a crystallization promoter into the liquid phase, and adjusting the pH value to 5.5-6.5 by using lime milk.
7. The equipment and the method for deep purification treatment of the leachate of the phosphogypsum slag warehouse according to claim 6 are characterized in that: the crystallization accelerator is loess, ceramsite or diatomite, and the mass ratio of the liquid phase entering the crystallization fluidized bed to the crystallization accelerator is 1400-1700: 1.
8. The method for deeply purifying the leachate of the phosphogypsum slag warehouse according to claim 4, which is characterized by comprising the following steps: the deep purifying agent is polyaluminium chloride, polyferric sulfate or aluminum sulfate, and in the magnetic coagulation equipment, the ratio of Al: (P + F) molar ratio of 1-9:1 or Fe: the molar ratio of (P + F) is 4.5-7.5:1, the reaction time is 20-80 min, and the stirring speed is 25-40 r/min.
9. The method for deeply purifying the leachate of the phosphogypsum slag warehouse according to claim 4, which is characterized by comprising the following steps: the mass ratio of the magnetic powder to the deep purifying agent is 1:4-1: 7.
10. The method for deeply purifying the leachate of the phosphogypsum slag warehouse according to claim 4, which is characterized by comprising the following steps: and C, transferring the solid phase obtained in the step B and/or the step C to a repulping tank, and repeating the step A.
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| CN103303884A (en) * | 2013-05-27 | 2013-09-18 | 瓮福（集团）有限责任公司 | Method for treating phosphorus concentrates and recovering phosphorus by using phosphogypsum slag dump pool water |
| CN207130082U (en) * | 2017-04-26 | 2018-03-23 | 广东卓信环境科技股份有限公司 | Magneto separate integrated apparatus |
| CN209113637U (en) * | 2018-10-30 | 2019-07-16 | 中国五环工程有限公司 | Gypsum stack percolation liquid treating system |
| CN110627177A (en) * | 2019-09-26 | 2019-12-31 | 北京朗新明环保科技有限公司 | Fluorine removal method for fluorine-containing wastewater and fluidized bed crystallization separator for fluorine removal |
| CN113336356A (en) * | 2021-05-08 | 2021-09-03 | 武汉工程大学 | Phosphogypsum leachate recycling treatment and utilization method |
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