CN115340204B - Continuous production type defluorination system based on fluidized bed - Google Patents
Continuous production type defluorination system based on fluidized bed Download PDFInfo
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- CN115340204B CN115340204B CN202210740878.3A CN202210740878A CN115340204B CN 115340204 B CN115340204 B CN 115340204B CN 202210740878 A CN202210740878 A CN 202210740878A CN 115340204 B CN115340204 B CN 115340204B
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- 238000010924 continuous production Methods 0.000 title claims abstract description 16
- 238000006115 defluorination reaction Methods 0.000 title claims description 14
- 239000013078 crystal Substances 0.000 claims abstract description 175
- 238000002425 crystallisation Methods 0.000 claims abstract description 144
- 230000008025 crystallization Effects 0.000 claims abstract description 143
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 124
- 239000011737 fluorine Substances 0.000 claims abstract description 124
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000002351 wastewater Substances 0.000 claims abstract description 57
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 46
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 43
- 239000000376 reactant Substances 0.000 claims abstract description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 27
- MPDDQFGQTCEFIX-UHFFFAOYSA-N [F].[Ca] Chemical compound [F].[Ca] MPDDQFGQTCEFIX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 239000012530 fluid Substances 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 51
- 239000007787 solid Substances 0.000 claims description 33
- 239000012629 purifying agent Substances 0.000 claims description 31
- 238000003860 storage Methods 0.000 claims description 30
- 238000010992 reflux Methods 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 238000005273 aeration Methods 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 14
- 230000001939 inductive effect Effects 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000001471 micro-filtration Methods 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- -1 fluorine ions Chemical class 0.000 abstract description 35
- 239000000411 inducer Substances 0.000 abstract description 17
- 239000012071 phase Substances 0.000 description 20
- 229910019142 PO4 Inorganic materials 0.000 description 16
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 14
- 229910001424 calcium ion Inorganic materials 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 13
- 230000001105 regulatory effect Effects 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 235000011116 calcium hydroxide Nutrition 0.000 description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- 159000000007 calcium salts Chemical class 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 150000000703 Cerium Chemical class 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000000429 assembly Methods 0.000 description 4
- 230000000712 assembly Effects 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 159000000009 barium salts Chemical class 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000010436 fluorite Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine 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
-
- 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
- C02F2101/101—Sulfur 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
- C02F2101/105—Phosphorus compounds
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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 discloses a continuous production type fluorine removal system based on a fluidized bed, which can treat fluorine-containing wastewater with a large fluorine concentration range, can treat fluorine-containing wastewater with a fluorine ion concentration of 200-3000 mg/L, generates a crystallization inducer by adding a crystallization reactant in an induced crystallization formation area at the lower part of the fluidized bed, and enables the fluorine concentration of a crystal growth area to be maintained in a metastable area of calcium fluoride stably by controlling the fluorine concentration of fluorine ions and the calcium-fluorine ratio, so that fluctuation of fluorine ions in the crystal growth area caused by the fluorine concentration of water inlet is avoided.
Description
Technical Field
The invention relates to a fluidized bed-based continuous production type fluorine removal system.
Background
Hydrofluoric acid is one of the most applied chemical substances in the manufacturing process of products in the electronic industry, and fluorine-containing wastewater generated by hydrofluoric acid and other mixed acid and alkali has the characteristics of large water quantity and high fluorine concentration, and meanwhile, the wastewater also contains other pollutants such as sulfate radical, phosphate radical, silicon, ammonia and the like, so that the wastewater needs to be properly treated. Compared with the common chemical precipitation or coagulating sedimentation method for treating the fluorine-containing wastewater, the method adopts the induced crystallization fluidized bed to carry out fluorine recycling recovery on the fluorine-containing wastewater, can solve the problem of fluorine-containing sludge disposal, and alsoCan produce artificial fluorite (also called fluorite, the main component is calcium fluoride, the chemical formula is CaF) 2 ) Has better application potential and can relieve the shortage problem of fluorite.
The fluidized bed induced crystallization technology is adopted, and calcium ions and fluorine ions are controlled in a metastable zone or a lower supersaturation degree in a reactor, so that the two ions cannot spontaneously nucleate, but grow on the surface of the added seed crystal, the granular calcium fluoride crystals with larger particle size can be obtained, and the resource utilization value is improved. The crystal seeds adopted in the common fluidized bed defluorination have the particles such as quartz sand and calcium carbonate, and have the advantages of low price, various sizes and the like, but the purity of the obtained calcium fluoride crystals can be reduced due to the introduction of the quartz sand and the calcium carbonate. The presence of impurity ions in the fluorine-containing wastewater also affects the purity of the crystallized product and the quality of the effluent. Liu Hongfei et al [1]Research shows that sulfate radical, silicon, phosphate radical and the like contained in the wastewater are easy to react with calcium ions to form precipitate, the removal of fluorine ions is interfered, meanwhile, the crystallization quality of calcium fluoride is reduced, and the content of suspended matters in the effluent is improved. The common fluidized bed defluorination process needs to operate according to the steps of seed crystal adding, water inlet reaction, operation stopping, crystal discharging, seed crystal adding again and the like, and has complicated operation, and the obtained calcium fluoride crystals have different quality due to different batches. When lime or calcium hydroxide is added as crystallization reactant, ca (OH) is easily formed in water due to the quality of the catalyst 2 The crystallization is easy to break, the grain size of the product is difficult to improve, and the effluent easily contains a large amount of fine suspended matters, so that the quality of the effluent is difficult to reach the standard. In addition, when the fluidized bed induces crystallization to treat fluorine-containing wastewater, the fluorine concentration of the inflowing water needs to be strictly controlled (the fluorine concentration of the inflowing water is generally 100-300 mg/L), the crystal seeds need to be periodically thrown in, the operation is stopped, the crystallization is discharged, and the effluent needs to be further thrown in a coagulant for deep fluorine removal, so that the engineering value of fluorine recycling is weakened to a certain extent.
Disclosure of Invention
The invention aims to: the invention aims to provide a continuous production type defluorination system based on a fluidized bed, which does not need to additionally (externally) add seed crystals in the process of inducing crystallization of the fluidized bed, and the calcium fluoride seed crystals are formed by inducing self-crystallization in the fluidized bed in a partitioning way, then calcium fluoride crystal grains with a certain particle size are grown in a growth area, and the purity of the obtained calcium fluoride crystal grains is high; the invention overcomes the defect that when the existing fluidized bed is adopted to induce crystallization to treat fluorine-containing wastewater, the concentration of fluorine in inlet water needs to be strictly controlled, the invention can treat the fluorine-containing wastewater with the concentration of 200-3000 mg/L, and continuous production can be realized without periodically throwing seed crystals and stopping operation and discharging crystallization, and the effluent does not need to be further added with coagulant for deep defluorination, so that no fluorine-containing sludge is generated in the whole process.
The technical scheme is as follows: the invention relates to a fluidized bed-based continuous production type fluorine removal system, which comprises a fluorine-containing wastewater tank, a tubular mixer, a ceramic membrane filter, a fluidized bed, a crystallization purifying agent storage tank, a crystallization reactant storage tank, an aeration fan, a multi-medium filter and a fluorine removal resin tower, wherein the fluorine-containing wastewater tank is connected with the tubular mixer; the fluidized bed is internally provided with a fluid director which divides the fluidized bed into an induced crystallization forming area and a crystal growing area, wherein the induced crystallization forming area is positioned below the fluid director, the crystal growing area is positioned above the fluid director, and a solid-liquid separation area is also arranged above the crystal growing area; the fluorine-containing wastewater tank and the crystallization purifying agent storage tank are respectively connected with a tubular mixer through a pump, the effluent of the tubular mixer flows through a ceramic membrane filter and then enters an induced crystallization forming area of the fluidized bed, the crystallization reactant storage tank is connected with two chemical feeding branches, the crystallization reactant storage tank is connected with the induced crystallization forming area of the fluidized bed through a first chemical feeding branch, and an aeration pipe connected with an aeration fan stretches into the induced crystallization forming area at the bottom of the fluidized bed; part of liquid in the solid-liquid separation area flows into the multi-medium filter and then flows through the fluorine removal resin tower to be discharged, and the other part of liquid in the solid-liquid separation area flows back into the flow director, and a second dosing branch of the crystallization reactant storage tank also extends into the flow director; the fluid director is enclosed by a plurality of fan-shaped blades and forms a cone structure, the top opening of the fluid director is fixedly connected with the bottom plate, the outer diameter of the top opening of the fluid director is consistent with the inner diameter of the fluidized bed, the two fan-shaped blades are spliced into a fan-shaped blade combination, a V-shaped included angle is formed by the fan-shaped blade combination, a gap is arranged between the adjacent fan-shaped blade combinations, liquid in a crystallization formation area is induced below the fluid director to reach a crystal growth area through the gap, wherein the crystal is expanded and fluidized under the action of water power, crystal seeds are provided for crystallization reactants and residual fluoride ions of the liquid to perform crystallization reaction, and the crystal growing in the crystal growth area falls into the fluid director and is sent into a crystal receiving groove outside the fluidized bed through a pipeline connected with the fluid director.
Wherein, the crystallization reactant storage tank is filled with 30 percent of calcium chloride solution by mass percent. CaF when calcium salt is quicklime and slaked lime 2 The precipitate gradually wraps Ca (OH) 2 The particles are settled together, so that the reaction cannot be completed, the dosage of the actual crystallization reactant is far higher than the theoretical value, and the actual dosage of calcium salt is greatly increased, therefore, compared with suspension liquid reactants such as quicklime, calcium hydroxide and the like, the calcium chloride solution is selected, on the one hand, a large amount of residual lime or calcium hydroxide is not precipitated during precipitation or crystallization, so that the dosage is high, on the other hand, the solubility of calcium chloride is high, the concentration of calcium ions in the solution can be effectively improved, the solubility of calcium fluoride is reduced by utilizing the homoionic effect (the concentration of calcium chloride in the system is higher, the solubility of calcium fluoride is reduced, and thus calcium fluoride precipitation is continuously formed), and the fluorine content in the solution is greatly reduced.
In the crystallization-inducing formation area, a chemical adding pipe connected with a crystallization reactant storage tank is arranged opposite to a water inlet pipe connected with a ceramic membrane filter, so that calcium salt and water are fully mixed.
The aeration pipelines are uniformly distributed at the bottom of the fluidized bed, the air vents of the aeration pipelines are downwards arranged, the air vents are downwards arranged and are not easy to be blocked by solids, calcium fluoride solids upwards flow under the stirring of air flow to form a gas-liquid-solid three-phase fully mixed fluid, and solid deposition is effectively prevented.
Wherein, the crystallization purifying agent storage tank is filled with crystallization purifying agent. The crystallization purifying agent is prepared by the following method: mixing barium oxide with purity of 99.99% and cerium oxide powder according to a mass ratio of 10-20:1, grinding to below 300 meshes, dissolving the mixed powder in pure water with an oxide concentration of 100g/L, stirring at 80-120 ℃, rapidly (rotating at 600-1000 rpm) pulping for 2-3 hours, reducing the temperature to 15 ℃ and stirring for 1-3 hours, filtering by using a PTFE microfiltration membrane with a membrane diameter of 0.45 mu m, and obtaining a clear solution (the steps of heating, rapid stirring, filtering and the like are all used for improving the solubility of barium salt and cerium salt in water); and (3) adding 0.5-2 mol/L of 38wt% hydrochloric acid, 0.4-0.8 mol/L of ammonium chloride and 0.5-2 mol/L of magnesium chloride into the clarified liquid in sequence, heating the mixed material to 40-60 ℃, stirring and reacting for 1-2 hours, and cooling to 25 ℃ after the reaction to obtain the crystallization purifying agent.
SO4 in fluorine-containing wastewater 2- 、PO4 3- Will be combined with Ca 2+ The precipitate generated by the reaction not only affects the purity of calcium fluoride crystal, but also reduces F - The removal rate of the water outlet of the system is affected. SO4 present in solution 2- Can interfere with the removal of fluoride ions, SO4 2- The higher the concentration, the higher the residual fluoride ion concentration; PO4 in wastewater 3- The concentration also produces interference on the defluorination effect, ca 3 (PO 4 ) 2 The precipitate formed faster than CaF 2 The rate of precipitate formation, thereby causing the growth of calcium fluoride crystals to be subjected to Ca 3 (PO 4 ) 2 Influence of precipitation, and PO4 3- The higher the concentration, the higher the residual fluoride ion concentration. Barium and cerium salts are used in combination with SO4 in crystallization purificants 2- 、PO4 3- Generating a precipitate to remove the impurity SO4 in the fluorine-containing wastewater 2- 、PO4 3- The method comprises the steps of carrying out a first treatment on the surface of the The magnesium chloride is used for generating a precipitate with silicon so as to remove impurity silicon in the fluorine-containing wastewater; ammonium chloride and hydrochloric acid are used as a dissolving agent, so that the solubility of barium salt and cerium salt is improved, insoluble particles of barium oxide and cerium oxide are avoided in the purifying agent, and introduced ammonium ions are removed by heating after mixing.
The deflector comprises eight groups of fan-shaped blade combinations, each group of fan-shaped blade combination is formed by splicing two fan-shaped blades, one side with the same side length is welded and fixed by 165-degree included angles, the bottom edges of the two fan-shaped blades are fixed on a bottom plate, V-shaped included angles (the V-shaped included angles form a flow guiding valley, and the valley bottom is sealed) between the two fan-shaped blades are protruded towards the direction away from the center of a fluidized bed, the eight groups of fan-shaped blade combinations are uniformly distributed on the bottom plate along the center of the fluidized bed in a circumference manner to form a peak-valley staggered form, the fan-shaped blades corresponding to the adjacent fan-shaped blade combinations are staggered up and down, and gaps (flow guiding peaks are formed at the gaps) are formed between the two fan-shaped blade combinations. The flow guide device is generally conical, flow guide peaks are arranged as side seams, gas-liquid-solid three-phase fluid in the induced crystallization formation area enters the crystal growth area from the side seams in a rotational flow mode, the purging effect of the rotational flow and the entrainment effect of high-speed backflow drive crystals with insufficient maturity in the flow guide device to expand, fluidization crystallization is carried out, mature crystals with the particle size of 500-600um slide down to a bottom mature crystal collecting tank along flow guide valleys, a backflow water outlet is 10-30cm higher than the collecting tank, and the mature crystals in the collecting tank cannot contact gas and liquid with larger flow and can not continue to grow.
Wherein, the bottom of the deflector is connected with two pipelines, one pipeline is a connecting pipe, the outlet section of the connecting pipe is positioned at the center of the deflector, the height of the outlet of the connecting pipe from the bottom plate of the deflector is 10 cm to 30cm, and the other end of the connecting pipe is connected with a supernatant return pipe; the other pipeline is a crystal discharge pipe, the pipe orifice of the crystal discharge pipe is welded at the lowest part of the flow director, the crystal discharge pipe extends out of the fluidized bed and is connected with the crystal receiving groove, and when the pneumatic valve is opened, the mature crystal in the flow director can automatically slide into the crystal receiving groove.
The included angle between the V-shaped included angle and the horizontal plane is 58 degrees, namely the fan-shaped blade combination is obliquely fixed on the bottom plate with the horizontal plane, the included angle between the connecting line of the two fan-shaped blades and the horizontal plane is 58 degrees, the V-shaped included angle is used for enabling mature crystals to slide to the bottom, the angle between the V-shaped included angle and the horizontal plane is 55-65 degrees, crystal grains can effectively slide down and can be converged to the bottom of a cone, the 58 degrees are suitable for crystals with the diameter of 500-600um to achieve good sliding speed, the included angle between the gap and the horizontal plane is 65 degrees, the included angle between the gap and the horizontal plane is mainly used for forming a proper rotational flow direction, the width of the gap is 0.5cm, the width of the gap is mainly used for controlling the rotational flow speed of an induced crystal formation area to rise to a crystal growth area, the width of the gap needs to be ensured, and the rotational flow speed is not too high or too low.
The fluorine removal system further comprises a PLC control box and fluorine ion sensors (online fluorine ion concentration detectors) respectively positioned in an induced crystallization formation area and a crystal growth area, metering pumps are respectively arranged on a water inlet pipeline, a first dosing branch, a second dosing branch and a reflux branch, the fluorine ion sensors in the induced crystallization formation area and the crystal growth area, the metering pumps on each branch and a starting valve on a crystal discharge pipe are respectively connected with the PLC control box through cables, the PLC control box controls the opening of the water inlet pipeline and the opening of the metering pumps on the first dosing branch through the fluorine ion sensors in the induced crystallization formation area, so that the calcium fluorine ratio of the induced crystallization formation area is 0.2-0.38, and the fluorine ion concentration in gas-liquid-solid three-phase fluid entering the crystal growth area after reaction is 200-500mg/L; the PLC control box controls the opening of the metering pumps on the second dosing branch and the return branch through the fluorine ion sensor in the crystal growth area, and controls the calcium-fluorine ratio in the mixed liquid of the return water, the crystallization reactant and the gas-liquid-solid three-phase fluid to be 0.45-0.52.
The specific operation process of the defluorination system comprises the following steps: regulating pH of fluorine-containing wastewater in a fluorine-containing wastewater pool to be 6-8, conveying the fluorine-containing wastewater to a tubular mixer by a metering pump I, conveying a crystallization purifying agent to the tubular mixer on a water inlet pipeline by the metering pump II, enabling metal ions in the crystallization purifying agent to react preferentially with sulfate radicals, silicate radicals, phosphate radicals and other impurity ions in the fluorine-containing wastewater to form a solid mixture, filtering the solid mixture by a ceramic membrane filter, then entering an induced crystallization forming area, conveying a calcium chloride solution into the induced crystallization forming area of a fluidized bed by a crystallization reactant storage tank 9 through a first chemical adding branch, arranging a pipeline of the first chemical adding branch in the fluidized bed by adopting a downward water distribution pipe opposite to a water outlet of a pipeline in the fluidized bed by a fluorine-containing wastewater inlet pipeline, and forming turbulence so as to facilitate rapid mixing; the calcium-fluorine ratio of the induced crystallization forming area is controlled to be 0.2-0.38 by the opening of the fluorine ion sensor, the metering pump I and the metering pump III on the first dosing branch, and on one hand, calcium fluoride seed crystals can be generated by the calcium-fluorine ratio, and on the other hand, the fluorine concentration in the gas-liquid-solid three-phase fluid can be reduced to 200-500mg/L; this region maintains a calcium to fluorine ratio of 0.2 to 0.38, and an excess of fluoride ions is present in the supersaturated region of calcium fluoride, which nucleates with calcium ions to form calcium fluoride solids, which act as crystal inducers in the crystal growth region. The stirring of the airflow of the aeration pipeline drives the calcium fluoride solids to flow upwards to form gas-liquid-solid three-phase fluid, so that the solids are effectively prevented from depositing. The residual fluorine concentration in the three-phase fluid is 200-500mg/L, which can reduce the solid content of the induced crystallization formation area and enable most fluorine to form mature crystals in the crystal growth area. The gas-liquid-solid three-phase fluid flows upwards, the flow guiding peak rotational flow of the flow director enters the crystal growing region, the reflux supernatant of the solid-liquid separation region is conveyed to the conical bottom part of the flow director through a metering pump IV to form 30-60 m/h high-speed fluid, and the calcium chloride solution is conveyed to the position above the crystal outlet of the flow director through the metering pump V, so that the calcium-fluorine ratio of the crystal growing region is 0.45-0.52, and the reaction region of calcium fluoride in the crystal growing region is controlled. If the concentration of the fluorine ions is too high in the crystal growth area, the reflux water, the crystallization reactant and the rotational flow liquid at the gap are rapidly mixed, the concentration of the fluorine ions and the crystallization reactant in the crystal growth area can be regulated by the reflux quantity, the calcium ions and the fluorine ions in the system are maintained in a metastable area of calcium fluoride and cannot spontaneously nucleate, the fluorine ions and the calcium ions are adsorbed to the surface of the crystallization inducer under the action of thermodynamic irregular movement of molecules and intermolecular attraction, and then react on the surface of the crystallization inducer to become a part of the crystallization inducer, so that the crystallization inducer is promoted to grow to form sandy calcium fluoride. In the crystal growth area, the rising flow rate of the system can be regulated by the reflux quantity, so that crystals are fluidized and expanded under the action of upward impact of gravity and water power, and along with the growth of the crystals, the gravity of the more mature crystals is larger than the buoyancy, and the crystals fall to the V-shaped valley of the flow director, and as the flow director is in an inverted cone shape, the smaller the downward flow area is, the purging effect of high-speed reflux and the entrainment effect of the rotational flow drive part of crystals with the particle size smaller than 500um upwards, so that the crystals continue to grow. The crystals with the particle size of 500-600um flow to the inclined collecting tank at the bottom of the cone along with the trough seam of the flow director. The collecting tank has no impact of three-phase rotational flow and backflow water, and the liquid flow is small, so that crystals in the tank can not continue to grow up, and the size of the crystals is maintained to be 500-600um. The pneumatic valve is started and opened for 15s every 24 hours, and calcium fluoride crystals with the particle size of 500-600um are discharged. When the pneumatic valve is opened, the water inlet and the backflow of the fluidized bed are not required to be stopped, and the backflow water outlet is 10-30cm higher than the bottom grain outlet, so that the backflow has no influence on the discharge of the bottom grains, only partial liquid can be driven to be discharged, and the liquid and the filtrate for washing out crystals can flow back to the fluorine-containing wastewater pool. The upper part of the crystal growth area is a solid-liquid separation area with gradually enlarged overflow area, the fluid flow speed in the area is reduced, and the gas phase and the liquid phase are gradually separated. The reflux water outlet is positioned in the middle of the solid-liquid separation area, so that the reflux water is ensured to contain no large particles. The fluorine concentration of the liquid clarified at the top is less than 15mg/L, the turbidity is less than 5NTU, the water pressure of the effluent water of the fluidized bed is utilized to automatically flow to a multi-medium filter, the multi-medium filter is utilized to remove the residual suspended matters, the effluent water of the multi-medium filter enters a resin tower, the fluorine ions in the water are adsorbed by utilizing the aluminum-containing groups of the resin, the effluent water of the resin tower is stably treated until the fluorine ion concentration in the effluent water is less than 1mg/L, and the resin concentrate water flows back to a fluorine-containing wastewater pool.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable technical effects:
(1) Before the fluorine-containing wastewater enters the fluidized bed, firstly removing impurity ions which influence the purity of calcium fluoride crystals from sulfate radicals, silicate radicals and phosphate radicals in the fluorine-containing wastewater by using a crystallization purifying agent, and finally, on one hand, effectively improving the effect of removing the fluorine ions by a calcium salt method in the fluidized bed, and on the other hand, forming calcium fluoride solids with the purity higher than 99.7%;
(2) The invention can treat fluorine-containing wastewater with large fluorine concentration range, can treat fluorine-containing wastewater with fluorine ion concentration of 200-3000 mg/L, generates a crystallization inducer by adding crystallization reactant in an induced crystallization forming area at the lower part of a fluidized bed, and enables the fluorine concentration range of entering a crystal growing area to be 200-500mg/L by controlling the fluorine ion concentration and the calcium-fluorine ratio, so that the crystal growing area is stably maintained in a metastable area of calcium fluoride, and the fluctuation of fluorine ions in the crystal growing area caused by the fluorine concentration of water inlet is avoided;
(3) According to the invention, the fluid bed is divided into the induced crystallization forming area and the crystal growing area by arranging the fluid director in the fluid bed, the fluid director is used as a boundary, calcium fluoride which is supersaturated in the induced crystallization forming area and spontaneously nucleates calcium ions and fluorine ions is used as a crystal inducer, and the calcium fluoride automatically flows up to the crystal growing area and is positioned in a metastable area of the calcium fluoride through a reflux quantity control system, so that the calcium ions and the fluorine ions are crystallized and grown on the inducer, thereby realizing self-generation seed crystal and induced crystallization defluorination, and no additional seed crystal is needed; on the other hand, continuous production of the system is realized by utilizing the flow guider and the pneumatic valve, water inlet and backflow are not required to be stopped in the process of collecting and discharging crystals, the grain size of the crystals is concentrated, the bottom of the collecting tank is inclined towards the transistor discharge, the transistor discharge is provided with the pneumatic gate valve, mature crystal seeds can be automatically opened and closed according to the setting timing, the grain size of the crystals flowing into the collecting tank is 500-600um, the purity and grain size of fluorine recycling products are ensured, and water inlet and backflow are not required to be stopped when the crystals are discharged;
(4) The fluorine removal system adopts fluorine removal resin to deeply remove fluorine, no sludge is generated in the whole process, the fluid bed effluent enters a resin tower after being filtered by multiple media, fluorine ions in the water are adsorbed by utilizing aluminum-containing radicals in the resin tower, and the fluorine ions in the effluent are stably treated by the resin effluent to be discharged below 1 mg/L.
Drawings
FIG. 1 is a schematic system diagram of a fluorine removal system of the present invention;
FIG. 2 is a schematic view of the structure of the deflector in the fluidized bed;
FIG. 3 is an enlarged view of a portion of the deflector;
fig. 4 is a schematic view of a fan blade assembly in a deflector.
Detailed Description
As shown in fig. 1 to 4, the fluidized bed-based continuous production type fluorine removal system of the present invention comprises a fluorine-containing wastewater tank 1, a tubular mixer 3, a ceramic membrane filter 4, a fluidized bed 12, a crystallization purifying agent storage tank 5, a crystallization reactant storage tank 9, an aeration fan 11, a multi-medium filter 14 and a fluorine removal resin tower 15; the fluidized bed 12 is internally provided with a deflector 121, the deflector 121 divides the fluidized bed 12 into an induced crystallization forming area 123 and a crystal growing area 124, wherein the induced crystallization forming area 123 is positioned below the deflector 121, the crystal growing area 124 is positioned above the deflector 121, and a solid-liquid separation area 125 is also arranged above the crystal growing area 124; the fluorine-containing wastewater tank 1 and the crystallization purifying agent storage tank 5 are respectively connected with the tubular mixer 3 through a pump, the effluent of the tubular mixer 3 flows through the ceramic membrane filter 4 and then enters the crystallization-inducing forming region 123 of the fluidized bed 12, the crystallization reactant storage tank 9 is connected with two chemical adding branches, the crystallization reactant storage tank 9 is connected with the crystallization-inducing forming region 123 of the fluidized bed through a first chemical adding branch 91, and an aeration pipe connected with the aeration fan 11 extends into the crystallization-inducing forming region 123 at the bottom of the fluidized bed 12; part of the liquid in the solid-liquid separation area 125 flows into the multi-medium filter 14 and then flows through the fluorine removal resin tower 15 to be discharged, and the other part of the liquid in the solid-liquid separation area 125 flows back into the deflector 121, and the second dosing branch 92 of the crystallization reactant storage tank 9 also extends into the deflector 121; the fluid director 121 is formed by surrounding a cone structure by a plurality of fan-shaped blades, the top opening of the fluid director 121 is fixedly connected with a bottom plate, the outer diameter of the top opening of the fluid director 121 is consistent with the inner diameter of the fluidized bed 12, gaps are arranged between the adjacent fan-shaped blades, liquid in the induced crystallization forming area 123 below the fluid director 121 reaches the crystal growing area 124 through the gaps, crystals growing in the crystal growing area 124 fall into the fluid director 121, and the crystals are sent into the crystal receiving groove 13 outside the fluidized bed 12 through a pipeline connected with the fluid director 121.
Wherein, the crystallization reactant storage tank 9 is filled with 30 percent of calcium chloride solution by mass percent. CaF when calcium salt is quicklime and slaked lime 2 The precipitate gradually wraps Ca (OH) 2 The particles are settled together, so that the reaction cannot be completed, the dosage of the actual crystallization reactant is far higher than the theoretical value, and the actual dosage of calcium salt is greatly increased, therefore, compared with suspension liquid reactants such as quicklime, calcium hydroxide and the like, the calcium chloride solution is selected, on one hand, a large amount of residual lime or calcium hydroxide is not precipitated during precipitation or crystallization, so that the dosage is high, on the other hand, the solubility of calcium chloride is high, the concentration of calcium ions in the solution can be effectively improved, the solubility of calcium fluoride is reduced by utilizing the homoionic effect, and the fluorine content is greatly reduced.
Wherein, in the crystallization-inducing formation area 123, a dosing pipe connected to the crystallization reagent reservoir 9 is disposed opposite to a water inlet pipe connected to the ceramic membrane filter 4, thereby sufficiently mixing calcium salt with the inlet water.
The aeration pipeline 111 is uniformly distributed at the bottom of the fluidized bed 12, the vent of the aeration pipeline 111 is downwards arranged, the vent is downwards arranged and is not easy to be blocked by solids, and calcium fluoride solids upwards flow under the stirring of air flow to form a gas-liquid-solid three-phase total mixed fluid, so that solid deposition is effectively prevented.
Wherein, the crystallization purifying agent storage tank 5 is filled with crystallization purifying agent. The crystallization purifying agent is prepared by the following method: mixing barium oxide with purity of 99.99% and cerium oxide powder at a mixing mass ratio of 10-20:1, grinding to below 300 meshes, dissolving the mixed powder in pure water at an oxide concentration of 100g/L, stirring at 80-120 ℃, rotating at 600-1000 rpm, pulping for 2-3 hours, reducing the temperature to 15 ℃, stirring for 1-3 hours, filtering by using a PTFE micro-filtration membrane with a pore diameter of 0.45 mu m, and obtaining a clear solution; and (3) adding 0.5-2 mol/L of 38wt% hydrochloric acid, 0.4-0.8 mol/L of ammonium chloride and 0.5-2 mol/L of magnesium chloride into the clarified liquid in sequence, heating the mixed material to 40-60 ℃, stirring and reacting for 1-2 hours, and cooling to 25 ℃ after the reaction to obtain the crystallization purifying agent. SO4 in fluorine-containing wastewater 2- 、PO4 3- Will be combined with Ca 2+ The precipitate generated by the reaction not only affects the purity of calcium fluoride crystal, but also reduces F - The removal rate of the water outlet of the system is affected. SO4 present in solution 2- Can interfere with the removal of fluoride ions, SO4 2- The higher the concentration, the higher the residual fluoride ion concentration; PO4 in wastewater 3- The concentration also produces interference on the defluorination effect, ca 3 PO 4 ) 2 The precipitate formed faster than CaF 2 The rate of precipitate formation, thereby causing the growth of calcium fluoride crystals to be subjected to Ca 3 PO 4 ) 2 Influence of precipitation, and PO4 3- The higher the concentration, the higher the residual fluoride ion concentration. Barium and cerium salts are used in combination with SO4 in crystallization purificants 2- 、PO4 3- Generating a precipitate to remove the impurity SO4 in the fluorine-containing wastewater 2- 、PO4 3- The method comprises the steps of carrying out a first treatment on the surface of the The magnesium chloride is used for generating a precipitate with silicon so as to remove impurity silicon in the fluorine-containing wastewater; ammonium chloride and hydrochloric acid are used as dissolving agents, so that the solubility of barium salt and cerium salt is improved, insoluble particles of barium oxide and cerium oxide are avoided in the purifying agent, and introduced ammonium ions are removed by heating after mixing.
The flow director 121 includes eight sets of fan-shaped blade assemblies 1211, each set of fan-shaped blade assemblies 1211 is formed by splicing two fan-shaped blades 1212, one side with the same side length is welded and fixed by 165 ° included angle, then the bottom edges of the two fan-shaped blades 1212 are fixed on a bottom plate 1213, V-shaped included angles (the V-shaped included angles form flow guiding valleys, valley bottom seals) between the two fan-shaped blades 1212 are protruded towards the direction away from the center of the fluidized bed, the eight sets of fan-shaped blade assemblies 1211 are uniformly distributed on the bottom plate 1213 along the circle center of the fluidized bed in a circumference manner to form a peak-valley staggered form, and gaps (flow guiding peaks are formed at the gaps) are formed between the two fan-shaped blades corresponding to the adjacent fan-shaped blade assemblies 1211. The deflector 121 is generally conical, the diversion peak is set as a side seam, gas-liquid-solid three-phase fluid of the induced crystallization formation area 123 enters the crystal growth area 124 from the side seam in a rotational flow manner, the purging effect of the rotational flow and the entrainment effect of high-speed backflow drive crystals with insufficient maturity in the deflector 121 to continuously fluidize and crystallize, the mature crystals with the grain size of 500-600um slide down to the bottom mature crystal collecting tank along the diversion valley, the backflow water outlet is 10-30cm higher than the collecting tank, the mature crystals in the collecting tank cannot contact gas and liquid with larger flow, and the crystals cannot continue growing. The bottom plate 1213 is inclined to the horizontal so that mature crystals falling within the collection trough can be readily discharged from the collection trough along the crystal discharge tube 129.
Wherein, the bottom of the deflector 121 is connected with two pipelines, one pipeline is a connecting pipe 130, the outlet section of the connecting pipe 130 is positioned at the center of the deflector 121, the outlet of the connecting pipe 130 is 10 cm to 30cm away from the bottom of the deflector 121, and the other end of the connecting pipe 130 is connected with a supernatant return pipe 128; the other pipe is a crystal discharge pipe 129, the orifice of the crystal discharge pipe 129 is welded at the lowest part of the deflector 121, and the crystal discharge pipe 129 extends out of the fluidized bed 12 and is connected with the crystal receiving groove 13. The V-shaped included angle is 58 degrees with the horizontal plane, the included angle between the gap and the horizontal plane is 65 degrees, and the width of the gap is 0.5cm.
The fluorine removal system further comprises a PLC control box and fluorine ion sensors respectively positioned in an induced crystallization forming area 123 and a crystal growing area 124, metering pumps are respectively arranged on a water inlet pipeline, a first dosing branch 91, a second dosing branch 92 and a reflux branch, the fluorine ion sensors in the induced crystallization forming area 123 and the crystal growing area 124, the metering pumps on each branch and a starting valve 122 on a crystal discharge pipe 129 are respectively connected with the PLC control box through cables, the PLC control box controls the opening of the metering pumps on the water inlet pipeline and the first dosing branch 91 through the fluorine ion sensors in the induced crystallization forming area 123, so that the calcium fluorine ratio of the induced crystallization forming area 123 is 0.2-0.38, and the fluorine ion concentration in gas-liquid-solid three-phase fluid entering the crystal growing area 124 after reaction is 200-500mg/L; the PLC control box controls the opening of the second dosing branch 92 and the metering pump on the return branch through the fluoride ion sensor in the crystal growing area 124, and controls the calcium-fluorine ratio in the mixed liquid of the return water, the crystallization reactant and the gas-liquid-solid three-phase fluid to be 0.45-0.52. Every 24 hours, the PLC control box controls the start valve 122 to open for 15 seconds, and mature crystals with the particle size of 500-600um in the fluid director 121 are discharged into the crystal receiving groove 13 outside the fluidized bed 12 through the crystal discharging pipe 129.
The specific operation process of the defluorination system comprises the following steps: regulating pH of fluorine-containing wastewater in the fluorine-containing wastewater pool 1 to be 6-8, conveying the fluorine-containing wastewater to a tubular mixer 3 by a metering pump I2, conveying a crystallization purifying agent to the tubular mixer 3 on a water inlet pipeline by a metering pump II6, enabling metal ions in the crystallization purifying agent to react with sulfate radical, silicate radical, phosphate radical and other impurity ions in the fluorine-containing wastewater preferentially to form a solid mixture, filtering the solid mixture by a ceramic membrane filter 4, and then entering an induced crystallization forming area 123, wherein the calcium-fluorine ratio of the induced crystallization forming area 123 is controlled to be 0.2-0.38 by a fluorine ion sensor and the opening of the metering pump I2 and a metering pump III102 on a first dosing branch 91, and on one hand, the calcium-fluorine ratio can generate calcium fluoride crystal seeds, so that the fluorine concentration in gas-liquid-solid three-phase fluid can reach 200-500mg/L; this region maintains a calcium to fluorine ratio of 0.2 to 0.38, with an excess of fluoride ions in the calcium fluoride supersaturated region, and homogeneous nucleation of fluoride ions with calcium ions to form calcium fluoride solids as the crystallization inducer for the crystal growth region 124. The stirring of the airflow of the aeration pipeline 111 drives the calcium fluoride solids to flow upwards to form gas-liquid-solid three-phase fluid, so that the solids are effectively prevented from depositing. The residual fluorine concentration in the three-phase fluid is 200-500mg/L. The gas-liquid-solid three-phase fluid flows upwards, the flow guiding peak whirl enters the crystal growing area 124 through the flow guiding device 121, the reflux supernatant fluid of the solid-liquid separation area 125 is conveyed to the conical bottom part of the flow guiding device 121 through the metering pump IV126 to form 10-60 m/h high-speed fluid, the calcium chloride solution is conveyed to the upper part of the crystal outlet of the flow guiding device 121 through the metering pump V101, the concentration of fluorine ions in the crystal growing area is controlled by the calcium-fluorine ratio of 0.45-0.52, when the concentration of the fluorine ions is too high in the crystal growing area, calcium fluoride floc is easy to generate, therefore, when the concentration of the fluorine ions is too high, the pumping quantity of the calcium ions is increased, the reflux water, the crystallization reactant and the whirl liquid at the gap are quickly mixed, and the reflux water can reduce the concentration of the fluorine ions and the crystallization reactant in the crystal growing area 124. In the crystal growth region 124, the system is in a calcium fluoride metastable region, spontaneous nucleation is impossible, fluoride ions and calcium ions are adsorbed to the surface of the crystallization inducer by the thermodynamic irregular movement of molecules and the attraction between molecules, and then react with the surface of the crystallization inducer to become a part of the crystallization inducer, so that the crystallization inducer is promoted to grow to form sandy calcium fluoride. In the crystal growth area 124, the crystals are fluidized and expanded under the action of gravity and upward impact of hydraulic backflow water, and as the crystals grow, the gravity of the more mature crystals is larger than the buoyancy, and the crystals fall to the V-shaped valley of the flow director, and as the flow director is in an inverted cone shape, the smaller the downward flow area is, the higher the flow-through sweeping effect and the entrainment effect of the rotational flow are, and part of crystals with the particle size smaller than 500um are driven upwards, so that the crystals continue to grow. The crystals with the particle size of 500-600um flow to the inclined collecting tank at the bottom of the cone along with the trough seam of the flow director. The collecting tank has no impact of three-phase rotational flow and backflow water, and the liquid flows little, so that crystals in the tank can not continue to grow. The pneumatic valve 122 was actuated every 24 hours for 15 seconds to discharge calcium fluoride crystals having a particle size of 500-600um. When the pneumatic valve 122 is opened, the water inlet and the backflow of the fluidized bed 12 do not need to be stopped, and the backflow water outlet is 10-30cm higher than the bottom grain outlet, so that the backflow has no influence on the discharge of the bottom grains, only partial liquid is driven to be discharged, and the liquid and the filtrate for washing out crystals can flow back to the fluorine-containing wastewater tank 1. The upper part of the crystal growth zone 124 is a solid-liquid separation zone 125 with gradually expanding flow area, in which the fluid flow rate is reduced and the gas-liquid two phases are gradually separated. The reflux water outlet is positioned in the middle of the solid-liquid separation zone 125, so that the reflux water is ensured to contain no large particles. The fluorine concentration of the liquid clarified at the top is less than 15mg/L, the turbidity is less than 5NTU, the water pressure of the effluent water with higher fluidized bed automatically flows to the multi-medium filter 14, the multi-medium filter 14 removes the residual suspended matters, the effluent water of the multi-medium filter 14 enters the resin tower 15, the fluorine ions in the water are adsorbed by the aluminum-containing groups of the resin, the effluent water of the resin tower 15 is stably treated until the fluorine ion concentration in the effluent water is less than 1mg/L, and the resin concentrated water flows back to the fluorine-containing wastewater pool 1.
The defluorination system of the invention is applied, and the corresponding treated wastewater is: waste acid cleaning liquid for certain photovoltaic plants in Hebei province: the concentration of fluorine ions is 2535.8mg/L, the total concentration of silicon is 398.4mg/L, the concentration of ammonia nitrogen is 103.7mg/L, the concentration of chlorine ions is 35.9mg/L, the concentration of phosphate radical is 39.3mg/L, the concentration of sulfate ions is 562.5mg/L, the water amount is 1.0ton/h, and the running time is 24 hours.
Preparing a crystallization purifying agent: mixing barium oxide with purity of 99.99% and cerium oxide powder at a mixing mass ratio of 15:1, grinding to below 300 meshes, dissolving the mixed powder in pure water at an oxide concentration of 100g/L, stirring at 80-120 ℃, rapidly stirring at 1000rpm, pulping for 2 hours, reducing the temperature to 15 ℃, stirring for 2 hours, filtering by using a PTFE micro-filtration membrane with a membrane aperture of 0.45 mu m, and obtaining a clear solution; and (3) adding 0.8mol/L of 38wt% hydrochloric acid, 0.6mol/L of ammonium chloride and 1.42mol/L of magnesium chloride into the clear solution in sequence, heating the mixture to 60 ℃, stirring and reacting for 2 hours, and cooling to 25 ℃ after the reaction to obtain the crystallization purifying agent solution.
The prepared crystallization purifying agent is filled into a crystallization purifying agent storage tank 5, the fluorine-containing wastewater is introduced into a fluorine-containing wastewater pool 1, the pH is regulated to 7.5, a calcium chloride solution with the mass fraction of 30% is prepared, and the crystallization purifying agent is filled into a crystallization reactant storage tank 9.
The pneumatic valve 122 is closed to discharge the wastewater in the fluorine-containing wastewater tank 1 at a volume of 1m 3 The flow rate of/h is conveyed to the water inlet at the bottom of the fluidized bed 12, the crystallization purifying agent is conveyed to the front end of the tubular mixer 3 by a 10L/h metering pump II6, the crystallization reactant is conveyed to the medicine inlet at the bottom of the fluidized bed 12 by an 18L/h metering pump III102, air is introduced into the bottommost air vent by a 500L/min aeration fan 11, the fluorine concentration in raw water is reduced to 350-400 mg/L by reaction in an induced crystallization forming area 123, crystallization inducer flows upwards under the inclusion of rising water flow and air flow, forms rotational flow through the diversion peak of the deflector 121, and continues to flow upwards.
The flow of the reflux pump (metering pump IV 126) is regulated to20m 3 And/h, starting reflux and conveying to a reflux port at the bottom of the flow director 121, conveying a crystallization reactant to a second dosing port of the flow director 121 by using a 3.5L/h metering pump V101, and growing fluorine ions and calcium ions on the inducer by taking the crystallization inducer as crystal nuclei to gradually grow into mature crystals.
The hydraulic load of the crystal growth zone 124 was maintained at 41.8m 3 /m 2 H, the gradually grown crystal expands under the drive of water flow, and the hydraulic load is reduced to 10.4m in the solid-liquid separation area 125 3 /m 2 And h, the gravity of the crystal is larger than the buoyancy of water flow, and the solid and the liquid are separated. When the grain size grows to 500-600um, the crystals sink to the flow guiding valley of the flow guider and slide down along the slope of the flow guiding valley to the bottom collecting area.
After 7 days of reaction, pneumatic valve 122 was opened to drain the collection zone of mature crystals. After 15s the pneumatic valve 122 is closed. The purity of the dried crystal is more than 99.7 percent, and the grain diameter is uniform.
The average concentration of the fluorine ions in the effluent water at the top of the fluidized bed 12 is about 12.9mg/L, the turbidity is 3.5, the water pressure is about 6m, gravity flows to the multi-medium filter 14, residual suspended matters are filtered out, the filter is backwashed regularly, and backwash water is discharged to the fluorine-containing wastewater tank 1, and the backwash frequency is 1 week and 4 times.
The effluent of the multi-medium filter 14 flows to the resin tower 15 for deep defluorination, and the effluent F of the resin tower 15 - The content is less than 1mg/L, the emission standard is met, and the resin saturation period is 60 days.
Comparative example 1
Introducing the fluorine-containing wastewater and tap water into a fluorine-containing wastewater pool, regulating the pH to 7.5, regulating the fluorine concentration to 300-400 mg/L, preparing a calcium chloride solution with the mass fraction of 30%, and filling the calcium chloride solution into a crystallization reactant storage tank.
The prepared fluorine-containing wastewater is treated by a commercial fluidized bed. Firstly, 5 percent of quartz sand crystal seeds with 100 meshes in volume fraction are added, and the wastewater in a fluorine-containing wastewater tank is treated by 1m 3 The flow rate of/h is conveyed to a water inlet at the bottom of the fluidized bed, and the crystallization reactant is conveyed to a drug inlet at the bottom of the fluidized bed by a 3.5L/h metering pump. The flow of the reflux pump is regulated to 20m 3 Starting reflux and conveying to a reflux port at the bottom of the fluidized bed, and inducing fluoride ions and calcium ions by using quartz sand seed crystals as crystal nucleiGrowing on the conductor, and gradually growing into mature crystals.
The hydraulic load of the crystal growth zone 124 was maintained at 41.8m 3 /m 2 H, the gradually grown crystal expands under the drive of water flow, and the hydraulic load is reduced to 10.4m in the solid-liquid separation area 125 3 /m 2 And h, the gravity of the crystal is larger than the buoyancy of water flow, and the solid and the liquid are separated.
After 5 days of reaction, the running water pump and each metering pump are stopped, after 5 minutes of precipitation, a crystallization discharge valve is opened, and crystals at the bottom of the fluidized bed are discharged. The purity of the dried crystals is about 90 percent, and the grain size difference is large.
After the crystal discharge is finished, the crystal discharge valve is closed, quartz sand seed crystals are added at the top again, and the water inlet pump and each metering pump are started to continuously treat fluorine-containing wastewater.
The average concentration of fluorine ions in the effluent water at the top of the fluidized bed is about 15mg/L, the turbidity is 3.5, the water pressure is about 6m, the gravity flows to a multi-medium filter, residual suspended matters are filtered, the filter is backwashed periodically, and backwash water is discharged to a fluorine-containing wastewater tank 1, and the backwash frequency is 1 week and 4 times.
The effluent of the multi-medium filter flows to the resin tower to deeply remove fluorine, and the effluent F of the resin tower - The content is less than 1mg/L, the emission standard is met, and the resin saturation period is 60 days.
As is clear from comparative example 1, the conventional fluidized bed (i.e., no fluid director in the fluidized bed) can only be operated in a sequencing batch manner and is cumbersome to operate.
Claims (7)
1. A fluidized bed-based continuous production type defluorination system, which is characterized in that: comprises a fluorine-containing wastewater pool (1), a tubular mixer (3), a ceramic membrane filter (4), a fluidized bed (12), a crystallization purifying agent storage tank (5), a crystallization reactant storage tank (9), an aeration fan (11), a multi-medium filter (14) and a fluorine-removing resin tower (15); a fluid director (121) is arranged in the fluidized bed (12), the fluid director (121) divides the fluidized bed (12) into an induced crystallization forming area (123) and a crystal growing area (124), wherein the induced crystallization forming area (123) is positioned below the fluid director (121), the crystal growing area (124) is positioned above the fluid director (121), and a solid-liquid separation area (125) is also arranged above the crystal growing area (124); the fluorine-containing wastewater tank (1) and the crystallization purifying agent storage tank (5) are respectively connected with the tubular mixer (3) through pumps, the effluent of the tubular mixer (3) flows through the ceramic membrane filter (4) and then enters the crystallization-inducing forming region (123) of the fluidized bed (12), the crystallization reactant storage tank (9) is connected with two chemical adding branches, the crystallization reactant storage tank (9) is connected with the crystallization-inducing forming region (123) of the fluidized bed through a first chemical adding branch (91), an aeration pipe connected with the aeration fan (11) stretches into the crystallization-inducing forming region (123) at the bottom of the fluidized bed (12), and the calcium-fluorine ratio of the crystallization-inducing forming region (123) is 0.2-0.38; part of the liquid in the solid-liquid separation area (125) flows into the multi-medium filter (14) and then flows out of the fluorine-removing resin tower (15), the other part of the liquid in the solid-liquid separation area (125) flows back into the flow director (121), and the second dosing branch (92) of the crystallization reactant storage tank (9) also stretches into the flow director (121); the fluid director (121) is formed by encircling a plurality of fan-shaped blades (1212) into a cone structure, the top of the fluid director (121) is provided with an opening, the bottom of the fluid director is connected with a bottom plate, the outer diameter of the opening at the top of the fluid director (121) is consistent with the inner diameter of the fluidized bed (12), the fan-shaped blades (1212) form a fan-shaped blade combination (1211), the fan-shaped blade combination (1211) is provided with a V-shaped included angle, gaps are arranged between the adjacent fan-shaped blade combinations (1211), liquid in an induced crystallization forming area (123) below the fluid director (121) reaches a crystal growing area (124) through the gaps, and the calcium-fluorine ratio of the crystal growing area (124) is 0.45-0.52; crystals grown in the crystal growth area (124) fall into the deflector (121) and are sent into the crystal receiving groove (13) outside the fluidized bed (12) through a pipeline connected with the deflector (121); the purity of the obtained calcium fluoride solid is higher than 99.7%;
wherein, the crystallization purifying agent storage tank (5) is filled with crystallization purifying agent; the crystallization purifying agent is prepared by the following method: mixing and grinding barium oxide with purity of 99.99% and cerium oxide powder to below 300 meshes, dissolving the mixed powder in pure water at an oxide concentration of 100g/L, stirring at 80-120 ℃, rapidly pulping for 2-3 hours, reducing the temperature to 15 ℃ and stirring for 1-3 hours, filtering by using a PTFE micro-filtration membrane with a membrane aperture of 0.45 mu m, and obtaining a clear solution; sequentially adding 0.5-2 mol/L of 38wt% hydrochloric acid, 0.4-0.8 mol/L of ammonium chloride and 0.5-2 mol/L of magnesium chloride into the clarified liquid, heating the mixed material to 40-60 ℃, stirring and reacting for 1-2 hours, and cooling to 25 ℃ after reacting to obtain a crystallization purifying agent;
the bottom of the flow director (121) is connected with two pipelines, one pipeline is a connecting pipe (130), the outlet section of the connecting pipe (130) is positioned at the center of the flow director (121), the height from the outlet of the connecting pipe (130) to the bottom plate of the flow director (121) is 10-30cm, and the other end of the connecting pipe (130) is connected with a supernatant return pipe (128); the other pipeline is a crystal discharge pipe (129), the orifice of the crystal discharge pipe (129) is welded at the lowest part of the inclined bottom plate, and the crystal discharge pipe (129) extends out of the fluidized bed (12) to be connected with a crystal receiving groove (13); every 24 hours, the pneumatic valve (122) on the crystal discharge pipe (129) is started to be opened for 15 seconds, calcium fluoride crystals with the particle size of 500-600 mu m are discharged, and when the pneumatic valve (122) is opened, the water inlet and the reflux of the fluidized bed do not need to be stopped.
2. The fluidized bed-based continuous production type fluorine removal system as set forth in claim 1, wherein: the crystallization reactant storage tank (9) is filled with 30% calcium chloride solution by mass fraction.
3. The fluidized bed-based continuous production type fluorine removal system as set forth in claim 1, wherein: in the crystallization-inducing formation area (123), a dosing pipe connected with a crystallization reactant storage tank (9) is arranged opposite to a water inlet pipe connected with a ceramic membrane filter (4).
4. The fluidized bed-based continuous production type fluorine removal system as set forth in claim 1, wherein: the aeration pipelines (111) are uniformly distributed at the bottom of the fluidized bed (12), and the air vents of the aeration pipelines (111) are downward arranged.
5. The fluidized bed-based continuous production type fluorine removal system as set forth in claim 1, wherein: the deflector (121) comprises eight groups of fan-shaped blade combinations (1211), each group of fan-shaped blade combinations (1211) is formed by splicing two fan-shaped blades (1212), one side of each fan-shaped blade (1212) with the same side length is welded and fixed at an included angle of 165 degrees, the bottom edges of the two fan-shaped blades (1212) are fixed on a bottom plate (1213), V-shaped included angles between the two fan-shaped blades (1212) are protruded towards the direction away from the center of the fluidized bed, the eight groups of fan-shaped blade combinations (1211) are uniformly distributed on the bottom plate (1213) along the circle center of the fluidized bed in a circumference mode to form a peak-valley staggered mode, and the fan-shaped blades corresponding to the adjacent fan-shaped blade combinations (1211) are staggered up and down to form gaps between the two fan-shaped blades.
6. The fluidized bed-based continuous production type fluorine removal system as set forth in claim 5, wherein: the V-shaped included angle is 58 degrees with the horizontal plane, the included angle between the gap and the horizontal plane is 65 degrees, and the width of the gap is 0.5cm.
7. The fluidized bed-based continuous production type fluorine removal system as set forth in claim 1, wherein: the device also comprises a PLC control box and fluorine ion sensors respectively positioned in an induced crystallization forming area (123) and a crystal growing area (124), metering pumps are respectively arranged on a water inlet pipeline, a first dosing branch (91), a second dosing branch (92) and a reflux branch, the fluorine ion sensors in the induced crystallization forming area (123) and the crystal growing area (124), the metering pumps on each branch and a pneumatic valve (122) on a crystal discharging pipe (129) are respectively connected with the PLC control box through cables, and the PLC control box controls the opening of the metering pumps on the water inlet pipeline and the first dosing branch (91) through the fluorine ion sensors in the induced crystallization forming area (123), so that the calcium-fluorine ratio of the induced crystallization forming area (123) is 0.2-0.38, and the fluorine ion concentration in gas-liquid-solid three-phase fluid entering the crystal growing area (124) after reaction is 200-500mg/L; the PLC control box controls the opening of the metering pump on the second dosing branch (92) and the reflux branch through a fluorine ion sensor in the crystal growth area (124), and controls the calcium-fluorine ratio in the mixed liquid of the reflux water, the crystallization reactant and the gas-liquid-solid three-phase fluid to be 0.45-0.52.
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