CN116425373A - System for high fluorine-containing waste water advanced treatment resourceful treatment of high pH - Google Patents
System for high fluorine-containing waste water advanced treatment resourceful treatment of high pH Download PDFInfo
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- 239000011737 fluorine Substances 0.000 title claims abstract description 56
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 56
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002351 wastewater Substances 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 238000002156 mixing Methods 0.000 claims abstract description 60
- 239000012528 membrane Substances 0.000 claims abstract description 41
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 37
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 37
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 22
- 238000005352 clarification Methods 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 238000001514 detection method Methods 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 34
- 238000003860 storage Methods 0.000 claims description 24
- 239000010802 sludge Substances 0.000 claims description 20
- 239000001569 carbon dioxide Substances 0.000 claims description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- 238000005189 flocculation Methods 0.000 claims description 9
- 230000016615 flocculation Effects 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 8
- -1 aluminum iron titanium Chemical group 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 18
- 239000012466 permeate Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 229920002401 polyacrylamide Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 6
- 239000000920 calcium hydroxide Substances 0.000 description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 6
- 238000006115 defluorination reaction Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000009388 chemical precipitation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 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
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- 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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Abstract
The invention discloses a high-pH high-fluorine-content wastewater advanced treatment recycling system, which belongs to the technical field of wastewater treatment, and comprises a primary fluorine removal system, a deep fluorine removal system and an online detection system, wherein the primary fluorine removal system comprises a primary water tank, a primary dosing unit, a primary mixing reaction unit, a tubular ultrafiltration membrane system and a concentration unit, the deep fluorine removal system comprises a second dosing unit, a neutralization reaction unit, a secondary mixing reaction unit and a clarification tank, the online detection system comprises a turbidity meter, a fluorine ion detector, a pH meter module and a control unit, the problems of long flow, large occupied area, multiple dosing types, large dosage of agents, high cost, low efficiency and the like in the high-pH and high-fluorine-content wastewater treatment are solved, and meanwhile, the recycling of calcium fluoride is realized further by reducing carbon gain to the maximum extent, and the system has the advantages of high-efficiency fluorine removal, energy conservation, cost reduction, carbon reduction gain, waste utilization, simplicity and practicability.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a system for deeply treating and recycling high-pH high-fluorine-containing wastewater.
Background
The production processes of electroplating, aluminum electrolysis, semiconductors, steel industry, glass manufacturing, phosphate fertilizer production, thermal power plants, fluorite mineral processing, fluoride salt, hydrofluoric acid, polyether ether ketone and the like can discharge a large amount of fluorine-containing wastewater, and the fluoride content is more than 100mg/L, even up to thousands and tens of thousands of mg/L. The chemical precipitation method and the coagulating sedimentation method are used more in the treatment of wastewater with high fluorine content.
The chemical precipitation method for removing fluorine is to add chemical substances such as calcium chloride, calcium hydroxide and calcium oxide into the fluorine-containing wastewater to enable the fluorine-containing wastewater and fluorine ions to form calcium fluoride precipitates, and the method has the characteristics of simplicity in operation, less investment and remarkable fluorine removal effect, but the calcium fluoride has certain solubility, the fluorine content in the treated wastewater is difficult to be less than 20mg/L, and the problems of large sludge quantity, serious secondary pollution and the like are caused.
The coagulation precipitation method for removing fluorine is to add coagulant into fluorine-containing wastewater, so that fluoride is adsorbed by formed colloid or precipitate, the coagulation precipitation method is suitable for a large treatment scale, has the characteristic of small addition amount of flocculant, but the effluent quality is not stable enough and the sludge amount is large, and the possibility that secondary treatment is needed for introducing the flocculant exists.
In the high pH and high fluorine-containing wastewater treatment process, in order to ensure the defluorination effect, a chemical precipitation method and a coagulating sedimentation method are commonly used in combination, namely, calcium chloride is added under the slightly alkaline condition to enable fluoride ions and calcium ions to form calcium fluoride precipitates, PAC (polyaluminum chloride) and PAM (polyacrylamide) are further added to enable fine calcium fluoride particles to be aggregated into large flocs, and the precipitation effect is improved, but two-stage or three-stage treatment is often needed. The combination has the problems of long process flow, large occupied area, multiple types of added medicaments, large medicament dosage, high operation cost and low fluorine removal efficiency.
Therefore, there is a need to provide a system for advanced treatment and recycling of wastewater with high pH and high fluorine content, which aims to solve the problems.
Disclosure of Invention
Aiming at the defects existing in the prior art, the embodiment of the invention aims to provide a system for deeply treating and recycling high-pH high-fluorine-containing wastewater, so as to solve the problems in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the system comprises a primary fluorine removal system, a deep fluorine removal system and an online detection system, wherein the primary fluorine removal system comprises a raw water tank, a primary dosing unit, a primary mixing reaction unit, a tubular ultrafiltration membrane system and a concentration unit, the deep fluorine removal system comprises a second dosing unit, a neutralization reaction unit, a secondary mixing reaction unit and a clarification tank, and the online detection system comprises a turbidity meter, a fluoride ion detector, a pH meter module and a PLC control unit;
the device comprises a primary water tank, a primary mixing reaction unit, a primary dosing unit, a primary mixing reaction unit, a tubular ultrafiltration membrane system, a concentration unit, a neutralization reaction unit, a concentration unit, a turbidity meter, a fluoride ion detector, a pH meter module and a PLC control unit, wherein the primary water tank is connected with the primary mixing reaction unit, the primary dosing unit is matched with the primary mixing reaction unit, the primary mixing reaction unit is connected with the tubular ultrafiltration membrane system and the concentration unit respectively, the tubular ultrafiltration membrane system and the concentration unit are connected with the neutralization reaction unit respectively, the neutralization reaction unit is connected with the secondary mixing reaction unit, the secondary mixing reaction unit is connected with a clarification tank, the concentration unit is connected with the turbidity meter, the fluoride ion detector and the pH meter module respectively.
As a further scheme of the invention, the primary mixing reaction unit comprises a first lifting pump and a primary mixing reaction tank, the first lifting pump is connected between the raw water tank and the primary mixing reaction tank, a first pH meter and a first stirrer are arranged in the primary mixing reaction tank, and the primary mixing reaction tank is connected with the primary dosing unit.
As a further scheme of the invention, the tubular ultrafiltration membrane system comprises a second lift pump, a tubular ultrafiltration membrane group and a sulfuric acid dosing unit, wherein the second lift pump is connected between the primary mixing reaction tank and the tubular ultrafiltration membrane group, and the tubular ultrafiltration membrane group is connected with a fluoride ion detector.
As a further scheme of the invention, the concentration unit comprises a calcium fluoride sludge temporary storage tank, a feed pump and a plate-and-frame filter press, wherein the calcium fluoride sludge temporary storage tank is connected with the primary mixing reaction tank through a pipeline, the feed pump is connected between the calcium fluoride sludge temporary storage tank and the plate-and-frame filter press, and the output end of the plate-and-frame filter press is provided with a turbidity meter.
As a further scheme of the invention, the second dosing unit comprises a high-efficiency fluorine-removing agent dosing device and a PAM dosing device, and the high-efficiency fluorine-removing agent is aluminum iron titanium composite salt.
As a further scheme of the invention, the neutralization reaction unit comprises a neutralization reaction tank and a carbon dioxide storage and air-entrapping system, the carbon dioxide storage and air-entrapping system comprises a carbon dioxide storage tank and a circulating pump, a second pH meter and a microporous aeration assembly are arranged in the neutralization reaction tank, the neutralization reaction tank is respectively connected with a tubular ultrafiltration membrane group and a plate-and-frame filter press through pipelines, and the carbon dioxide storage tank and the circulating pump are respectively connected with the microporous aeration assembly.
As a further scheme of the invention, the secondary mixed reaction unit comprises a secondary mixed reaction tank, a second stirrer is arranged in the secondary mixed reaction tank, the high-efficiency fluorine-removing agent adding device is connected with the secondary mixed reaction tank, and the secondary mixed reaction tank is connected with the neutralization reaction tank through a pipeline.
As a further scheme of the invention, the clarifying tank is connected with the secondary mixing reaction tank through a pipeline, the clarifying tank comprises a flocculation area and a clarifying area, the PAM adding device is connected with the flocculation area, an inclined tube is arranged in the clarifying area, and the clarifying area is connected with the fluoride ion detector.
As a further scheme of the invention, the PLC control unit is connected with the first pH meter, the second pH meter, the first-stage dosing unit, the circulating pump, the turbidity meter, the fluoride ion detector and the high-efficiency fluorine-removing agent dosing device.
In summary, compared with the prior art, the embodiment of the invention has the following beneficial effects:
the invention solves the problems of long flow, large occupied area, multiple types of added medicaments, large medicament dosage, high operation cost, low fluorine removal efficiency and the like in the treatment of the wastewater with high pH value and high fluorine content, can further reduce carbon gain, maximally realize the recycling of calcium fluoride, and has the effects of high efficiency fluorine removal, energy conservation, cost reduction, carbon reduction gain, waste utilization, simplicity, convenience and practicability.
In order to more clearly illustrate the structural features and efficacy of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and examples.
Drawings
Fig. 1 is a flow chart of an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
In one embodiment of the invention, referring to fig. 1, the method for deeply treating and recycling high-pH high-fluorine-containing wastewater comprises a primary fluorine removal system, a deep fluorine removal system and an online detection system, wherein the primary fluorine removal system comprises a raw water tank, a primary dosing unit, a primary mixed reaction unit, a tubular ultrafiltration membrane system and a concentration unit, the deep fluorine removal system comprises a second dosing unit, a neutralization reaction unit, a secondary mixed reaction unit and a clarification tank, and the online detection system comprises a turbidity meter, a fluoride ion detector, a pH meter module and a PLC (programmable logic controller) control unit;
wherein the raw water tank is connected with a primary mixing reaction unit, the primary dosing unit is matched with the primary mixing reaction unit, the primary mixing reaction unit is respectively connected with a tubular ultrafiltration membrane system and a concentration unit, the tubular ultrafiltration membrane system and the concentration unit are respectively connected with a neutralization reaction unit, the neutralization reaction unit is connected with a secondary mixing reaction unit, the second-stage mixing reaction unit is connected with the clarification tank, the concentration unit is connected with the turbidity meter, the fluoride ion detector is respectively connected with the mixing reaction unit and the tubular ultrafiltration membrane system, the pH meter module is respectively connected with the first-stage mixing reaction unit and the neutralization reaction unit, and the PLC control unit is respectively electrically connected with the turbidity meter, the fluoride ion detector and the pH meter module.
In this embodiment, the pH meter module includes a first pH meter and a second pH meter, and the system can be flexibly operated and precisely controlled through the PLC control unit, the turbidity meter, the pH meter module and the fluoride ion detector.
In one embodiment of the present invention, referring to fig. 1, the primary mixing reaction unit includes a first lift pump and a primary mixing reaction tank, the first lift pump is connected between the raw water tank and the primary mixing reaction tank, a first pH meter and a first stirrer are disposed in the primary mixing reaction tank, and the primary dosing unit is connected with the primary mixing reaction tank;
the tubular ultrafiltration membrane system comprises a second lifting pump, a tubular ultrafiltration membrane group and a sulfuric acid dosing unit, wherein the second lifting pump is connected between the primary mixed reaction tank and the tubular ultrafiltration membrane group, and the tubular ultrafiltration membrane group is connected with a fluoride ion detector;
the concentration unit comprises a calcium fluoride sludge temporary storage box, a feed pump and a plate-and-frame filter press, wherein the calcium fluoride sludge temporary storage box is connected with the primary mixing reaction tank through a pipeline, the feed pump is connected between the calcium fluoride sludge temporary storage box and the plate-and-frame filter press, and the output end of the plate-and-frame filter press is provided with a turbidity meter;
the second dosing unit comprises a high-efficiency fluorine-removing agent dosing device and a PAM dosing device, and the high-efficiency fluorine-removing agent is aluminum iron titanium composite salt;
the neutralization reaction unit comprises a neutralization reaction tank and a carbon dioxide storage and gas filling system, the carbon dioxide storage and gas filling system comprises a carbon dioxide storage tank and a circulating pump, a second pH meter and a microporous aeration assembly are arranged in the neutralization reaction tank, the neutralization reaction tank is respectively connected with a tubular ultrafiltration membrane group and a plate-and-frame filter press through pipelines, and the carbon dioxide storage tank and the circulating pump are respectively connected with the microporous aeration assembly;
the second-stage mixed reaction unit comprises a second-stage mixed reaction tank, a second stirrer is arranged in the second-stage mixed reaction tank, the high-efficiency fluorine-removing agent adding device is connected with the second-stage mixed reaction tank, and the second-stage mixed reaction tank is connected with the neutralization reaction tank through a pipeline;
the clarification tank is connected with the secondary mixing reaction tank through a pipeline, the clarification tank comprises a flocculation area and a clarification area, the PAM adding device is connected with the flocculation area, an inclined tube is arranged in the clarification area, and the clarification area is connected with the fluoride ion detector.
In this embodiment, annotate in the one-level dosing unit and have calcium hydroxide emulsion, the one-level dosing unit is according to pH and fluoride ion content control calcium hydroxide emulsion's in the raw water throwing, the former water tank is used for collecting and adjusting fluorine-containing waste water and receives the unqualified permeate from plate and frame filter press, PLC control unit and first dosing unit, circulating pump, turbidimeter, fluoride ion detector and high-efficient defluorinating agent throwing device electric connection, specifically:
the method comprises the steps that fluorine-containing wastewater is discharged to a raw water tank, is lifted by a first lifting pump and enters a first-stage mixing reaction tank, and a first-stage dosing unit doses excessive calcium hydroxide emulsion into the wastewater according to the pH value fed back by a first pH meter, wherein on one hand, the pH value of the wastewater is adjusted to be 12 or 8, and on the other hand, under the action of a first stirrer, the calcium hydroxide emulsion and the wastewater are fully mixed and reacted, so that white calcium fluoride particles are generated; the wastewater is lifted to a tubular ultrafiltration membrane group by a second lifting pump after fully mixing reaction, the average pore diameter of the tubular ultrafiltration membrane is 0.1um, the molecular weight cut-off is 10 ten thousand daltons, the concentration of the calcium fluoride-containing wastewater can be realized, the mass fraction after concentration is about 8%, the produced high solid content concentrated water is discharged to a calcium fluoride sludge temporary storage tank, and the produced permeate enters a neutralization reaction tank; the neutralization reaction tank adopts a closed structure, gas in an air chamber at the upper part of the neutralization reaction tank is diffused into the wastewater by a microporous aeration assembly through a circulating pump, carbon dioxide in a carbon dioxide storage tank is diffused into the wastewater by the microporous aeration assembly, and the pH is regulated to 7.0-9.0; under the stirring action of a second stirrer, the high-efficiency fluorine removing agent solution added into the secondary mixing reaction tank fully reacts with residual fluorine ions in the wastewater; adding anionic PAM into a flocculation area at the front end of a clarification tank, aggregating suspended fluoride particles into large flocs, separating by the clarification tank under the action of gravity, temporarily storing the generated fluorine-containing sludge in a mud area at the bottom of the clarification tank, and discharging the generated supernatant reaching the standard; the calcium fluoride sludge in the calcium fluoride sludge temporary storage tank and the chemical sludge at the bottom of the clarifier are transported to the plate-and-frame filter press in batches through a screw pump; the method comprises the steps that a turbidity meter detects permeate liquid generated in a filter pressing process, a PLC control unit controls valve action according to a turbidity meter feedback signal for permeate liquid with turbidity meeting process requirements, the permeate liquid is discharged to a neutralization reaction tank, and a PLC control unit controls valve action according to a turbidity meter feedback signal for permeate liquid with higher turbidity, so that backflow to a raw water tank is achieved; the fluoride ion detector monitors permeate liquid generated by the tubular ultrafiltration membrane group and the plate-and-frame filter press on line in real time, and for permeate liquid reaching the standard, the PLC control unit controls the action of the control valve according to a feedback signal of the fluoride ion detector, so that the permeate liquid can be directly discharged without a deep fluoride removal system, in addition, supernatant liquid of the clarifier also needs to be detected in real time, and a detection result is uploaded to the PLC control unit so as to further adjust the dosage, thereby realizing accurate control of the dosage;
the PLC control unit is respectively connected with the first pH meter, the second pH meter, the first-level dosing unit, the circulating pump, the turbidity meter, the fluoride ion detector and the high-efficiency defluorinating agent dosing device;
the invention can treat the wastewater with high pH and high fluorine content by adopting the tubular ultrafiltration membrane group; the pH of the wastewater is reduced by using carbon dioxide gas, the sulfuric acid consumption is reduced, and the operation danger is reduced; the neutralization reaction tank adopts a closed structure, carbon dioxide gas is recycled, and the utilization efficiency is improved; when the tubular ultrafiltration membrane group just starts to run, the generated concentrated solution directly enters a concentration unit, so that the design scale of the tubular ultrafiltration membrane group is reduced, and the investment cost is reduced; the system can be flexibly operated and accurately controlled through the PLC control unit, the turbidity meter, the pH meter module and the fluoride ion detector; the calcium fluoride sludge generated by the primary defluorination can be recycled and utilized, and the utilization rate of the product is improved.
In one embodiment of the present invention, referring to FIG. 1, a refining plant of a polymer company produces a fluorine-containing process wastewater of 120m 3 And/d, the water quality requirements of the water inlet and outlet of the project are as follows:
in the example, the fluorine-containing concentrated water is discharged into a raw water tank to be fully mixed and homogenized, and the residence time is 6h;
the homogenized wastewater is lifted to a primary mixing reaction tank by a pump, the residence time is 30min, and simultaneously a certain amount of 10% calcium hydroxide emulsion is added into the water to generate CaF 2 Solid, mass fraction 4%;
the coagulated wastewater is sent into a tubular ultrafiltration membrane group by a second lift pump, and the design scale of the tubular ultrafiltration membrane is 129m 3 And/d, the cross flow speed is 4m/s, the membrane flux is designed to be 100LMH, 3 total membrane area is 31.8m 2 The membrane system design recovery rate is 50%, the mass fraction of the concentrated water is 8%, the permeate reaching the standard after filter pressing and the membrane group produced water enter a deep defluorination system, the permeate not reaching the standard flows back to the original water tank, and the total recovery rate of the tubular ultrafiltration membrane group and the filter pressing system is 89.74%.
The retention time of the neutralization reaction tank is 30min, carbon dioxide gas is added into the neutralization reaction tank, the pH value of the neutralization reaction tank is regulated to 8.5, meanwhile, an efficient fluorine removing agent is added, and the fluorine removing agent and fluorine ions are fully contacted and reacted under the stirring of a second stirrer; the retention time of the flocculation area of the clarification tank is 20min, and anion PAM is added into the flocculation area, so that the particle size of alum blossom formed by the high-efficiency fluorine removing agent and fluorine ions is increased, and the sedimentation and separation are facilitated.
The sludge generated by the primary defluorination process and the deep defluorination process is dehydrated and concentrated alternately, the mass fraction of calcium fluoride sludge generated by the filter pressing system is 7.23t each day, and the mass fraction of chemical sludge generated by the deep defluorination system is about 40% and is 0.15t/d.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (6)
1. The system is characterized by comprising a primary fluorine removal system, a deep fluorine removal system and an online detection system, wherein the primary fluorine removal system comprises a raw water tank, a primary dosing unit, a primary mixing reaction unit, a tubular ultrafiltration membrane system and a concentration unit, the deep fluorine removal system comprises a second dosing unit, a neutralization reaction unit, a secondary mixing reaction unit and a clarification tank, and the online detection system comprises a turbidity meter, a fluoride ion detector, a pH meter module and a PLC control unit;
the system comprises a primary mixing reaction unit, a primary dosing unit, a primary ultrafiltration membrane system, a neutralization reaction unit, a secondary mixing reaction unit, a pH meter module, a turbidity meter, a fluoride ion detector and a pH meter module, wherein the primary water tank is connected with the primary mixing reaction unit, the primary dosing unit is matched with the primary mixing reaction unit, the primary mixing reaction unit is connected with the tubular ultrafiltration membrane system and the concentration unit respectively, the tubular ultrafiltration membrane system and the concentration unit are connected with the neutralization reaction unit respectively, the neutralization reaction unit is connected with the secondary mixing reaction unit, the secondary mixing reaction unit is connected with the clarifier, the concentration unit is connected with the turbidity meter, the fluoride ion detector and the pH meter module respectively, and the pH meter module is electrically connected with the primary mixing reaction unit and the neutralization reaction unit respectively;
the primary mixing reaction unit comprises a first lifting pump and a primary mixing reaction tank, the first lifting pump is connected between the raw water tank and the primary mixing reaction tank, a first pH meter and a first stirrer are arranged in the mixing reaction tank, and the primary mixing reaction tank is connected with the primary dosing unit;
the concentration unit comprises a calcium fluoride sludge temporary storage box, a feed pump and a plate-and-frame filter press, wherein the calcium fluoride sludge temporary storage box is connected with the primary mixing reaction tank through a pipeline, the feed pump is connected between the calcium fluoride sludge temporary storage box and the plate-and-frame filter press, and the output end of the plate-and-frame filter press is provided with a turbidity meter;
the neutralization reaction unit comprises a neutralization reaction tank and a carbon dioxide storage and air-entrapping system, the carbon dioxide storage and air-entrapping system comprises a carbon dioxide storage tank and a circulating pump, a second pH meter and a microporous aeration assembly are arranged in the neutralization reaction tank, the neutralization reaction tank is respectively connected with a tubular ultrafiltration membrane group and a plate-and-frame filter press through pipelines, and the carbon dioxide storage tank and the circulating pump are respectively connected with the microporous aeration assembly.
2. The system for deeply treating and recycling high-pH and high-fluorine-containing wastewater according to claim 1, wherein the tubular ultrafiltration membrane system comprises a second lift pump, a tubular ultrafiltration membrane group and a sulfuric acid dosing unit, the second lift pump is connected between the primary mixing reaction tank and the tubular ultrafiltration membrane group, and the tubular ultrafiltration membrane group is connected with a fluorine ion detector.
3. The system for deeply treating and recycling high-pH and high-fluorine-containing wastewater according to claim 1, wherein the second dosing unit comprises a high-efficiency fluorine-removing agent dosing device and a PAM dosing device, and the high-efficiency fluorine-removing agent is aluminum iron titanium composite salt.
4. The advanced treatment and recycling system for high-pH and high-fluorine-containing wastewater according to claim 3, wherein the secondary mixing reaction unit comprises a secondary mixing reaction tank, a second stirrer is arranged in the secondary mixing reaction tank, the high-efficiency fluorine-removal agent adding device is connected with the secondary mixing reaction tank, and the secondary mixing reaction tank is connected with the neutralization reaction tank through a pipeline.
5. The system for deeply treating and recycling high-pH and high-fluorine-containing wastewater according to claim 3, wherein the clarification tank is connected with the secondary mixing reaction tank through a pipeline, the clarification tank comprises a flocculation area and a clarification area, the PAM adding device is connected with the flocculation area, an inclined tube is arranged in the clarification area, and the clarification area is connected with the fluoride ion detector.
6. The advanced treatment and recycling system for high-pH and high-fluorine-containing wastewater according to claim 4, wherein the PLC control unit is respectively connected with the primary dosing unit, the circulating pump and the high-efficiency fluorine-removing agent adding device.
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| CN202310692282.5A CN116425373A (en) | 2023-06-13 | 2023-06-13 | System for high fluorine-containing waste water advanced treatment resourceful treatment of high pH |
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| CN202310692282.5A CN116425373A (en) | 2023-06-13 | 2023-06-13 | System for high fluorine-containing waste water advanced treatment resourceful treatment of high pH |
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| JPH0747371A (en) * | 1993-08-04 | 1995-02-21 | Kurita Water Ind Ltd | Treatment of fluoride-containing water |
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| CN210915662U (en) * | 2019-11-06 | 2020-07-03 | 山西绿洁环保有限公司 | Special defluorination system of coal chemical industry waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0747371A (en) * | 1993-08-04 | 1995-02-21 | Kurita Water Ind Ltd | Treatment of fluoride-containing water |
| JP2006218354A (en) * | 2005-02-08 | 2006-08-24 | Kurita Water Ind Ltd | Method for treating fluorine-containing waste water |
| JP2015016447A (en) * | 2013-07-12 | 2015-01-29 | 旭化成ケミカルズ株式会社 | Method and system for treating fluorine-containing waste water |
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