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CN113620477A - Defluorination device and method for high-salinity wastewater - Google Patents

Defluorination device and method for high-salinity wastewater Download PDF

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CN113620477A
CN113620477A CN202111069158.0A CN202111069158A CN113620477A CN 113620477 A CN113620477 A CN 113620477A CN 202111069158 A CN202111069158 A CN 202111069158A CN 113620477 A CN113620477 A CN 113620477A
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defluorination
tubular microfiltration
fluorine
wastewater
resin adsorption
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杨帆
裘慕贤
李树庭
张俊云
熊斐
朱筱滢
朱荣伟
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Baowu Water Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/583Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/12Halogens or halogen-containing compounds
    • C02F2101/14Fluorine or fluorine-containing compounds

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Abstract

本发明公开了一种针对高盐废水的除氟装置以及方法,针对高盐废水的除氟装置包括除氟反应系统、管式微滤循环系统、树脂吸附系统。除氟反应系统用于接收含氟废水,对含氟废水进行第一道处理以实现絮凝。管式微滤循环系统用于接收除氟反应系统输出的废水,对除氟反应系统输出的废水进行第二道处理以实现管式微滤。树脂吸附系统用于接收管式微滤循环系统输出的废水,对管式微滤循环系统输出的废水进行第三道处理以实现树脂吸附。利用本申请的除氟装置实现絮凝、管式微滤以及树脂吸附耦合,极大地提高了对高浓盐水中氟的去除率,可使得氟离子去除率达95‑99%,且出水中不增加钙、镁离子,有效避免出水对后续电渗析和蒸发结晶装置堵塞、腐蚀问题。

Figure 202111069158

The invention discloses a defluorination device and a method for high-salt waste water. The defluorination device for high-salt waste water comprises a defluorination reaction system, a tubular microfiltration circulation system and a resin adsorption system. The defluorination reaction system is used to receive fluorine-containing wastewater, and perform the first treatment on the fluorine-containing wastewater to achieve flocculation. The tubular microfiltration circulation system is used to receive the waste water output by the defluorination reaction system, and perform a second treatment on the waste water output by the defluorination reaction system to realize the tubular microfiltration. The resin adsorption system is used to receive the wastewater output by the tubular microfiltration circulation system, and perform the third treatment on the wastewater output by the tubular microfiltration circulation system to realize resin adsorption. The coupling of flocculation, tubular microfiltration and resin adsorption is realized by using the fluorine removal device of the present application, which greatly improves the removal rate of fluorine in high-concentration brine, and can make the removal rate of fluoride ions reach 95-99%, and the effluent does not increase calcium. , magnesium ions, effectively avoid the blockage and corrosion of the effluent to the subsequent electrodialysis and evaporative crystallization devices.

Figure 202111069158

Description

Defluorination device and method for high-salinity wastewater
Technical Field
The invention relates to the technical field of high-salinity water treatment of water, in particular to a defluorination device and method aiming at high-salinity wastewater.
Background
With the attention paid to pollutant wastewater, more and more evaporative crystallization devices are built, and the high-salt and high-fluorine wastewater can have great influence on the evaporative crystallization devices at present. High-concentration fluorine-containing brine enters electrodialysis treatment, so that membrane scaling is easily caused, and meanwhile, fluorine ions enter polar water to corrode an electrode coating. High concentration fluorine-containing brine enters into the evaporative crystallization device, the sodium chloride evaporative crystallization device generally adopts titanium material, the surface of the titanium material can form a compact and stable oxidation film to prevent corrosion, fluoride and hydrogen ions are combined to form hydrogen fluoride, the hydrogen fluoride can be preferentially adsorbed on the surface of the titanium and combined with the titanium ions to form soluble fluoride, the titanium is subjected to pitting corrosion, and the service life of the evaporative crystallization device is influenced.
In the prior art, lime or calcium chloride is generally added when fluorine-containing wastewater is treated, calcium ions and fluoride ions react to generate calcium fluoride precipitate, the fluoride ions are removed through precipitation, but other ions in high-concentration salt water influence the solubility of the calcium fluoride, when the wastewater contains high-concentration sodium chloride and sodium sulfate, the concentration of the fluoride ions in the effluent is about 20-30mg/l, the concentration of the calcium ions is about 50-100mg/l, and the calcium ions and the fluoride ions seriously influence the operation of a subsequent electrodialysis and crystallization device.
Therefore, how to improve the fluorine removal capability becomes a technical problem to be solved urgently in the field.
It is noted that the information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a defluorination device and a defluorination method for high-salinity wastewater, which are used for solving the problem that the prior art scheme has low removal rate of fluorine ions in the wastewater.
In order to solve the technical problems, the invention provides a defluorination device aiming at high-salinity wastewater, which comprises a defluorination reaction system, a tubular microfiltration circulating system and a resin adsorption system, wherein the defluorination reaction system comprises a tubular microfiltration circulating system and a tubular microfiltration circulating system;
the defluorination reaction system is used for receiving fluorine-containing wastewater and carrying out first treatment on the fluorine-containing wastewater to realize flocculation;
the tubular microfiltration circulating system is used for receiving the wastewater output by the defluorination reaction system and carrying out second treatment on the wastewater output by the defluorination reaction system so as to realize tubular microfiltration;
the resin adsorption system is used for receiving the wastewater output by the tubular microfiltration circulating system and carrying out third treatment on the wastewater output by the tubular microfiltration circulating system so as to realize resin adsorption.
Optionally, the defluorination reaction system comprises a reaction tank, a neutralization tank and a circulation tank;
the fluorine-containing wastewater sequentially passes through the reaction tank, the neutralization tank and the circulation tank to realize flocculation.
Optionally, a first stirrer and a first pH meter are arranged in the reaction tank.
Optionally, a second stirrer and a second pH meter are arranged in the neutralization tank.
Optionally, a circulation tank liquid level meter and a third stirrer are arranged in the circulation tank.
Optionally, the tubular microfiltration circulating system comprises a circulating pump, a tubular microfiltration membrane and a water production pipe;
and wastewater output by the defluorination reaction system sequentially passes through the circulating pump, the tubular microfiltration membrane and the water production pipe to realize tubular microfiltration.
Optionally, the tubular microfiltration circulating system further comprises a basket filter;
the input port of the basket filter is connected with the defluorination reaction system, and the output port of the basket filter is connected with the input port of the circulating pump.
Optionally, the resin adsorption system comprises a resin tower for performing resin adsorption on the wastewater output by the tubular microfiltration circulating system.
Optionally, the fluorine removal device for the high-salinity wastewater further comprises a resin regeneration system;
the resin regeneration system is used for treating the resin adsorption system so as to recover the defluorination function of the resin adsorption system.
Optionally, the resin regeneration system comprises an acid regeneration module and an alkali regeneration module;
the acid regeneration module is used for carrying out acid regeneration treatment on the resin adsorption system, and the alkali regeneration module is used for carrying out alkali regeneration treatment on the resin adsorption system.
Based on the same invention concept, the invention also provides a defluorination method aiming at the high-salinity wastewater, which comprises the following steps:
the method comprises the following steps that a defluorination reaction system receives fluorine-containing wastewater, and the fluorine-containing wastewater is subjected to primary treatment to realize flocculation;
the tubular microfiltration circulating system receives the wastewater output by the defluorination reaction system and carries out second treatment on the wastewater output by the defluorination reaction system so as to realize tubular microfiltration;
the resin adsorption system is used for receiving the wastewater output by the tubular microfiltration circulating system and carrying out third treatment on the wastewater output by the tubular microfiltration circulating system so as to realize resin adsorption.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a defluorination device aiming at high-salinity wastewater, which comprises a defluorination reaction system, a tubular microfiltration circulating system and a resin adsorption system. The defluorination reaction system is used for receiving fluorine-containing wastewater and carrying out first treatment on the fluorine-containing wastewater to realize flocculation. And the tubular microfiltration circulating system is used for receiving the wastewater output by the defluorination reaction system and carrying out second treatment on the wastewater output by the defluorination reaction system so as to realize tubular microfiltration. The resin adsorption system is used for receiving the wastewater output by the tubular microfiltration circulating system and carrying out third treatment on the wastewater output by the tubular microfiltration circulating system so as to realize resin adsorption. Utilize the defluorination device to high salt waste water of this application to realize flocculation, tubular micro-filtration and resin adsorption coupling, greatly improved the clearance to fluorine in the high enriched brine, can make the fluorine ion clearance reach 95-99%, and do not increase calcium, magnesium ion in the play water, effectively avoid going out water to follow-up electrodialysis and evaporation crystallization device jam, corrosion problem.
Drawings
FIG. 1 is a schematic structural diagram of a defluorination apparatus for high-salinity wastewater according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a defluorination method for high-salinity wastewater according to an embodiment of the invention;
1-defluorination agent, 2-first stirrer, 3-first pH meter, 4-hydrochloric acid, 5-second stirrer, 6-second pH meter, 7-sodium hydroxide, 8-circulating pool liquid level meter, 9-third stirrer, 10-reaction pool, 11-neutralization pool, 12-circulating pool, 13-connecting pipe, 14-pipe filtration water inlet pipe, 15-sludge pump, 16-high pressure industrial water, 17-basket filter, 18-circulating pump, 19-flowmeter, 20-pipe microfiltration membrane, 21-microfiltration product water, 22-microfiltration product water pool, 23-resin water inlet pump, 24-flowmeter, 25-resin tower, 26-RO product water, 27-flowmeter, 28-hydrochloric acid tank, 29-sodium hydroxide tank, 30-rotameter, 31-ejector, 32-rotameter, 33-regeneration waste liquid pool, 34-stirrer and 35-regeneration waste liquid pump.
Detailed Description
The following describes in more detail embodiments of the present invention with reference to the schematic drawings. The advantages and features of the present invention will become more apparent from the following description. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
In the description of the present invention, it is to be understood that the terms "center", "upper", "lower", "left", "right", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
Referring to fig. 1, an embodiment of the invention provides a fluorine removal device for high-salinity wastewater, which includes a fluorine removal reaction system, a tubular micro-filtration circulation system, and a resin adsorption system. The defluorination reaction system is used for receiving fluorine-containing wastewater and carrying out first treatment on the fluorine-containing wastewater to realize flocculation. And the tubular microfiltration circulating system is used for receiving the wastewater output by the defluorination reaction system and carrying out second treatment on the wastewater output by the defluorination reaction system so as to realize tubular microfiltration. The resin adsorption system is used for receiving the wastewater output by the tubular microfiltration circulating system and carrying out third treatment on the wastewater output by the tubular microfiltration circulating system so as to realize resin adsorption.
The difference with the prior art is that this embodiment provides a fluorine removal device to high salt waste water, including fluorine removal reaction system, tubular micro-filtration circulation system, resin adsorption system. The defluorination reaction system is used for receiving fluorine-containing wastewater and carrying out first treatment on the fluorine-containing wastewater to realize flocculation. And the tubular microfiltration circulating system is used for receiving the wastewater output by the defluorination reaction system and carrying out second treatment on the wastewater output by the defluorination reaction system so as to realize tubular microfiltration. The resin adsorption system is used for receiving the wastewater output by the tubular microfiltration circulating system and carrying out third treatment on the wastewater output by the tubular microfiltration circulating system so as to realize resin adsorption. Utilize the defluorination device to high salt waste water of this application to realize flocculation, tubular micro-filtration and resin adsorption coupling, greatly improved the clearance to fluorine in the high enriched brine, can make the fluorine ion clearance reach 95-99%, and do not increase calcium, magnesium ion in the play water, effectively avoid going out water to follow-up electrodialysis and evaporation crystallization device jam, corrosion problem.
Optionally, the defluorination reaction system comprises a reaction tank 10, a neutralization tank 11 and a circulating tank 12. The fluorine-containing wastewater sequentially passes through the reaction tank 10, the neutralization tank 11 and the circulation tank 12 to realize flocculation.
Specifically, in this embodiment, the defluorination reaction system comprises a reaction tank 10, a neutralization tank 11, and a circulation tank 12, the fluorine-containing wastewater is piped to the reaction tank 10, a first stirrer 2 and a first pH meter 3 are arranged in the reaction tank 10, and Al in the defluorination agent 1 is injected into the reaction tank 103+And F-With complexation and intermediate generation of aluminium hydrolysis and amorphous Al (OH)3Floc pair F-Ion exchange, adsorption and sweeping to produce NaAlF6、AlF3And NaF and the like, so as to remove fluorine ions in the fluorine-containing wastewater. The wastewater is transferred from a reaction tank 10 to a neutralization tank 11, a second stirrer 5 and a second pH meter 6 are arranged in the neutralization tank 11, and the pH value in the neutralization tank 11 is ensured to be within the range of 6.5-7.5 by adjusting and injecting hydrochloric acid 4. Waste water enters a circulating tank 12 through a connecting pipe 13, a liquid level meter 8 and a third stirrer 9 of the circulating tank 12 are arranged in the circulating tank 12, the bottom of the circulating tank 12 is conical, and sludge can be deposited in a conical hopper when the device runs. The sludge device consists of high-pressure industrial water 16 and a screw sludge pump 15. Excess sludge in the system can be sent to a sludge dewatering device for treatment through a screw sludge pump 15. When the inlet pipeline of the screw sludge pump 15 is blocked, the flushing can be carried out by high-pressure industrial water 16. The device treats high-concentration brine, so that the reaction tank 10, the neutralization tank 11 and the circulation tank 12 in the device are subjected to corrosion prevention, the hydraulic retention time of the reaction tank 10 and the neutralization tank 11 is kept at 15-30min and the hydraulic retention time of the circulation tank 12 is 1-3h in order to ensure the full mixing reaction of the fluorine-attached medicament. The rotating speed of the blades of the first stirrer 2 in the reaction tank 10 is 30-60r/min, the rotating speed of the blades of the second stirrer 5 in the neutralization tank 11 is 10-20r/min, and the rotating speed of the blades of the third stirrer 9 in the circulation tank 12 is 5-15 r/min.
Optionally, the tubular microfiltration circulating system comprises a circulation pump 18, a tubular microfiltration membrane, a water production pipe. The wastewater output by the defluorination reaction system passes through the circulating pump 18, the tubular microfiltration membrane and the water production pipe in sequence to realize tubular microfiltration.
Optionally, the tubular microfiltration circulating system further comprises a basket filter 17, wherein an input port of the basket filter 17 is connected with the defluorination reaction system, and an output port of the basket filter 17 is connected with an input port of the circulating pump 18.
Specifically, in this embodiment, the tubular microfiltration circulating system includes a circulating pump 18, a tubular microfiltration membrane, and a water production pipe, wherein the wastewater containing floc sludge flows into the circulating pump 18 through a basket filter 17 via a bottom tubular filtration inlet pipe 14 of the sedimentation tank, the water inlet pneumatic valve and the water return pneumatic valve are opened under the lift of the circulating pump 18, the circulating flow is maintained, the circulating flow/water inlet ratio is maintained at 600 + 1000%, and the wastewater flows into the water production pipe via the tubular microfiltration membrane and flows into the microfiltration water production tank 22. The tubular microfiltration circulating liquid is returned to the circulating tank 12 through a pipeline. The liquid level meter is interlocked with the start and stop of the circulating pump 18, and the liquid level meter is started at a high liquid level and stopped at a low liquid level. The liquid level meter is interlocked with a wastewater water inlet pump, the water inlet pump stops when the liquid level meter is at a high liquid level, and the water inlet pump starts when the liquid level meter is at a low liquid level. The basket filter 17 may be a wire-wound precision filter element or a mesh filter. The filtration precision of the wire-wound precise filter element is 50-200 mu m, and the aperture of the mesh filter is 100-300 mu m. The tubular micro-filtration membrane can adopt 1/2 and 1 inch internal pressure tube series, the membranes can adopt 4, 15, 37 and 61 cores in series arrangement, the membrane shell is made of PVC material, the membranes are made of PVDF or PTFE material, the membrane filtration pore diameter is 0.05 mu m, the water flux of the defluorination wastewater is controlled to be 200-400L/m2.h, and the membrane adaptive pH range is 1-14. The tubular microfiltration membrane is adopted to control the water inlet pressure to be 2.5-3.0bar, the sludge concentration in the inlet water is controlled to be 2000-10000ppm, pollutants can be effectively intercepted, the device has small floor area and high integrated automation degree, and the solid-liquid separation can be effectively realized. After being treated by a defluorination reaction system and a tubular microfiltration circulating system, the fluorine ions in the effluent are less than 10 mg/L.
Optionally, the resin adsorption system comprises a resin tower 25, and the resin tower 25 is used for performing resin adsorption on the wastewater output by the tubular microfiltration circulating system.
Specifically, after being treated by a defluorination reaction system and a tubular microfiltration circulating system, the wastewater enters a resin adsorption system. The wastewater enters a resin tower 25 through a first flow meter after being boosted by a lifting pump of a resin inlet pump 23 from a microfiltration water production tank 22, and is subjected to full adsorption reaction in the resin tower 25, and then microfiltration water production 21 is treated in a subsequent working section. The resin is styrene-divinylbenzene skeleton polymer resin with macroporous structure and active aluminum group capable of adsorbing fluorion from water to eliminate fluorion concentration. After resin adsorption treatment, the fluorine ion concentration of the inlet water is reduced from 10mg/l to below 1 mg/l. The resin tower 25 is filled with defluorination resin, the adsorption capacity of the defluorination resin is 1.5-4.0g/L, the granularity is 0.5-1.0mm, and the density is 1.05-1.15 g/ml. When the tower is in operation, the flow velocity in the tower is controlled at 8.2-12.6m/h, wastewater enters from the top of the tower, and after the wastewater flows through the resin permeation filter cap, the wastewater produces water from a bottom pipeline.
Further, the resin operation period is more than 24 hours, and after the operation time is finished, the resin regeneration program can be entered. Correspondingly, the defluorination device for the high-salinity wastewater further comprises a resin regeneration system; the resin regeneration system is used for treating the resin adsorption system so as to recover the defluorination function of the resin adsorption system.
Optionally, the resin regeneration system includes an acid regeneration module and an alkali regeneration module, the acid regeneration module is configured to perform acid regeneration treatment on the resin adsorption system, and the alkali regeneration module is configured to perform alkali regeneration treatment on the resin adsorption system.
Specifically, in the present embodiment, the resin regeneration system employs sodium hydroxide 7 and hydrochloric acid 4 as the regeneration liquid. Regeneration is first with acid and then with base. The RO produced water 26 (reverse osmosis water) is reused, and the concentration of acid and alkali is 30%. The regeneration process comprises the following steps: backwashing, standing, acid regeneration, slow washing, alkali regeneration and backwashing. The flow rate is 5-8m/h during backwashing, and the water consumption is 1-2 BV; the flow rate is 2-4m/h during slow washing, and the dosage is 1.5-2.0 BV; the flow rate is 2-3m/h during regeneration, and the water consumption is 2-2.5 BV; the acid regeneration process comprises the following steps: and (3) opening a regenerated water pneumatic valve, enabling the RO produced water 26 to enter the resin ejector 31 through a pipeline, sucking the hydrochloric acid 4 in a negative pressure area, enabling the solution of the RO produced water 26 mixed with the hydrochloric acid 4 to enter a resin regeneration tower from the bottom through a rotor flow meter, and enabling regenerated waste liquid to flow to a regenerated waste liquid pool 33 from a regenerated waste liquid pipe at the top of the tower after the solution is exchanged with resin. Controlling the concentration of the regenerated acid solution hydrochloric acid 4 to be 5-8%. The alkali regeneration process comprises the following steps: the main step is basically the same as the acid regeneration, and sodium hydroxide 7 is absorbed during the main regeneration. Controlling the concentration of the regenerated alkali solution sodium hydroxide 7 to be 5-6.5%.
The defluorination device for high-salinity wastewater provided by the embodiment realizes flocculation, tubular microfiltration and resin adsorption coupling, has high removal rate on fluorine in high-concentration brine, has the inlet water fluorine ion concentration of 150-200mg/l and the outlet water fluorine ion concentration of 1-3mg/l, achieves the fluorine ion removal rate of 95-99%, does not add calcium and magnesium ions in the outlet water, and effectively avoids the problems of blockage and corrosion of the outlet water on a subsequent electrodialysis and evaporation crystallizer. In addition, for deep recycling or zero discharge of wastewater, the problem of removing fluorine from high-concentration brine has important environmental protection significance for deep recycling treatment of the high-concentration brine, and for zero discharge devices, the removal of fluoride from the high-concentration brine has important significance for electrodialysis concentration and long-period stable operation of a sodium chloride MVR device.
From the above analysis description, the defluorination apparatus for high salinity wastewater of the present application has the following characteristics: the method adopts two-stage deep fluorine removal, wherein one-stage deep fluorine removal adopts chemical agents, and the second-stage deep fluorine removal adopts resin. In the chemical agent fluorine removal section, fluorine removal agent 1 is added into reaction tank 10, and then acid and alkali are added to track and adjust the pH value in reaction tank 10, so as to remove fluorine ions. The resin can adsorb fluoride ions by deeply removing the fluoride in the resin, and the fluoride ions in the water can be reduced to a very low level. After the fluorine is removed by the resin, the fluorine ion in the effluent can be reduced to 1-3 mg/l. ② controlling the defluorination process of chemical agents, in the process, after adding defluorination agent 1, strictly controlling the pH value, the pH value is 6.5-7.6, thus the agent can fully react with fluorinion to generate precipitate for removal. Thirdly, before the resin is subjected to defluorination, membrane treatment is selected, and meanwhile, the membrane treatment can be a tubular microfiltration membrane 20, a ceramic filtration membrane or an ultrafiltration membrane (pressure type or immersed type ultrafiltration). Fourthly, tubular microfiltration is adopted, the concentration of suspended matters is 2000-10000mg/l, and the pH range is 1-14. Fifthly, the regenerated waste liquid returns to the water inlet chemical defluorination process section, the fluoride ions absorbed by the resin recover the defluorination function through regeneration, the regenerated waste liquid contains high-concentration fluoride ions, and the waste liquid is not separately provided with a treatment process. Sixthly, the fluorine removal resin is regenerated by acid and alkali according to the technological parameters in the regeneration process, the regeneration concentration is 5-8 percent, and fluorine ions can be effectively removed.
Based on the same inventive concept, please refer to fig. 2, the embodiment of the present invention further provides a method for removing fluorine from high salinity wastewater, comprising:
s1: the method comprises the following steps that a defluorination reaction system receives fluorine-containing wastewater, and the fluorine-containing wastewater is subjected to primary treatment to realize flocculation;
s2: the tubular microfiltration circulating system receives the wastewater output by the defluorination reaction system and carries out second treatment on the wastewater output by the defluorination reaction system so as to realize tubular microfiltration;
s3: the resin adsorption system is used for receiving the wastewater output by the tubular microfiltration circulating system and carrying out third treatment on the wastewater output by the tubular microfiltration circulating system so as to realize resin adsorption.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a defluorination device aiming at high-salinity wastewater, which comprises a defluorination reaction system, a tubular microfiltration circulating system and a resin adsorption system. The defluorination reaction system is used for receiving fluorine-containing wastewater and carrying out first treatment on the fluorine-containing wastewater to realize flocculation. And the tubular microfiltration circulating system is used for receiving the wastewater output by the defluorination reaction system and carrying out second treatment on the wastewater output by the defluorination reaction system so as to realize tubular microfiltration. The resin adsorption system is used for receiving the wastewater output by the tubular microfiltration circulating system and carrying out third treatment on the wastewater output by the tubular microfiltration circulating system so as to realize resin adsorption. Utilize the defluorination device to high salt waste water of this application to realize flocculation, tubular micro-filtration and resin adsorption coupling, greatly improved the clearance to fluorine in the high enriched brine, can make the fluorine ion clearance reach 95-99%, and do not increase calcium, magnesium ion in the play water, effectively avoid going out water to follow-up electrodialysis and evaporation crystallization device jam, corrosion problem.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example" or "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. And the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments. Furthermore, various embodiments or examples described in this specification can be combined and combined by those skilled in the art.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (11)

1.一种针对高盐废水的除氟装置,其特征在于,包括除氟反应系统、管式微滤循环系统、树脂吸附系统;1. a defluorination device for high-salt waste water, is characterized in that, comprises defluorination reaction system, tubular microfiltration circulation system, resin adsorption system; 所述除氟反应系统用于接收含氟废水,对所述含氟废水进行第一道处理以实现絮凝;The defluorination reaction system is used for receiving fluorine-containing wastewater, and performing the first treatment on the fluorine-containing wastewater to realize flocculation; 所述管式微滤循环系统用于接收所述除氟反应系统输出的废水,对所述除氟反应系统输出的废水进行第二道处理以实现管式微滤;The tubular microfiltration circulation system is used for receiving the waste water output by the defluorination reaction system, and performing a second treatment on the waste water output by the defluorination reaction system to realize the tubular microfiltration; 所述树脂吸附系统用于接收所述管式微滤循环系统输出的废水,对所述管式微滤循环系统输出的废水进行第三道处理以实现树脂吸附。The resin adsorption system is used for receiving the waste water output by the tubular microfiltration circulation system, and performing a third treatment on the waste water output by the tubular microfiltration circulation system to realize resin adsorption. 2.如权利要求1所述的针对高盐废水的除氟装置,其特征在于,所述除氟反应系统包括反应池、中和池、循环池;2. The defluorination device for high-salt wastewater according to claim 1, wherein the defluorination reaction system comprises a reaction tank, a neutralization tank, and a circulation tank; 所述含氟废水依次经过所述反应池、所述中和池以及所述循环池以实现絮凝。The fluorine-containing wastewater passes through the reaction tank, the neutralization tank and the circulation tank in sequence to achieve flocculation. 3.如权利要求2所述的针对高盐废水的除氟装置,其特征在于,所述反应池中设置有第一搅拌机和第一pH计。3 . The defluorination device for high-salt wastewater according to claim 2 , wherein the reaction tank is provided with a first mixer and a first pH meter. 4 . 4.如权利要求3所述的针对高盐废水的除氟装置,其特征在于,所述中和池中设置有第二搅拌机和第二pH计。4. The fluoride removal device for high-salt wastewater according to claim 3, wherein a second mixer and a second pH meter are provided in the neutralization tank. 5.如权利要求4所述的针对高盐废水的除氟装置,其特征在于,所述循环池中设置有循环池液位计和第三搅拌机。5 . The defluorination device for high-salt wastewater according to claim 4 , wherein the circulating pool is provided with a circulating pool level gauge and a third mixer. 6 . 6.如权利要求1所述的针对高盐废水的除氟装置,其特征在于,所述管式微滤循环系统包括循环泵、管式微滤膜、产水管;6. The defluorination device for high-salt wastewater according to claim 1, wherein the tubular microfiltration circulation system comprises a circulating pump, a tubular microfiltration membrane, and a water production pipe; 所述除氟反应系统输出的废水依次经过所述循环泵、所述管式微滤膜以及所述产水管已实现管式微滤。The waste water output from the defluorination reaction system passes through the circulating pump, the tubular microfiltration membrane and the water production pipe in sequence to achieve tubular microfiltration. 7.如权利要求6所述的针对高盐废水的除氟装置,其特征在于,所述管式微滤循环系统还包括篮式过滤器;7. The defluorination device for high-salt wastewater as claimed in claim 6, wherein the tubular microfiltration circulation system further comprises a basket filter; 所述篮式过滤器的输入口连接所述除氟反应系统,所述篮式过滤器的输出口连接所述循环泵的输入口。The input port of the basket filter is connected to the defluorination reaction system, and the output port of the basket filter is connected to the input port of the circulating pump. 8.如权利要求1所述的针对高盐废水的除氟装置,其特征在于,所述树脂吸附系统包括树脂塔,所述树脂塔用于对管式微滤循环系统输出的废水进行树脂吸附。8 . The fluorine removal device for high-salt wastewater according to claim 1 , wherein the resin adsorption system comprises a resin tower, and the resin tower is used to perform resin adsorption on the wastewater output from the tubular microfiltration circulation system. 9 . 9.如权利要求1所述的针对高盐废水的除氟装置,其特征在于,所述针对高盐废水的除氟装置还包括树脂再生系统;9. The defluorination device for high-salt wastewater according to claim 1, wherein the defluorination device for high-salt wastewater also comprises a resin regeneration system; 所述树脂再生系统用于对所述树脂吸附系统进行处理以使所述树脂吸附系统恢复除氟功能。The resin regeneration system is used for treating the resin adsorption system to restore the fluorine removal function of the resin adsorption system. 10.如权利要求9所述的针对高盐废水的除氟装置,其特征在于,所述树脂再生系统包括酸再生模块以及碱再生模块;10. The fluorine removal device for high-salt wastewater according to claim 9, wherein the resin regeneration system comprises an acid regeneration module and an alkali regeneration module; 所述酸再生模块用于对所述树脂吸附系统进行酸再生处理,所述碱再生模块用于对所述树脂吸附系统进行碱再生处理。The acid regeneration module is used for performing acid regeneration treatment on the resin adsorption system, and the alkali regeneration module is used for performing alkali regeneration treatment on the resin adsorption system. 11.一种针对高盐废水的除氟方法,其特征在于,包括:11. A defluorination method for high-salt wastewater, characterized in that, comprising: 除氟反应系统接收含氟废水,对所述含氟废水进行第一道处理以实现絮凝;The defluorination reaction system receives the fluorine-containing wastewater, and performs the first treatment on the fluorine-containing wastewater to realize flocculation; 管式微滤循环系统接收所述除氟反应系统输出的废水,对所述除氟反应系统输出的废水进行第二道处理以实现管式微滤;The tubular microfiltration circulation system receives the waste water output by the defluorination reaction system, and performs a second treatment on the waste water output by the defluorination reaction system to realize the tubular microfiltration; 树脂吸附系统用于接收所述管式微滤循环系统输出的废水,对所述管式微滤循环系统输出的废水进行第三道处理以实现树脂吸附。The resin adsorption system is used for receiving the wastewater output by the tubular microfiltration circulation system, and performing a third treatment on the wastewater output by the tubular microfiltration circulation system to realize resin adsorption.
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