CN113620477A - Defluorination device and method for high-salinity wastewater - Google Patents
Defluorination device and method for high-salinity wastewater Download PDFInfo
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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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- wastewater
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- fluorine
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- 239000002351 wastewater Substances 0.000 title claims abstract description 121
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000001471 micro-filtration Methods 0.000 claims abstract description 87
- 229920005989 resin Polymers 0.000 claims abstract description 87
- 239000011347 resin Substances 0.000 claims abstract description 87
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 63
- 239000011737 fluorine Substances 0.000 claims abstract description 63
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000001179 sorption measurement Methods 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000011282 treatment Methods 0.000 claims abstract description 40
- 238000005189 flocculation Methods 0.000 claims abstract description 18
- 230000016615 flocculation Effects 0.000 claims abstract description 18
- 238000011221 initial treatment Methods 0.000 claims abstract description 4
- 238000011069 regeneration method Methods 0.000 claims description 44
- 230000008929 regeneration Effects 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 17
- 238000006386 neutralization reaction Methods 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 13
- 239000012267 brine Substances 0.000 abstract description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 11
- 238000002425 crystallisation Methods 0.000 abstract description 10
- 230000008025 crystallization Effects 0.000 abstract description 10
- 238000000909 electrodialysis Methods 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011575 calcium Substances 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 238000001704 evaporation Methods 0.000 abstract description 5
- 230000008020 evaporation Effects 0.000 abstract description 5
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 5
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 description 23
- -1 fluorine ions Chemical class 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000010802 sludge Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 238000011001 backwashing Methods 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical group C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910020826 NaAlF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000005536 corrosion prevention Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Images
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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
-
- 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
- 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 defluorination device and method aiming at high-salinity wastewater. The defluorination reaction system is used for receiving fluorine-containing wastewater and carrying out primary 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 secondary 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 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.
Description
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. A defluorination device aiming at high-salinity wastewater is characterized by comprising 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;
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.
2. The apparatus for removing fluorine from high salinity wastewater according to claim 1, wherein said reaction system for removing fluorine comprises a reaction tank, a neutralization tank, a circulation tank;
the fluorine-containing wastewater sequentially passes through the reaction tank, the neutralization tank and the circulation tank to realize flocculation.
3. The apparatus for removing fluorine from high salinity wastewater according to claim 2, wherein a first stirrer and a first pH meter are arranged in the reaction tank.
4. The apparatus for removing fluorine from high salinity wastewater according to claim 3, wherein a second stirrer and a second pH meter are arranged in the neutralization tank.
5. The apparatus for removing fluorine in high salinity wastewater according to claim 4, wherein a circulation tank level meter and a third stirrer are arranged in the circulation tank.
6. The apparatus for removing fluorine from high salinity wastewater according to claim 1, wherein the tubular microfiltration circulating system comprises a circulating pump, a tubular microfiltration membrane, 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.
7. The apparatus for removing fluorine from high salinity wastewater according to claim 6, wherein said 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.
8. The apparatus for removing fluorine in high salinity wastewater according to claim 1, wherein the resin adsorption system comprises a resin tower for performing resin adsorption on the wastewater output by the tubular micro-filtration circulation system.
9. The apparatus for defluorinating high-salinity wastewater according to claim 1, wherein the apparatus for defluorinating 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.
10. The apparatus for defluorinating high salinity wastewater of claim 9, wherein 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.
11. A defluorination method aiming at high-salinity wastewater is characterized by comprising 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.
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